Polymer Poly Research Articles

Halide Perovskite Inducing Anomalous Nonvolatile Polarization in Poly(vinylidene fluoride)-based Flexible Nanocomposites

Ferroelectric materials have important applications in transduction, data storage, and nonlinear optics. Inorganic ferroelectrics such as lead zirconate titanate possess large polarization, though they are rigid and brittle. Ferroelectric polymers are light weight and flexible, yet their polarization is low, bottlenecked at 10 μC cm−2. Here we show poly(vinylidene fluoride) nanocomposite with only 0.94% of self-nucleated CH3NH3PbBr3 nanocrystals exhibits anomalously large polarization (~19.6 μC cm−2) while retaining superior stretchability and photoluminance, resulting in unprecedented electromechanical figures of merit among ferroelectrics. Comprehensive analysis suggests the enhancement is accomplished via delicate defect engineering, with field-induced Frenkel pairs in halide perovskite stabilized by the poled ferroelectric polymer through interfacial coupling. The strategy is general, working in poly(vinylidene fluoride-co-hexafluoropropylene) as well, and the nanocomposite is stable. The study thus presents a solution for overcoming the electromechanical dilemma of ferroelectrics while enabling additional optic-activity, ideal for multifunctional flexible electronics applications.

A four-in-one multifunctional self-assembly hydrogel composed of natural drugs for repairing myocardial infarction

To meet the multiple demands of myocardial repair, it would be a novel strategy for myocardial repair if multiple drugs could be constructed into an integrated multifunctional drug formulation. In this study, four drugs with different functions (thioctic acid with antioxidant effects, quercetin with anti-inflammatory and antioxidant effects, arginine with pro-angiogenic effects, and Mn2+ with imaging functions) were selected to construct a four-in-one injectable hydrogel (thioctic acid-arginine-quercetin-Mn2+) through chemical bonding and supramolecular interactions. First, thioctic acid polymerized to a redox-sensitive degradable polymer—poly(thioctic acid) containing disulfide bonds in the main chains through ring-opening polymerization. Quercetin was conjugated to the main chain of the poly(thioctic acid) molecules via thiyl radical-polyphenol Michael addition. Arginine cross-linked the carboxyl groups side chains of the poly(thioctic acid) molecules through hydrogen bonding. Mn2+ further cross-linked the carboxyl groups' side chains of the poly(thioctic acid) molecules through ionic bonding. The hydrogel has antioxidant properties, promotes neovascularization, inhibits inflammatory, improves intracellular Ca2+ overload and mitochondrial dysfunction, protects adenosine triphosphatase (ATPase) activity, and maintains intracellular energy supply, which can reduce the size of myocardial infarcts, and improves cardiac function. This construction method of preparing integrated multifunctional hydrogels from natural drugs will provide a new therapeutic strategy for myocardial repair.

Implications of Low-concentration Polymer on the Physical Stability of Glassy Griseofulvin: Role of the Segmental Mobility.

Crystallization of amorphous pharmaceutical solids are widely reported to be affected by the addition of polymer, while the underlying mechanism require deep study. Herein, crystal growth behaviors of glassy griseofulvin (GSF) doped with various 1% w/w polymer were systematically studied. From the molecular structure, GSF cannot form the hydrogen bonding interactions with the selected polymer poly(vinyl acetate), polyvinyl pyrrolidone (PVP), 60:40 vinyl pyrrolidone-vinyl acetate copolymer (PVP/VA 64), and poly(ethylene oxide) (PEO). 1% w/w polymer exhibited weak or no detectable effects on the glass transition temperature (Tg) of GSF. However, crystal growth rates of GSF was altered from 4.27-fold increase to 2.57-fold decrease at 8 ℃ below Tg of GSF. Interestingly, the ability to accelerate and inhibit the growth rates of GSF crystals correlated well with Tg of polymer, indicating the controlling role of segmental mobility of polymer. Moreover, ring-banded growth of GSF was observed in the polymer-doped systems. Normal compact bulk and ring-banded crystals of GSF were both characterized as the thermodynamically stable form I. More importantly, formation of ring-banded crystals of GSF can significantly weaken the inhibitory effects of polymer on the crystallization of glassy GSF.

Voltage-assisted 3D printing of polymer composite dielectric films with low energy loss and high energy storage density

PVDF-based polymers have garnered significant attention in the field of high-power density electrostatic capacitors due to their exceptional dielectric strength. However, their practical applications are constrained by low charge-discharge efficiency (η) and energy storage density (Ue), which stem from high ferroelectric relaxation and low breakdown strength (Eb). Here, a hydrogenated glassy polymer poly(styrene-methyl methacrylate-methylallyl alcohol) (PSMA) is designed and synthesized to be homogeneously distributed in PVDF through voltage-assisted 3D printing-hot pressing, resulting in a flexible composite film. The findings demonstrate that PSMA, rich in hydrogen bonds and high modulus strength, effectively mitigates the ferroelectric phase transition of PVDF to enhance η. Additionally, the voltage-assisted 3D printing process induces an entropy gain mechanism, facilitating the uniform distribution of the two phases and enhancing the interfacial properties for enhancing Eb. Remarkably, the study achieves prominent growth in energy storage performance, with Ue and η reaching 18.1 J/cm3 and 80 % at 525 MV/m, respectively. These remarkable results highlight the potential of 3D printing technology in enhancing the energy storage performance of PVDF-based dielectrics.

D-π-A chromophores based on novel macroacceptors - Fused (azinylmethylene)malononitriles: Linear and nonlinear optical properties in solution and in poled polymer films

D-π-A chromophores based on novel macroacceptors − fused azinylmethylenemalononitriles (fused azine = pyrido [2,3-b]pyrazine, quinoline, quinoxaline and quinoxalin-2-one) − have been synthesized and their linear and nonlinear optical properties in gas, solution and in poled PMMA-based films have been investigated by DFT, UV–vis and second harmonic generation technique. The transition from chromophores with an azine acceptor to ones with azinylmethylenemalononitrile acceptors leads to a 10-fold increase in calculated μβ values. Poled polymer films doped with studied chromophores at 25 wt% load exhibit quadratic nonlinear optical activity with d33 values up to 42 pm/V.

Electrocatalytic Poly(3,4-ethylenedioxythiophene) for Electrochemical Conversion of 5-Hydroxymethylfurfural.

This study investigates the utilization of the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) as a catalytic material for the 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA). PEDOT films doped with different counterions were electrodeposited on graphite foil. In particular, the mobile anion perchlorate and the polymeric ionomers polystyrenesulfonate, Nafion, and Aquivion were used. The electrocatalytic properties of PEDOT films were evaluated toward the TEMPO redox mediator in the absence and the presence of HMF as a substrate for oxidation reactions. The electrocatalytic HMF oxidation was confirmed to occur at PEDOT electrodes, and it was also found that the chemical nature of PEDOT counterions controls the electrocatalytic conversion of HMF by modulating the kinetics of the electrochemical generation of the oxoammonium cation TEMPO(+). Potentiostatic electrolysis experiments showed that both the reference graphite electrode and PEDOT substrates were able to convert HMF to FDCA with an 80% faradaic efficiency (FE) and a >90% yield (FDCA), but, compared to graphite, the complete conversion of HMF to FDCA required a ca. 30% shorter time when using PEDOT electrodes doped with perchlorate or Aquivion, thanks to their ability to sustain a higher current density in the initial phase of the electrolysis. In addition, while all PEDOT films were chemically stable under the electrochemical conditions herein described, only PEDOT films doped with Aquivion were also mechanically robust and stable against delamination. Thus, the new PEDOT/Aquivion composite may represent the best choice for the implementation of PEDOT-based electrodes in TEMPO-mediated electrocatalytic applications.

Enhanced Interlayer Adhesion of 3D Printed Poly(lactide acid) with Ultralow Hyperbranched Poly(ester imide)s

The layer-by-layer process of fused deposition modeling (FDM) is well-known for introducing anisotropy in 3D printed parts due to weak interlayer adhesion. Moreover, the existing physical blend modification methods still face the side effects caused by the heavy use of additives, such as high cost, poor biocompatibility and weakening of primary properties. In this study, hyperbranched polymers poly(ester imide)s (HBPEIs) were blended into the poly(lactic acid) (PLA) matrix to enhance the interlayer adhesion of 3D printed parts. The application effect of HBPEIs in different processing modes was discussed. The effect of different amounts of HBPEIs on the mechanical properties of PLA specimens was investigated. Results showed that by adding just 0.1 wt% HBPEIs, the maximum tensile strength for samples printed with a 90° raster orientation increased from 23.1 MPa to 46.6 MPa while maintaining an isotropic behavior at around 95.9 %. Microstructures, rheological behaviors, and thermal properties of the printed specimens were characterized and compared to understand the underlying enhancement mechanism. It suggested that HBPEIs significantly improved interlayer adhesion by promoting chain diffusion and cold-crystallization between layers. This study showed that using ultralow additives can significantly enhance the interlayer adhesion in FDM parts.

Microcapsules of Poly(butylene adipate-co-terephthalate) (PBAT) Loaded with Aliphatic Isocyanates for Adhesive Applications.

This work introduces the encapsulation of hexamethylene diisocyanate derivatives (HDI, TriHDI, and PHDI) with the biodegradable polymer poly(butylene adipate-co-terephthalate) (PBAT) through a solvent evaporation method. These microcapsules (MCs) were then employed in adhesive formulations for footwear. Moreover, MCs containing PHDI were produced in a closed vessel, demonstrating the potential for recovering and reusing organic solvents for the first time. The MCs were achieved with an isocyanate payload reaching up to 68 wt %, displaying a spherical shape, a core-shell structure, and thin walls without holes or cracks. The application of MCs as cross-linking agents for adhesives was evaluated following industry standards. The adhesives' strength surpassed the minimum requirement by a significant margin. Creep tests demonstrated that the formulation with MCs exhibits superior thermostability. Furthermore, the formulation with MCs-PHDI presented the best results reported to date for this type of system, as no displacement was observed in the bonded substrates. Environmental assessment indicates that adhesives with MCs have higher global warming potential (+16.2%) and energy consumption (+10.8%) than the standard commercial adhesives, but under alternative realistic scenarios, the differences can be insignificant. Therefore, adhesive formulations incorporating MCs promise to be on par with traditional adhesive systems regarding environmental impacts while providing benefits such as improved and safe handling of isocyanates and excellent bonding effectiveness.

PEDOT-coated rice husk-based activated carbon: Boosting lead-acid battery performance

Despite the surge in novel energy storage systems, lead-acid batteries remain entrenched in the market, chiefly attributed to their well-established technology, affordability, and dependable safety profile. Yet, they are not without shortcomings, notably their limited energy density and abbreviated cycle life. The profound impact of positive electrode materials on lead-acid batteries is undeniable, as these materials directly dictate the batteries' charging and discharging efficiency, energy density, cycle longevity, and overall stability. Here we report on an innovative positive active material additive, wherein the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) is coated onto rice husk-based activated carbon (RHAC) surfaces via in-situ polymerization in solution to form a composite material (PEDOT@RHAC). Astonishingly, lead-acid batteries fortified with PEDOT@RHAC within their positive plates showcased remarkable electrochemical prowess. Incorporating PEDOT@RHAC into the positive plates of lead-acid batteries has demonstrated exceptional electrochemical performance. The enhanced deep cycling capability of these batteries is evident, with a substantial increase in cycle life by 2.08 times and an augmentation in discharge capacity by 1.3 times compared to the control batteries. This positive electrode additive plays a pivotal role in augmenting the overall performance and extending the lifespan of lead-acid batteries, potentially paving the way for their broader commercial application.

Enhancing the attraction of positively charged precursors of conductive polymer poly(3,4-ethylenedioxythiophene) by anchoring sulfonate groups in cellulose fibres

Interfacial interactions are key to the development of high-performance coatings such as conductive polymer layers on fibrous materials. In this work, we present an approach of strengthening the interaction by forming ionic bonds between cellulose fibres and the conductive polymer layer by introducing a sulfonate group on cellulose fibres. The ionic bonds are formed between anchored sulfonate group and the positively charged precursor 3,4-ethylenedioxythiophene (EDOT), followed by the deposition and polymerisation of poly(3,4-ethylenedioxythiophene):sulfate (PEDOT:SO4) on the fibrous substrate surface. The conductance of the PEDOT:SO4 coated substrate with anchored sulfonate groups coated may be 1.7 times higher compared to the conductance of the unmodified cellulose substrate depending on experimental conditions. EDX measurements confirm the presence of sulfur and a shift of zeta potential at lower pH supports the evidence of the anionic anchored groups on the fibre surface. Our study therefore provides a new way to enhance the affinity of fibrous cellulose materials towards polymer conductive coatings.

3D-printed scaffolds for tissue engineering applications using thermosensitive hydrogels based on biopolymer blends

Three-dimensional (3D) printing is an emerging technology for the construction of complex 3D constructs used for tissue engineering applications. In this study, we are proposing the preparation of 3D printing hydrogel inks consisting of the synthetic polymers poly(caprolactone) and poly(lactic acid), the biopolymer chitosan, and naturally derived gelatin. In addition, pluronic F-127 was used to improve the miscibility between the hydrophobic and hydrophilic components due to its amphiphilic character, as well as for its good 3D printability. The printability of the hydrogel inks was optimized by varying the composition, the extrusion nozzle, and the temperature, while the integrity of the 3D scaffolds was secured via sol–gel transition. The produced hydrogels with PCL-pluronic-chitosan-gelatin/15-20-4-2 wt% (PC3.75-Pl5-CG) and PLA-pluronic-chitosan-gelatin/10-20-4-2 wt% (PL2.5-Pl5-CG) presented the best printability, producing smooth and uniform porous scaffolds. The prepared hydrogels were formed via the interactions between the polymers through hydrogen bonding. Additionally, the produced hydrogels exhibited temperature-dependent swelling behavior, and the scaffolds with PCL presented lower swelling capacity than the scaffolds with PLA. The produced scaffolds presented slower hydrolyzation rate in simulated body fluid (SBF) at 25 °C compared to 37 °C. Biological studies proved that the 3D-printed porous scaffolds were non-cytotoxic and promoted human adipose-derived mesenchymal stem cell adhesion.Graphical abstract

Controlled photothermal ablative processing of commercial polymers minimizing undesired thermal effects under high frequency femtosecond laser irradiation

The response of three commercial polymers (poly(vinyl chloride) (PVC), poly(ethylene terephthalate) (PET) and polypropylene (PP)) with different thermal properties under high repetition rates (1 kHz-1 MHz) with femtosecond (450 fs) multi-pulse laser irradiation at λ = 515 nm (1.4 J/cm2) is reported resulting in a complete study with controlling the ablation depth and minimizing collateral thermal effects. Tunable ablation depth is achieved accurately by varying the repetition rate at a constant fluence. The results are compared to a photothermal model that aims at explaining the heat accumulation effect of successive pulses as a function of the repetition rate and predicts three different heat regimes (non-cumulative, cumulative and saturation). The threshold frequencies for each regime can be estimated from the model, providing control for selecting frequency values and thermal regimes. Thermal analyses are performed to characterize the materials, concluding that thermal parameters are vital for selecting optimal materials and laser processing parameters.

3D-Printed Fluorescent Hydrogel Consisting of Conjugated Polymer and Biomacromolecule for Fast and Sensitive Detection of Cr(VI) in Vegetables.

Portable fluorescent film sensors offer a solution to the contamination issue in homogeneous sensor detection systems. However, their special structure leads to low sensitivity and a long response time, resulting in a significant scientific challenge limiting their development and application. In this work, we propose a dual design strategy to prepare highly sensitive film sensors for rapidly detecting Cr2O72-. Specifically, P(Fmoc-Osu)-SA hydrogel films were developed by integrating the biological macromolecule sodium alginate (SA) with the conjugated polymer poly(N-(9-Fluorenylmethoxycarbonyloxy)succinimide) (P(Fmoc-Osu)), using both mold and inkjet 3D printing methods. The "molecular wire effect" of the sensing unit P(Fmoc-Osu) and the water channel within the film substrate are responsible for the improved sensitivity and the reduced response time of this thin film sensor. P(Fmoc-Osu)-SA hydrogel films prepared by these two methods can rapidly detect Cr2O72- with limits of detection of 1.18 and 0.078 nM, respectively. Considering that 3D-printed hydrogel films can be tailored to different shapes according to detection needs, the P(Fmoc-Osu)-SA hydrogel films produced from this method were effectively applied in vegetable samples. This study provides an innovative and effective strategy for the development of biocompatible hydrogel sensors that offer the potential for determining trace amounts of Cr2O72- in agriculture.

Large electrocaloric effect near room temperature induced by domain switching in ferroelectric nanocomposites

The solid-state refrigeration technique based on the electrocaloric effect (ECE) of ferroelectric materials has been regarded as a promising alternative to vapor compression systems due to its advantages of high efficiency and easy miniaturization. However, the small adiabatic temperature change (ATC) and narrow operating temperature range of ferroelectric materials are key obstacles for their practical applications of ECE refrigeration. To improve the ECE performance of ferroelectric polymer poly(vinylidene fluoride) [P(VDF-TrFE)], PbZr1−xTixO3 (PZT) nanoparticles with larger polarization is herein introduced to form ferroelectric nanocomposites. The phase-field simulation is employed to investigate the dynamic hysteresis loops and corresponding domain evolution of the ferroelectric nanocomposites. The temperature-dependent ATC values are calculated using the indirect method based on the Maxwell relation. The appearance of the double hysteresis loop is observed in P(VDF-TrFE) nanocomposite filled with PbZr0.1Ti0.9O3 nanoparticles [P(VDF-TrFE)–PZT0.9], which is mainly caused by a microscopic domain transition from single domain to polar vortex. Compared to the P(VDF-TrFE), enhanced ATC values associated with the domain transition are unveiled in P(VDF-TrFE)–PZT0.9, and the temperature range of excellent ECE is also effectively broadened. In addition, as the component x of filled PZT nanoparticles increases to cross the morphotropic phase boundary (MPB), the maximum ATC value shows a significant increase. The results presented in this work not only explain the mechanism of domain transition induced excellent ECE in the P(VDF-TrFE)–PZT nanocomposite, but also stimulate future studies on enhancing ECE of P(VDF-TrFE) by introducing ferroelectric nanofillers.

High-temperature energy storage with a new tri-layers polymer composites via hybrid assembly engineering

Dielectric film capacitors are fundamental components in advanced electrical fields such as smart grids and hybrid electric vehicle. The commercial film capacitors made by biaxially oriented polypropylene (BOPP) have high energy efficiency, but low energy density of only 2.0-3.0 J/cm3, while the inferior thermal stability restricts their high temperature applications. In this work, hybrid assembly engineering is proposed to design composite films with a new polymer of poly(acrylonitrile butadiene styrene) (ABS) as the matrix, boron nitride nanosheets (BNNS) and Na0.5Bi0.5TiO3-Sr0.7Bi0.2TiO3 (NBT-SBT) as two different fillers to improve high-temperature performance. The optimized composites SBS (NBT-SBT/ABS composites layer in the outside and BNNS/ABS composites layer in the middle) exhibit excellent high temperature energy storage characteristics, and its underlying mechanism is also understood by phase-field simulations. In particular, the maximum energy density at 120 °C can reach 15.0 J/cm3 at 575 MV/m, which is 8 times that of BOPP, while the efficiency is maintained at 89 %, far exceeding the performance of BOPP (<70 % at 120 °C). Together with their excellent cycling reliability (106 cycles) and thermal stability, this strategy shows a great potential for high-temperature and high-power energy storage capacitors.

Influence of Chemical Composition and Structure on the Cooperative Fluctuation in Supercooled Glass-Forming Liquids.

The kinetics of the glass transition and the characteristic size of the fluctuating spatio-temporal domains in supercooled glass-forming liquids, i.e., the Cooperatively Rearranging Regions (CRR), were measured upon cooling over a broad range of cooling rates using Differential Scanning Calorimetry (DSC) and chip-based Fast Scanning Calorimetry (FSC). The investigations were conducted on a selection of fragile glass formers (fragility indices between 80 and 140), with a large variance in the atomic or molecular structure but comparable thermal glass transition temperatures Tg, with the aim of evaluating the influence of chemical composition and structure on the CRR size and the associated temperature fluctuation. The selected materials are two polymers (poly(vinyl acetate) (PVAc), poly(lactic acid) (PLA)) as well as the simplest chalcogenide glass-former (selenium). It turned out that the CRR size plotted against the reduced temperature T/Tg follows the same trend, irrespective of the considered glass-former.

Enhancing output current in degradable flexible piezoelectric nanogenerators through internal electrode construction

Conventional piezoelectric nanogenerators (PNGs) face challenges in terms of degradation and reusability, which have negative environmental implications. On the other hand, biocompatible and degradable piezoelectric materials often exhibit lower piezoelectric response. In this study, potassium sodium niobate (KNN) powder and the biodegradable polymer poly(ε-caprolactone) (PCL) were used to fabricate piezoelectric composite films through solution casting. By constructing staggered electrodes, the total polarized charges quantity is increased, achieving a larger current output. The three-unit PNG (3-PNG) based on the composite film with 15 wt% KNN powder, reaches a maximum output current of 0.85 μA, which exhibits higher charging efficiency compared to 1-PNG. Moreover, the prepared 3-PNG can effectively harvest mechanical energy from human activities and maintain a stable output after 10,000 cycles of bending and releasing. The film exhibits complete degradation when exposed to acidic, neutral, and alkaline solutions. This research provides a promising option for environmentally friendly piezoelectric materials selected and output performance enhanced through optimized structural designs, making them more suitable for practical applications.

Enhancing the Maturation of Human Pluripotent Stem Cell-Derived Cardiomyocytes with an n-Type Organic Semiconductor Coating.

Human pluripotent stem cell-derived cardiomyocytes (hPSC-CMs) are a promising cell source for cardiac regenerative medicine and in vitro modeling. However, hPSC-CMs exhibit immature structural and functional properties compared with adult cardiomyocytes. Various electrical, mechanical, and biochemical cues have been applied to enhance hPSC-CM maturation but with limited success. In this work, we investigated the potential application of the semiconducting polymer poly{[N,N'-bis(2-octyldodecyl)-naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2)) as a light-sensitive material to stimulate hPSC-CMs optically. Our results indicated that P(NDI2OD-T2)-mediated photostimulation caused cell damage at irradiances applied long-term above 36 μW/mm2 and did not regulate cardiac monolayer beating (after maturation) at higher intensities applied in a transient fashion. However, we discovered that the cells grown on P(NDI2OD-T2)-coated substrates showed significantly enhanced expression of cardiomyocyte maturation markers in the absence of a light exposure stimulus. A combination of techniques, such as atomic force microscopy, scanning electron microscopy, and quartz crystal microbalance with dissipation monitoring, which we applied to investigate the interface of the cell with the n-type coating, revealed that P(NDI2OD-T2) impacted the nanostructure, adsorption, and viscoelasticity of the Matrigel coating used as a cell adhesion promoter matrix. This modified cellular microenvironment promoted the expression of cardiomyocyte maturation markers related to contraction, calcium handling, metabolism, and conduction. Overall, our findings demonstrate that conjugated polymers such as P(NDI2OD-T2) can be used as passive coatings to direct stem cell fate through interfacial engineering of cell growth substrates.

Inkjet printed acrylate-urethane modified poly(3,4-ethylenedioxythiophene) flexible conductive films

Abstract Flexible electronics is a new generation of electronic devices in which electronic components are integrated into flexible substrates. It is used in the fabrication of displays, solar cells, integrated circuits, and increasingly in the fabrication of electronic skin (E-skin), which can mimic the properties of human skin by being able to follow skin movements and flexures without loss of mechanical and electrical properties. E-skin is suitable for integrating various sensors to monitor personal health. Conductive polymers are used in flexible electronics due to their electrical conductivity, low mass, and stability. However, their main disadvantage is their brittleness, which is why they don’t possess flexibility property without modification. Therefore, in this work, the conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT) was used as the main chain and the side branches of poly(acrylate-urethane) (PAU) were grafted onto it by atom transfer radical polymerization (ATRP) onto it, obtaining the grafted copolymer PEDOT-g-PAU. In this way, the main chain of PEDOT retains the property of electrical conductivity without losing conjugation, while the side branches of PAU have the ability to crosslink non-covalently through hydrogen bonds with PAU side branches of adjacent polymer molecules due to the presence of oxygen in their structure. The presence of hydrogen bonds allows increasing the stretchability and flexibility of the material, and they also have the ability to spontaneously renew themselves when they break due to excessive stress. Three different synthesis conditions were used to obtain polymers of different structure, which were characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and measurement of electrical conductivity with a four-point probe (4PP) method. The obtained graft copolymer was prepared in the form of ink and printed on a polyurethane (PU) substrate using inkjet technique. The conductivity of the printed layer, its elongation and adhesion were investigated, while possible delamination of the printed polymer layer was also monitored. The results showed that the PEDOT-g-PAU copolymer was successfully synthesized and inkjet printing on PU film was successful. The obtained material has satisfactory electrical and mechanical properties and could be used for the integration of fully functional biosensors with further optimization of the composition.

Preparation and characterization of double-shell phase change material microcapsules with flame retardancy and temperature regulation capability as low-emission building fillers

The building application of phase change materials (PCMs) has attracted widespread attention due to energy conservation and emission reduction. In this study, designed and prepared by two-step polymerization poly melamine tetramethylene phosphonium sulfate (PMTMPS) coating the raw phase change materials microcapsules (MPCMs), which were novel double-shell microcapsules (D-MPCMs). D-MPCMs further achieved low smoke and low toxicity in the fire based on enhancing the temperature regulation performance of MPCMs. The chemical structure of D-MPCMs was characterized by Fourier transform infrared (FTIR) spectroscopy, and 13C solid-state nuclear magnetic resonance (NMR). Transmission electron microscope (TEM) confirmed that D-MPCMs were successfully prepared, whose shapes were regular spherical. The results of differential scanning calorimetry (DSC) showed that D-MPCMs revealed excellent phase transition enthalpy (80.51 J/g). Then, the resultant D-MPCMs had good thermal reliability and stability from the thermogravimetric analysis (TGA), characterized by a residual mass of D-MPCMs was 17 % more than that of MPCMs. In the cone calorimeter test (CCT), we confirmed that the coated PMTMPS significantly reduced the fire risk parameters of the rigid polyurethane foam (RPUF) containing D-MPCMs (D-MPCM/RPUF) referring to the heat release rate (HRR), total heat release (THR), and total smoke production (TSP). D-MPCM/RPUF exhibited the lowest peak values of HRR and TSP, which were 400.115 kW/m2 and 10.512 m2, respectively. In addition, the PMTMPS shell significantly enhanced the solar photo-thermal conversion performance of the D-MPCMs. To sum up, D-MPCMs have great potential to improve flame retardancy, environmental protection, and temperature regulation capability for building thermal insulation materials.