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Elastomers have many industrial, medical and commercial applications, however, their huge demand raises an important question of how to dispose of the out-of-service elastomers. Ideal elastomers that are concurrently tough, recyclable, and degradable are in urgent need, but their preparation remains a rigorous challenge. Herein, a polycaprolactone (PCL) based polyurethane elastomer is designed and prepared to meet this demand. Owing to the presence of dynamic coordination bond and the occurrence of strain-induced crystallization, the obtained elastomer exhibits a high toughness of ≈372 MJ m-3 and an unprecedented fracture energy of ≈646 kJ m-2 , which is much higher than natural rubber (≈50 MJ m-3 for toughness and ≈10 kJ m-2 for fracture energy). In addition, the elastomer can be recycled at least three times using solvent without losing its mechanical properties and can be degraded by lipase in ≈2 months. Finally, biological experiments demonstrate that the elastomer possesses good biocompatibility and can facilitate wound healing in mice when used as sutures. It is believed that the obtained elastomer meets the requirements for next-generation elastomers and is expected to be used in emerging fields such as biomedicine, flexible electronics, robotics and beyond.

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Advanced elastomers are increasingly used in emerging areas, for example, flexible electronics and devices, and these real-world applications often require elastomers to be stretchable, tough and fire safe. However, to date there are few successes in achieving such a performance portfolio due to their different governing mechanisms. Herein, a stretchable, supertough, and self-extinguishing polyurethane elastomers by introducing dynamic π-π stacking motifs and phosphorus-containing moieties are reported. The resultant elastomer shows a large break strain of ≈2260% and a record-high toughness (ca. 460 MJ m-3 ), which arises from its dynamic microphase-separated microstructure resulting in increased entropic elasticity, and strain-hardening at large strains. The elastomer also exhibits a self-extinguishing ability thanks to the presence of both phosphorus-containing units and π-π stacking interactions. Its promising applications as a reliable yet recyclable substrate for strain sensors are demonstrated. The work will help to expedite next-generation sustainable advanced elastomers for flexible electronics and devices applications.

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This work concerns the waste management method of algae biomass wastes (ABW). For this purpose, we prepared bio-based thermoplastic polyurethane elastomer (bio-TPU) composites. Algae biomass wastes are derived from algal oil extraction of Chlorella vulgaris and from biomass of Enteromorpha and Zostera marina. ABWs were used in the bio-TPUs composites as a filler in the quantity of 1, 5, 10, and 15 wt.%. The bio-based composites were prepared via the in situ method. Polymer matrix was synthesized from a bio-based polyester polyol, diisocyanate mixture (composed of partially bio-based and synthetic diisocyanates), and bio-based 1,3 propanediol. In this study, the chemical structure, morphology, thermal and mechanical properties of prepared composites were investigated. Based on the conducted research, it was determined that the type and the content of algae waste influence the properties of the bio-based polyurethane matrix. In general, the addition of algae biomass wastes led to obtain materials characterized by good mechanical properties and noticeable positive ecological impact by increasing the total amount of green components in prepared bio-TPU-based composites from 68.7% to 73.54%.

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Polype ntafluoropropane glycidyl ether (PPFEE), a new random block hydroxyl-terminated polyfluoroether, was synthesized successfully by cationic ring-opening polymerization of 2-(2,2,3,3,3-pentafluoropropoxymethyl) oxirane, and its molecular structure was confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectrometry, and gel permeation chromatography. The PPFEE-based polyurethane elastomers featuring fluorine in their side chains were prepared using PPFEE as soft segments, polyisocyanate polyaryl polymethylene isocyanate as hard segments, and dibutyltin dilaurate as catalysts under different curing conditions. The microphase separation, mechanical performance, and thermal behavior of the elastomers were investigated by differential scanning calorimetry, uniaxial tensile test, and thermal gravimetric analysis, respectively. Based on the results, the percentage of hard segments dissolved into the soft segments of elastomers was opposite to the change in breaking strength. The PPFEE-based polyurethane elastomer cured with 20 wt% PAPI at the curing temperature of 50 °C displayed the maximum tensile elongation of 2.26 MPa with an elongation at break of nearly 150%. The increased contents of PAPI can effectively strengthen the tensile strength, and the maximum tensile elongation was 3.04 MPa with an elongation at break of nearly 90% when the content of PAPI was 26 wt%. In addition, the PPFEE-based polyurethane elastomers exhibited excellent resistance to thermal decomposition and a sharp weight loss temperature at around 371 °C. All the results demonstrated that the PPFEE may be a potential polymeric binder as one of the ingredients applied to future propellant formulations.

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Polyurethane elastomers (PUE), with superior mechanical properties and excellent corrosion resistance, are applied widely to the protective capability of structures under low-speed impact. However, they are prone to instantaneous phase transition, irreversible deformation and rupture even arising from holes under high-speed impact. In this paper, mussel adhesion proteins were applied to modify carbon nanofibers (CNFs) in a non-covalent way, and creatively mixed with PUE. This can improve the dispersity and interfacial compatibility of nanofillers in the PUE matrix. In addition, the homogeneous dispersion of modified nanofillers can serve as "reinforcing steel bars". The nanofillers and PUE matrix can form "mud and brick" structures, which show superb mechanical properties and impact resistance. Specifically, the reinforcement of 1.0 wt.% modified fillers in PUE is 103.51%, 95.12% and 119.85% higher than the neat PUE in compression modulus, storage modulus and energy absorption capability, respectively. The results have great implications in the design of composite parts for aerospace and army vehicles under extreme circumstances.

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Liquid metal (LM)-polymer composites that combine the thermal and electrical conductivity of LMs with the shape-morphing capability of polymers are attracting a great deal of attention in the fields of reconfigurable electronics and soft robotics. However, investigation of the synergetic effect between the shape-changing properties of LMs and polymer matrices is lacking. Herein, a self-healable and recyclable dual-shape memory composite, comprising an LM (gallium) and a Diels-Alder (DA) crosslinked crystalline polyurethane (PU) elastomer, is reported. The composite exhibits a bilayer structure and achieves excellent shape programming abilities, due to the phase transitions of the LM and the crystalline PU elastomers. To demonstrate these shape-morphing abilities, a heat-triggered soft gripper, which can grasp and release objects according to the environmental temperature, is designed and built. Similarly, combining the electrical conductivity and the dual-shape memory effect of the composite, a light-controlled reconfigurable switch for a circuit is produced. In addition, due to the reversible nature of DA bonds, the composite is self-healable and recyclable. Both the LM and PU elastomer are recyclable, demonstrating the extremely high recycling efficiency (up to 96.7%) of the LM, as well as similar mechanical properties between the reprocessed elastomers and the pristine ones.

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This study concerns green thermoplastic polyurethanes (TPU) obtained by controlling the chemical structure of flexible segments. Two types of bio-based polyether polyols-poly(trimethylene glycol)s-with average molecular weights ca. 1000 and 2700 Da were used (PO3G1000 and PO3G2700, respectively). TPUs were prepared via a two-step method. Hard segments consisted of 4,4'-diphenylmethane diisocyanates and the bio-based 1,4-butanodiol (used as a chain extender and used to control the [NCO]/[OH] molar ratio). The impacts of the structure of flexible segments, the amount of each type of prepolymer, and the [NCO]/[OH] molar ratio on the chemical structure and selected properties of the TPUs were verified. By regulating the number of flexible segments of a given type, different selected properties of TPU materials were obtained. Thermal analysis confirmed the high thermal stability of the prepared materials and revealed that TPUs based on a higher amount of prepolymer synthesized from PO3G2700 have a tendency for cold crystallization. An increase in the amount of PO3G1000 at the flexible segments caused an increase in the tensile strength and decrease in the elongation at break. Melt flow index results demonstrated that the increase in the amount of prepolymer based on PO3G1000 resulted in TPUs favorable in terms of machining.

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Bio-based polymeric materials and green routes for their preparation are current issues of many research works. In this work, we used the diisocyanate mixture based on partially bio-based diisocyanate origin and typical petrochemical diisocyanate for the preparation of novel bio-based thermoplastic polyurethane elastomers (bio-TPUs). We studied the influence of the diisocyanate mixture composition on the chemical structure, thermal, thermomechanical, and mechanical properties of obtained bio-TPUs. Diisocyanate mixture and bio-based 1,4-butanediol (as a low molecular chain extender) created bio-based hard blocks (HS). The diisocyanate mixture contained up to 75 wt % of partially bio-based diisocyanate. It is worth mentioning that the structure and amount of HS impact the phase separation, processing, thermal or mechanical properties of polyurethanes. The soft blocks (SS) in the bio-TPU's materials were built from α,ω-oligo(ethylene-butylene adipate) diol. Hereby, bio-TPUs differed in hard segments content (c.a. 30; 34; 40, and 53%). We found that already increase of bio-based diisocyanate content of the bio-TPU impact the changes in their thermal stability which was measured by TGA. Based on DMTA results we observed changes in the viscoelastic behavior of bio-TPUs. The DSC analysis revealed decreasing in glass transition temperature and melting temperature of hard segments. In general, obtained materials were characterized by good mechanical properties. The results confirmed the validity of undertaken research problem related to obtaining bio-TPUs consist of bio-based hard building blocks. The application of partially bio-based diisocyanate mixtures and bio-based chain extender for bio-TPU synthesis leads to sustainable chemistry. Therefore the total level of "green carbons" increases with the increase of bio-based diisocyanate content in the bio-TPU structure. Obtained results constitute promising data for further works related to the preparation of fully bio-based thermoplastic polyurethane elastomers and development in the field of bio-based polymeric materials.

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Due to the current trends in sustainable development and the reduction in the use of fossil fuels (Green Deal strategy and the circular economy), and thus, the increased interest of the polyurethane industry in polyols derived from renewable sources, it is important to study the impact of these polyols on the flammability of new bioelastomers. The goal of this study was to check the influence of biobased polyols, such as tall oil (TO)-based polyols, soybean oil (SO)-based polyol, and rapeseed oil (RO)-based polyol, on the reduction in the burning and fume emissions of polyurethane and poly(urea)urethane elastomers (EPURs and EPUURs). The thermal stability of these materials was tested using thermogravimetric analysis (TGA). In turn, the flame retardancy and smoke emissions were checked using a cone calorimetry test. The released gases were identified using TGA coupled with Fourier transform infrared (FT-IR) spectroscopy (TGA/FT-IR). Moreover, the morphological and structural characteristics of the char residues were characterized using FT-IR and scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS). The obtained data were compared to the results received for elastomers produced with petroleum substrates. The addition of biobased polyols led to a reduction in the burning as a result of the formation of char, especially RO polyol. Moreover, the TO and RO polyols increased the thermal stability of the elastomers.

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Application of bio-based diisocyanates with low volatility instead petrochemical diisocyanates has positive impact on environment by reduction of hazardous effects on living organisms and lead to bio-based polyurethanes (bio-PUs) with good usage properties. This work was focused on the synthesis and chosen properties examination of partially bio-based thermoplastic polyurethane elastomers (bio-PUs) obtained using diisocyanate mixtures, polytetrahydrofurane (PolyTHF) and bio-1,3-propanediol (bio-PDO). Two types of diisocyanate mixtures were prepared as follows: aliphatic-aliphatic based on hexamethylene diisocyanate with partially bio-based aliphatic diisocyanate Tolonate™ X FLO 100 (HDI-FLO) and aromatic-aliphatic based on diphenylmethane diisocyanate with partially bio-based diisocyanate (MDI-FLO) with reduction of 25 mass% of petrochemical diisocyanate. Bio-PUs were obtained via prepolymer method. Thermoplastic polyurethane elastomers have been examined in the terms of chemical structure and thermal, thermomechanical, mechanical and physicochemical properties. Bio-PU based on HDI-FLO diisocyanate mixture exhibited higher thermal stability. The beginning of thermal decomposition took a place at lower temperature ca. 30 ºC) and lower rate than the MDI-PU based materials. DMA analysis showed that HDI-FLO based polyurethanes exhibited greater capacity to accumulate energy and higher stiffness. Both materials characterized similar tensile strength and hardness, but with difference that TPU based on HDI-FLO relieved greater elongation at break about 360% reached 813%. Taking into account versatile properties of bio-TPU, these material can find application in many branches of industry.

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There is a huge requirement of elastomers for use in tires, seals, and shock absorbers every year worldwide. In view of a sustainable society, the next generation of elastomers is expected to combine outstanding healing, recycling, and damage-tolerant capacities with high strength, elasticity, and toughness. However, it remains challenging to fabricate such elastomers because the mechanisms for the properties mentioned above are mutually exclusive. Herein, the fabrication of healable, recyclable, and mechanically tough polyurethane (PU) elastomers with outstanding damage tolerance by coordination of multiblock polymers of poly(dimethylsiloxane) (PDMS)/polycaprolactone (PCL) containing hydrogen and coordination bonding motifs with Zn2+ ions is reported. The organization of bipyridine groups coordinated with Zn2+ ions, carbamate groups cross-linked with hydrogen bonds, and crystallized PCL segments generates phase-separated dynamic hierarchical domains. Serving as rigid nanofillers capable of deformation and disintegration under an external force, the dynamic hierarchical domains can strengthen the elastomers and significantly enhance their toughness and fracture energy. As a result, the elastomers exhibit a tensile strength of ≈52.4 MPa, a toughness of ≈363.8 MJ m-3 , and an exceptional fracture energy of ≈192.9 kJ m-2 . Furthermore, the elastomers can be conveniently healed and recycled to regain their original mechanical properties and integrity under heating.

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Thermoplastic polyurethane elastomers (TPUs) are widely used in a variety of applications as a result of flexible and superior performance. However, few scholars pay close attention on the design and synthesis of TPUs through the self-determined laboratory process, especially on definite of chemical structures and upon the influence on properties. To investigate the properties of synthesized modifier based on chemical structure, firstly each kind of unknown structure and composition ratio of TPUs was determined by using a new method. Furthermore, the thermal characteristics and mechanical properties of modifiers were exposed by thermal characteristics and mechanics performance tests. The experimental results indicate that TPUs for use as an asphalt modifier can successfully be synthesized with the aid of semi-prepolymer method. The linear backbone structure of TPUs with different hard segment contents were determined by micro test methods. The polyester-based TPUs had thermal behavior better than the polyether-based TPUs; conversely, the low temperature performance of polyether-based TPUs was superior. Most importantly, it was found that the relative molecular mass of TPUs exhibited a weak effect on the mechanical properties, whereas the crystallinity of hard segment showed a significant influence on the properties of TPUs.

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Elastomer compositions containing various particulate fillers can be formulated according to the specific functions required of them. Stress softening-which is also known as the Mullins effect-occurs during high loading and unloading paths in certain supramolecular elastomer materials. Previous experiments have revealed that the load-displacement response differs according to the filler used, demonstrating an unusual model of correspondence between the constitutive materials. Using a spherical indentation method and numerical simulation, we investigated the Mullins effect on polyurethane (PU) compositions subjected to cyclic uniaxial compressive load. The PU compositions comprised rigid particulate fillers (i.e., nano-silica and carbon black). The neo-Hooke model and the Ogden-Roxburgh Mullins model were used to describe the nonlinear deformation behavior of the soft materials. Based on finite element methods and parameter optimization, the load-displacement curves of various filled PUs were analyzed and fitted, enabling constitutive parameter prediction and inverse modeling. Hence, correspondence relationships between material components and constitutive parameters were established. Such relationships are instructive for the preparation of materials with specific properties. The method described herein is a more quantitative approach to the formulation of elastomer compositions comprising particulate fillers.

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Advanced stretchable electronic sensors with a complex structure place higher requirements on the mechanical properties and manufacturing process of the stretchable substrate materials. Herein, three kinds of polyurethane acrylate oligomers were synthesized successfully and mixed with a commercial acrylate monomer (isobornyl acrylate) to prepare photocurable resins with a low viscosity for a digital light processing three-dimensional (3D) printer without custom equipment. Results showed that the resin containing poly(tetrahydrofuran) units (PPTMGA-40) exhibited optimal mechanical properties and shape recoverability. The tensile strength and elongation at break of PPTMGA-40 were 15.7 MPa and 414.3%, respectively. The unprecedented fatigue resistance of PPTMGA-40 allowed it to withstand 100 compression cycles at 80% strain without fracture. The transmittance of PPTMGA-40 reached 89.4% at 550 nm, showing high transparency. An ionic hydrogel was coated on the surface of 3D-printed structures to fabricate stretchable sensors, and their conductivity, transparency, and mechanical performance were characterized. A robust piezoresistive strain sensor with a high strength (∼6 MPa) and a wearable finger guard sensor were fabricated, demonstrating that this hydrogel-elastomer system can meet the requirements of applications for advanced stretchable electronic sensors and expand the usage scope.

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BACKGROUND: The 3D printing is relevant as a manufacturing technology of functional models for forensic, pharmaceutical and bioanalytical applications such as drug delivery systems, sample preparation and point-of-care tests. OBJECTIVE: Melting behavior and autofluorescence of materials are decisive for optimal printing and applicability of the product which are influenced by varying unknown additives. METHODS: We have produced devices for bioanalytical applications from commercially available thermoplastic polymers using a melt-layer process. We characterized them by differential scanning calorimetry, fluorescence spectroscopy and functional assays (DNA capture assay, model for cell adhesion, bacterial adhesion and biofilm formation test). RESULTS: From 14 tested colored, transparent and black materials we found only deep black acrylonitrile-butadiene-styrene (ABS) and some black polylactic acid (PLA) useable for fluorescence-based assays, with low autofluorescence only in the short-wave range of 300-400 nm. PLA was suitable for standard bioanalytical purposes due to a glass transition temperature of approximately 60°C, resistance to common laboratory chemicals and easy print processing. For temperature-critical methods, such as hybridization reactions up to 90°C, ABS was better suited. CONCLUSIONS: Autofluorescence was not a disadvantage per se but can also be used as a reference signal in assays. The rapid development of individual protocols for sample processing and analysis required the availability of a material with consistent quality over time. For fluorescence-based assays, the use of commercial standard materials did not seem to meet this requirement.

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Waxy corn starch modified polyurethane elastomers were synthesized by step growth polymerization reaction between NCO-terminated prepolymer and chain extenders (1,4-butanediol/starch). Isophorone diisocyanates (IPDI) was reacted with hydroxyl terminated polybutadiene (HTPB) to synthesize prepolymer that was reacted with different moles of 1,4-butanediol (1,4-BDO) and starch to produced five samples of polyurethane. These specimens were analyzed by Fourier transformed infrared (FTIR) and proton Nuclear Magnetic Resonance (1H NMR) spectroscopy to determine the structural information. However, role of starch as chain extender was examined by gel permeation chromatography (GPC). Additionally, starch increased the thermal stability of PUs as compared to the conventional chain extender (1,4-BDO). Over all, this work has been designed to develop biodegradable polyurethanes that could be used in biomedical systems.

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In this work, the preparation of novel biocompatible polyurethane (PU) elastomers were carried out using curcumin and 1,4-butanediol (1,4-BDO) via step growth polymerization reaction of hydroxyl terminated polybutadiene (HTPB), toluene diisocyanate (TDI) and chitin to improve the biocompatibility, antibacterial and antioxidant properties of PU elastomers. Five samples were synthesized by varying moles ratio of curcumin and 1,4-BDO. The structural study of blends was done by FTIR spectroscopy which confirmed the incorporation of curcumin and 1,4-BDO into the polyurethane matrix. TGA analysis of polyurethane (PU) blends showed good thermal stability with 0.25 M curcumin and 1.75 M 1,4-BDO. Measurements of antibacterial properties were done via agar diffusion method which showed outstanding potential against selected strains of bacteria. The results revealed that biocompatibility, antibacterial and antioxidant potential of purposed polyurethanes elastomers were improved by the incorporation of curcumin which might be the precursor of biomedical applications. Collectively, this work is a footstep towards the synthesis of innovative biocompatible materials which made it suitable for biological applications.

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This current study aims to study of the thermal behavior of the polyurethane elastomers (PUEs) by varying blends of 1, 4-butanediol and chitosan (CS) into the backbone of polyurethane (PU). The polycaprolactone diol (PCL) was used as a macrodiol while a mixture of CS and 1, 4-butanediol was reacted to extend the polymer. For the preparation of NCO-endcapped polyurethane prepolymer; one equivalent of PCL was reacted with three equivalents of toluene diisocyanate (TDI). The obtained pre-polymer was further extended with CS and 1, 4-butanediol (2 mol) individually and with different blends. The characterization of the structure was determined using FTIR and NMR spectroscopy. The glass transition temperature of prepared polyurethanes was measured by differential scanning calorimetry (DSC). The results obtained showed that, the thermal behavior of PUs was enhanced as the CS contents were increased in the PU backbone. The crystalline behavior of CS increased the hydrophobicity of the prepared PUs. Moreover; the water absorption, contact angle, swelling behavior, work of water adhesion and surface free energy of the synthesized PUs were affected with the addition of chitosan. Finally, it has been concluded resultant chitosan based PU has a potential for biomedical implant i.e., non-absorbable suture.

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Amphiphilic polyurethane elastomers (APUE) were synthesized using a two-step polyaddition reaction based on the hydroxyl-terminated polydimethylsiloxane (PDMS) and polyethylene glycol (PEG) soft segments with the molecular weights (Mw's) of 2000 and 1000, respectively. The effects of the PDMS/PEG contents on the properties and structures of the APUE were investigated. It was found that the APUE possessed high elongation, moderate tensile strength, and good thermal properties. In addition, the APUE showed tunable oxygen permeability (Dk) and water vapor transmission rate (WVTR), and a similar WVTR to that of skin could be obtained for the optimized sample (APUE2). Importantly, APUE also exhibited excellent antibacterial efficacy against two kinds of bacteria along with impressive cytocompatibility. All of the results demonstrated that the synthesized APUE will hold substantial potential for biomaterial applications.

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The presented results make an original contribution to the development of knowledge on the prediction and/or modeling of the abrasive wear properties of polyurethanes. A series of segmented linear polyurethane elastomers (PUR)-In which the hard segments consist of 4,4'-methylene bis(phenylisocyanate) and 1,4-butanodiol, whilst polyether, polycarbonate, or polyester polyols constitute the soft segments-Were synthesized and characterized. The hardness and wear performance as functions of the variable chemical composition of polyurethane elastomers were evaluated in order to define the relationship between studied factors. The microstructure was characterized in detail, including analysis of the hydrogen bonding by Fourier transformed infrared (FT-IR) spectroscopy and the phase structure by X-ray scattering (WAXS) and differential scanning calorimetry (DSC) methods. The presented studies provide the key features of the polymer composition affecting the abrasive resistance as well as attempts to explain the origin of the differences in the polyurethane elastomers' performance.