We'll report on two series all-aromatic main-chain reactive oligomers that can be crosslinked in either the nematic phase or in the isotropic phase. This series is unique in that both model systems have an identical backbone geometry, comprised of hydroquinone with or without a phenyl substituent and phenyl substituted terephthalic acid. Crosslinking the oligomers (M_n of 1–9 kg/mol) via maleimide end-groups in the nematic or isotropic phase yields networks with similar crosslink densities (M_c) and similar thermal properties. Crosslinked films exhibit high decomposition temperatures (>395°C) and amorphous thermoset films exhibit T_g's in the 141–190°C range whereas nematic thermoset films give T_g's that range from 143 to 176°C, as measured by DMTA. However, the phase type appears to have a major effect on the stress–strain behavior of the films. All films prepared by crosslinking un-aligned nematic oligomers show poor stress–strain behavior (σ = 20–63 MPa, ε = 0.5%–5.4%), whereas crosslinking the amorphous oligomers results in films with excellent stress–strain properties (σ = 94–97 MPa, ε = 7.1%–13.3%). The superior toughness of the cured amorphous films can be attributed to the larger free volume induced by steric crowding of the phenyl substituents in the polymer repeat unit.

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The elastic modulus of corrosion product (E_cp) has been reported with significant variations in the literature. This study aims to investigate the E_cp of naturally-generated chloride-induced corrosion products formed in different concrete mixes. Microstructural characterization was conducted through nano-indentation, electron microscopy and Raman spectroscopy. The corrosion products were mainly composed of a goethite matrix with portions of maghemite, independently of the concrete composition. Microscopic analysis suggest that layers of corrosion products grow at different times and under different physico-chemical conditions. Our measurements showed that E_cp varied between 80−100 GPa, which can be suggested for numerical models of corrosion induced cracking.

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Gelatins are proteinaceous natural materials that are widely used in areas such as conservation and restoration of artifacts as adhesives and consolidants, in pharmaceutics as drug delivery carriers, and in the food industry as structurants. Herein, type A porcine gelatin adhesive films are prepared via solution casting method and their physical and mechanical properties are investigated using X-ray diffraction (XRD), differential scanning calorimetry, contact angle measurement, dynamic mechanical analysis, and uniaxial tensile tests. The results demonstrate a linear correlation between microstructure of gelatin films in terms of their triple-helix content and their macroscopic mechanical properties such as tensile strength and gel (Bloom) strength. Moreover, the findings of this study can help the scientists, in, e.g., art conservation and restoration, to predict the mechanical performance of these adhesives by performing a less material demanding and nondestructive physical measurement such as XRD.

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In this paper we will describe the synthesis and properties of two series of high molecular weight segmented block copolymers from all-aromatic amorphous (AM) or liquid crystal (LC) telechelic ester-based maleimide-functionalized oligomers (M_n = 5 kg mol^-1) and telechelic thiol-terminated poly(dimethylsiloxane) (PDMS, M_n = 1, 5 and 10 kg mol^-1). The multiblock copolymers were prepared via highly efficient thiol-ene click chemistry, and have M_ns ranging from 22 to 58 kg mol^-1. The segmented block copolymers prepared from mesogenic (LC) units show micro-phase separation and liquid crystallinity even with a PDMS content as high as 65 wt%. The AM5K-based series is completely amorphous. The multiblock copolymers with PDMS5K and 10K show two T_gs at ∼-120 °C and ∼120 °C, respectively, implying the presence of a (micro)phase separated system. The multiblock copolymer prepared from AM5K and PDMS1K displays excellent stress-strain behavior at 25 °C, with a tensile strength of 123.6 MPa, an elastic modulus of 3.4 GPa, an elongation at break of 31.2% and toughness of 30.7 MJ m^-3. The LC5K based multiblock copolymer films exhibit poor stress-strain behavior, which is the result of a higher degree of phase separation and low phase intermixing, as confirmed by TEM measurements. The shape memory properties of the PDMS-containing segmented block copolymers in the temperature range of -150 to 150 °C were tested using a rheometer in torsion mode. The glass transitions originating from the rigid aromatic blocks and flexible PDMS blocks were used as the reversible switches for designing T_g-based dual- and triple-shape memory polymer films. The AM5K-b-PDMS1K and LC5K-b-PDMS1K multiblock copolymers show dual-shape memory behavior in the temperature range of 20-150 °C. The PDMS5K based analogs show triple shape-memory behavior in the temperature range of -150-150 °C.

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In this work, we propose the use of regular branching of polyurethanes as a way to regulate chain dynamics and govern crystallization in highly dense hydrogen-bonded systems. As a result, robust and healable polyurethanes can be obtained. To this end, we synthesized a range of aliphatic propane diol derivatives with alkyl branches ranging from butyl (C4) to octadecanyl (C18). The series of brush polyurethanes was synthesized by polyaddition of the diols and hexamethylene diisocyanate. Polyurethanes with very short (C 4) and very long (C = 18) brush lengths did not lead to any significant healing due to crystallization. An intermediate amorphous regime appears for polymers with middle branch lengths (C = 4 to 8) showing a fine control of material toughness. For these systems, the side chain length regulates tube dilation, and significant macroscopic healing of cut samples was observed and studied in detail using melt rheology and tensile testing. Despite the high healing degrees observed immediately after repair, it was found that samples with medium to long length brushes lost their interfacial strength at the healed site after being heated to the healing temperature for some time after the optimal time to reach full healing. Dedicated testing suggests that annealed samples, while keeping initial tackiness, are not able to completely heal the cut interface. We attribute such behavior to annealing-induced interfacial crystallization promoted by the aliphatic branches. Interestingly, no such loss of healing due to annealing was observed for samples synthesized with C4 and C7 diols, which is identified as the optimal healing regime. These results point at the positive effect of branching on healing, provided that a critical chain length is not surpassed, as well as the need to study healing behavior long after the optimal healing times.

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Isomeric tri-aryl ketone amines, 1,3-bis(3-aminobenzoyl)benzene (133 BABB), 1,3-bis(4-aminobenzoyl)benzene (134 BABB), and 1,4-bis(4-aminobenzoyl)benzene (144 BABB) are synthesized and cured with diglycidyl ether of bisphenol A and diglycidyl ether of bisphenol F in this work. Differential scanning calorimetry and near-infrared spectroscopy reveal higher rate constants and enhanced secondary amine conversion with increasing para substitution attributed to resonance effects and the electron withdrawing nature of the carbonyl linkages. Glass transition temperatures increase from 133 BABB to 134 BABB, but decrease modestly for the 144 BABB hardener. With increasing para substitution, the flexural modulus and strength both decrease while the strain to failure increases but all BABB amines displaying higher mechanical properties than the corresponding 4,4-diaminodiphenyl sulfone (44 DDS) networks. The thermal stability of the BABB networks is found to be modestly lower than 44 DDS, but char yields are significantly higher. Changes in thermal and mechanical properties are described in terms of molecular structure and equilibrium packing density.

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We have prepared semi-crystalline polyamide (PA) thermosets using reactive side-group functionalized copolyamides as precursors. Reactive meta- and para-based phenylethynyl diacid chlorides (IPE and TPE) were synthesized and incorporated in poly(decamethylene terephthalamide) (PA 10T) using a low temperature solution polymerization method. The phenylethynyl-based comonomers disrupt crystallization of the final copolyamides and lower the onset of melting. Copolyamides containing 5, 10 and 15 mol% of the reactive comonomer could be cured at 350 °C into freestanding PA thermoset films. All thermoset films are stable up to 400 °C, as confirmed by DMTA, which is the result of network formation. The thermosets exhibit both a crystalline phase and a crosslinked amorphous phase. Depending on the concentration of the side-groups, the degree of crystallinity of the final thermosets can be controlled and suppressed by 52–76% compared to the PA 10T reference polymer. Most notable is the fact that the IPE-15 thermoset film exhibits outstanding stress–strain behavior, i.e. elongation at break (∼17%) and toughness (766 MJ·m⁻³).

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In this work we report the effect of the hard block dianhydride structure on the overall properties of partially bio-based semi-aromatic polyimides. For the study, four polyimides were synthesized using aliphatic fatty dimer diamine (DD1) as the soft block and four different commercially available aromatic dianhydrides as the hard block: 4,4'-(4,4'-isopropylidenediphenoxy) bis-(phthalic anhydride) (BPADA), 4,4'-oxydiphthalic anhydride (ODPA), 4,4′-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) and 3,3′,4,4′-biphenyltetracarboxylic dianhydride (BPDA). The polymers synthesized were fully organo-soluble thermoplastic branched polyimides with glass transition temperatures close to room temperature. The detailed analysis took into account several aspects of the dianhydrides structure (planarity, rigidity, bridging group between the phtalimides, electronic properties) and related them to the results obtained by differential scanning calorimetry, rheology, fluorescence and broadband dielectric spectroscopy. Moreover, the effect of physical parameters (crystallization and electronic interactions) on the relaxation behavior are discussed. Despite the presence of the bulky branched soft block given by the dimer diamine, all polyimides showed intermolecular charge transfer complexes, whose impact depends on the electronic properties of the dianhydride hard block. Furthermore, the results showed that polyimides containing flexible and bulky hard blocks turned out fully amorphous while the more rigid dianhydride (BPDA) led to a nanophase separated morphology with low degree of crystallinity resulting in constrained segmental relaxation with high effect on its mechanical response with the annealing time. This work represents the first detailed report on the development and characterization of polyimides based on a bio-based fatty dimer diamine. The results highlight the potential of polymer property design by controlled engineering of the aromatic dianhydride blocks. @en

State-of-the-art perovskite-based solar cells employ expensive, organic hole transporting materials (HTMs) such as Spiro-OMeTAD that, in turn, limits the commercialization of this promising technology. Herein an HTM (EDOT-Amide-TPA) is reported in which a functional amide-based backbone is introduced, which allows this material to be synthesized in a simple condensation reaction with an estimated cost of <$5 g⁻¹. When employed in perovskite solar cells, EDOT-Amide-TPA demonstrates stabilized power conversion efficiencies up to 20.0% and reproducibly outperforms Spiro-OMeTAD in direct comparisons. Time resolved microwave conductivity measurements indicate that the observed improvement originates from a faster hole injection rate from the perovskite to EDOT-Amide-TPA. Additionally, the devices exhibit an improved lifetime, which is assigned to the coordination of the amide bond to the Li-additive, offering a novel strategy to hamper the migration of additives. It is shown that, despite the lack of a conjugated backbone, the amide-based HTM can outperform state-of-the-art HTMs at a fraction of the cost, thereby providing a novel set of design strategies to develop new, low-cost HTMs.

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The current state-of-the-art hole transporting materials (HTM) for perovskite solar cells are generally synthesized via cross-coupling reactions that require expensive catalysts, inert reaction conditions and extensive product purification, resulting in high costs and therefore limiting large-scale commercialisation. Here we describe a series of HTMs prepared via simple and clean Schiff-base condensation chemistry with an estimated material cost in the range of 4-54 $ per g. The optoelectronic and thermal properties of the materials are linked to the changes in the chemical structure of the HTMs, which allow us to extract design rules for new materials, supported by density functional theory calculations. Charge transport measurements show hole mobilities in the range of 10^-5 to 10^-7 cm² V^-1 s^-1. Upon addition of LiTFSI the HTMs can be oxidized, resulting in a large increase in the conductivity of the hole transporting layer (HTL). When employed as HTL in perovskite solar cells, power conversion efficiencies close to those of spiro-OMeTAD are obtained. In particular, devices prepared with Diazo-OMeTPA show a higher open-circuit voltage. Furthermore, we show that azomethine-based HTMs can act as effective moisture barriers, resulting in a significant increase in the stability of the underlying perovskite film. We assign the improved properties to the presence of a dipole in our molecules which promotes a close molecular packing and thus leads to a high density of the as-formed HTM films, preventing the ingress of water. This work shows that HTMs prepared via condensation chemistry are not only a low-cost alternative to spiro-OMeTAD, but also act as a functional barrier against moisture-induced degradation in perovskite solar cells.

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This work presents a detailed study into the rheological properties and fracture healing behaviour of two poly(urea-urethane) polymers containing (i) hydrogen bonds and (ii) hydrogen bonds and disulphide linkages. The experimental procedure here presented using the temperature and time superposition allowed for the identification of the contribution of each reversible bond type to the network behaviour (rheology) and healing (fracture). During the experimental data analysis it was found that the same shift factors required to construct the rheological master curves from separate isothermal small-amplitude oscillatory shear (SAOS) measurements at different temperatures could also be applied to obtain a master curve for the fracture healing data as a function of healing time and temperature. This work shows therefore the apparent direct relationship between rheological response and macroscopic fracture healing.

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A self-healing sulfur vulcanized natural rubber (NR) is here reported using the common ingredients in a traditional NR formulation. The dynamic character of the di- and polysulfide bonds naturally present in covalently cross-linked rubbers was found to be responsible for the healing ability and the full recovery of mechanical properties at moderate temperatures provided the material was employed in a nonfully cured starting state. Results show that a compromise between mechanical performance and healing capability can be reached by tailoring the amount of sulfur, the cross-linking density, and the disulfide/polysulfide ratio. The healing efficiency was found to depend on the postcuring storage time, the time between damage creation and re-establishment of mechanical contact, and the actual healing time. Furthermore, a dedicated electron spin resonance (ESR) test allowed establishing the underlying healing principle based on temperature-induced free sulfur radicals. The main observations presented here can serve as the basis for the design and preparation of other self-healing polymers with long-term durability based on di-/ polysulfide bridges and other reversible moieties @en