scholarly journals Shape-Memory Assisted Scratch-Healing of Transparent Thiol-Ene Coatings

Materials ◽  
2019 ◽  
Vol 12 (3) ◽  
pp. 482 ◽  
Author(s):  
Algirdas Lazauskas ◽  
Dalius Jucius ◽  
Valentinas Baltrušaitis ◽  
Rimantas Gudaitis ◽  
Igoris Prosyčevas ◽  
...  

A photopolymerizable thiol-ene composition was prepared as a mixture of pentaerythritol tetrakis(3-mercaptopropionate) (PETMP) and 1,3,5-triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (TTT), with 1 wt. % of 2,2-dimethoxy-2-phenylacetophenone (DMPA) photoinitiator. A systematic analytical analysis that investigated the crosslinked PETMP-TTT polymer coatings employed Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, differential scanning calorimetry, thermogravimetric analysis, pencil hardness, thermo-mechanical cyclic tensile, scratch testing, and atomic force microscopy. These coatings exhibited high optical transparency and shape-memory that assisted scratch-healing properties. Scratches produced on the PETMP-TTT polymer coatings with different constant loadings (1.2 N, 1.5 N, and 2.7 N) were completely healed after the external stimulus was applied. The strain recovery ratio and total strain recovery ratio for PETMP-TTT polymer were found to be better than 94 ± 1% and 97 ± 1%, respectively. The crosslinked PETMP-TTT polymer network was also capable of initiating scratch recovery at ambient temperature conditions.

2013 ◽  
Vol 1453 ◽  
Author(s):  
Bonifacio Alvarado-Tenorio ◽  
Angel Romo-Uribe ◽  
Patrick T. Mather

ABSTRACTShape memory nanocomposites were produced following a simple one-step synthesis route initiated by a series of molar mixtures of POSS thiol nanocages and pentaerythritol tetrakis (3mercaptopropionate), and a diacrylate polycaprolactone (PCL) with Mn=3,000 g/mol. Simultaneous wide- and small- angle X ray scattering (WAXS/SAXS), differential scanning calorimetry (DSC) and atomic force microscopy (AFM) experiments were carried out and results were correlated on microstructure. Molecular identification was performed by Fourier transformed infrared (FTIR-ATR). Thermomechanical shape memory cycles revealed that the nanocomposites achieved excellent shape recovery (99%) and shape fixity (100%) parameters. Dynamic mechanical analysis showed that elastomeric modulus decrease in function of the POSS thiol molar concentration and this result is correlated with the decrease in average crosslink density (ν). WAXS studies revealed orthorhombic crystallites for PCL combined with an amorphous POSS phase when the molar concentration of POSS was low (2.5%, 5%, 10%). However, increasing the molar concentration of POSS thiol until 20%, a broad and weak reflection centered around 2θ =7.9° which corresponded to imperfect POSS crystals. At the nanoscale, SAXS analysis showed lamellar nanostructure formation for all POSS/polycaprolactone crosslinked networks. Strikingly, induced anisotropic orientation of polycaprolactone lamellar nanostructure was observed when the concentration of POSS increased to 10 and 20 mol%.


2021 ◽  
Vol 10 (1) ◽  
pp. 37-48
Author(s):  
Sijia Li ◽  
Chun Shao ◽  
Zhikun Miao ◽  
Panfang Lu

Abstract Waste biomass can be used as a raw material for food packaging. Different concentrations of gelatin (GEL) were introduced into the leftover rice (LR) system to form an interpenetrating polymer network (IPN) for improving the properties of the films. The structure and morphology of films were evaluated by Fourier transform infrared, scanning electron microscopy, and atomic force microscopy, which showed good compatibility between LR and GEL. The moisture content and oil absorption rate of IPN films were down by 105% and 182%, respectively, which showed better water and oil resistance than the LR film. In addition, increasing GEL concentration led to enhancement in the tensile strength of films from 2.42 to 11.40 MPa. The water contact angle value of the IPN films (117.53°) increased by 147% than the LR film (47.56°). The low haze of IPN films was obtained with the increment of the mutual entanglement of LR and GEL. The 30–50% GEL addition improved the water vapor barrier and thermal stability properties of the IPN films. This study highlights that LR as waste biomass can have a practical application in food packaging.


Polymers ◽  
2021 ◽  
Vol 13 (6) ◽  
pp. 878
Author(s):  
Krystyna Wnuczek ◽  
Andrzej Puszka ◽  
Łukasz Klapiszewski ◽  
Beata Podkościelna

This study presents the preparation and the thermo-mechanical characteristics of polymeric blends based on di(meth)acrylates monomers. Bisphenol A glycerolate diacrylate (BPA.GDA) or ethylene glycol dimethacrylate (EGDMA) were used as crosslinking monomers. Methyl methacrylate (MMA) was used as an active solvent in both copolymerization approaches. Commercial polycarbonate (PC) was used as a modifying soluble additive. The preparation of blends and method of polymerization by using UV initiator (Irqacure® 651) was proposed. Two parallel sets of MMA-based materials were obtained. The first included more harmless linear hydrocarbons (EGDMA + MMA), whereas the second included the usually used aromatic copolymers (BPA.GDA + MMA). The influence of different amounts of PC on the physicochemical properties was discussed in detail. Chemical structures of the copolymers were confirmed by attenuated total reflection–Fourier transform infrared (ATR/FT-IR) spectroscopy. Thermo-mechanical properties of the synthesized materials were investigated by means of differential scanning calorimetry (DSC), thermogravimetric (TG/DTG) analyses, and dynamic mechanical analysis (DMA). The hardness of the obtained materials was also tested. In order to evaluate the surface of the materials, their images were obtained with the use of atomic force microscopy (AFM).


2015 ◽  
Vol 1754 ◽  
pp. 69-74
Author(s):  
Ravi Gaikwad ◽  
Tinu Abraham ◽  
Aharnish Hande ◽  
Fatemeh Bakhtiari ◽  
Siddhartha Das ◽  
...  

ABSTRACTAtomic force microscopy is employed to study the structural changes in the morphology and physical characteristics of asphaltene aggregates as a function of temperature. The exotic fractal structure obtained by evaporation-driven asphaltene aggregates shows an interesting dynamics for a large range of temperatures from 25°C to 80°C. The changes in the topography, surface potential and adhesion are unnoticeable until 70°C. However, a significant change in the dynamics and material properties is displayed in the range of 70°C - 80°C, during which the aspahltene aggregates acquire ‘liquid-like’ mobility and fuse together. This behaviour is attributed to the transition from the pure amorphous phase to a crystalline liquid phase which occurs at approximately 70°C as shown by using Differential Scanning Calorimetry (DSC). Additionally, the charged nature of asphaltenes and bitumen is also explored using kelvin probe microscopy. Such observations can lead to the development of a rational approach to the fundamental understanding of asphaltene aggregation dynamics and may help in devising novel techniques for the handling and separation of asphaltene aggregates using dielectrophoretic methods.


Author(s):  
Kannan Dasharathi ◽  
John A. Shaw

Results are reported from an ongoing experimental investigation of the effects of thermo-oxidative aging on the mechanical behavior of an epoxy shape memory polymer (SMP). Chemo-rheological degradation due to macromolecular scission and cross-linking is one of the main factors contributing to the chemical aging of thermo-responsive SMPs. This aging may manifest as residual strain or irreversible material property changes, which can affect the performance and limit the useful life of a SMP. A relatively new epoxy SMP based on the diglycidyl ether of bisphenol A is synthesized, and specimens are tested under uni-axial tension using a dynamic mechanical analyzer. Fundamental viscoelastic behavior and thermal expansion coefficients are first characterized, showing a glass transition near 60 °C. Shape memory cycle experiments are performed at shape fixing temperatures of 80, 125, 150 and 175 °C, and the effect of fixing time at each temperature is examined upon subsequent strain recovery at 80 °C. Performance parameters such as recovery ratio, speed of recovery and residual strain are quantified as a function of shape fixing time and temperature. No effect of chemical aging was seen at a fixing temperature of 80 °C, although the recovery ratio decreases initially with increasing fixing time and stabilizes near 92 %. Only minor effects of chemical aging are seen in the mechanical responses for fixing temperatures of 125 and 150 °C, but specimens exhibit progressively more noticeable color changes that indicate oxidation. Significant effects are observed at the highest fixing temperature of 175 °C, where chemical aging at longer fixing times results in a reduction in recovery rate across the rubber-glass transition temperature, progressively larger residual strains, lack of complete strain recovery at 80 °C, and higher temperatures to achieve 90 % strain recovery.


Polymers ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 646 ◽  
Author(s):  
Ivan Bessonov ◽  
Anastasia Moysenovich ◽  
Anastasia Arkhipova ◽  
Mariam Ezernitskaya ◽  
Yuri Efremov ◽  
...  

Previously, we have described the preparation of a novel fibroin methacrylamide (FbMA), a polymer network with improved functionality, capable of photocrosslinking into Fb hydrogels with elevated stiffness. However, it was unclear how this new functionality affects the structure of the material and its beta-sheet-associated crystallinity. Here, we show that the proposed method of Fb methacrylation does not disturb the protein’s ability to self-aggregate into the stable beta-sheet-based crystalline domains. Fourier transform infrared spectroscopy (FTIR) shows that, although the precursor ethanol-untreated Fb films exhibited a slightly higher degree of beta-sheet content than the FbMA films (46.9% for Fb-F-aq and 41.5% for FbMA-F-aq), both materials could equally achieve the highest possible beta-sheet content after ethanol treatment (49.8% for Fb-F-et and 49.0% for FbMA-F-et). The elasticity modulus for the FbMA-F-et films was twofold higher than that of the Fb-F-et as measured by the uniaxial tension (130 ± 1 MPa vs. 64 ± 6 MPa), and 1.4 times higher (51 ± 11 MPa vs. 36 ± 4 MPa) as measured by atomic force microscopy. The culturing of human MG63 osteoblast-like cells on Fb-F-et, FbMA-F-et-w/oUV, and FbMA-F-et substrates revealed that the photocrosslinking-induced increment of stiffness increases the area covered by the cells, rearrangement of actin cytoskeleton, and vinculin distribution in focal contacts, altogether enhancing the osteoinductive activity of the substrate.


Coatings ◽  
2018 ◽  
Vol 9 (1) ◽  
pp. 13 ◽  
Author(s):  
Joost Brancart ◽  
Robrecht Verhelle ◽  
Jessica Mangialetto ◽  
Guy Van Assche

While thermally reversible polymer network coatings based on the Diels-Alder reaction are widely studied, the mechanisms responsible for the heating-mediated healing of damage is still not well understood. The combination of microscopic evaluation techniques and fundamental insights for the thermoreversible network formation in the bulk and coating shed light on the mechanisms behind the damage healing events. The thermomechanical properties of thermoset and elastomer coatings, crosslinked by the furan-maleimide Diels-Alder cycloaddition reaction, were studied in bulk and compared to the thermal behaviour applied as coatings onto aluminium substrates. The damage sealing of thermoset (Tg = 79 °C) and elastomer (Tg = −49 °C) coatings were studied using nano-lithography and atomic force microscopy (AFM). The sealing event is studied and modelled at multiple temperatures and correlated to the changes in the network structure and corresponding thermomechanical properties.


2020 ◽  
Vol 40 (2) ◽  
pp. 136-142 ◽  
Author(s):  
Homa Maleki ◽  
Hossein Barani

AbstractThe stereocomplex formation is a promising method to improve the properties of poly(lactide) (PLA)-based products due to the strong interaction of the side-by-side arrangement of the molecular chains. Recently, electrospinning method has been applied to prepare PLA stereocomplex, which is more convenient. The objective of the current study is to make stereocomplexed PLA nanofibers using electrospinning method and compare their properties and structures with pure poly(l-lactide) (PLLA) fibers. The stereocomplexed fibers were electrospun from a blend solution of high molecular weight PLLA and poly(d-lactide) (1:1 ratio). The morphology of the obtained electrospun fibers was examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM). Differential scanning calorimetry was applied to study their thermal properties and crystallinity. Fourier transform infrared spectroscopy (FTIR) test was conducted on the samples to characterize their chemical properties. The SEM and AFM images indicated that smooth uniform fibers with a cylindrical structure were produced. Besides, the FTIR results and thermal properties confirmed that only stereocomplex crystallites formed in the resulting fibers via the electrospinning method.


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