scholarly journals The Influence of the Furan and Maleimide Stoichiometry on the Thermoreversible Diels–Alder Network Polymerization

Polymers ◽  
2021 ◽  
Vol 13 (15) ◽  
pp. 2522
Author(s):  
Ali Safaei ◽  
Seppe Terryn ◽  
Bram Vanderborght ◽  
Guy Van Assche ◽  
Joost Brancart
Keyword(s):  
Transition Temperature ◽  
Functional Groups ◽  
Polymer Networks ◽  
Viscoelastic Behavior ◽  
Mechanical Analysis ◽  
Thermomechanical Properties ◽  
Diels Alder ◽  
Stoichiometric Ratio ◽  
Self Healing ◽  
Scanning Calorimetry

In recent work, the thermoreversible Diels–Alder reaction between furan and maleimide functional groups has been studied extensively in the context of self-healing elastomers and thermosets. To elaborate the influence of the stoichiometric ratio between the maleimide and furan reactive groups on the thermomechanical properties and viscoelastic behavior of formed reversible covalent polymer networks, a series of Diels–Alder-based networks with different stoichiometric ratios was synthesized. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and dynamic rheology measurements were performed on the reversible polymer networks, to relate the reversible network structure to the material properties and reactivity. Such knowledge allows the design and optimization of the thermomechanical behavior of the reversible networks for intended applications. Lowering the maleimide-to-furan ratio creates a deficit of maleimide functional groups, resulting in a decrease in the crosslink density of the system, and a consequent decrease in the glass transition temperature, Young’s modulus, and gel transition temperature. The excess of unreacted furan in the system results in faster reaction and healing kinetics and a shift of the reaction equilibrium.

scholarly journals Influence of the Glass Transition Temperature and the Density of Crosslinking Groups on the Reversibility of Diels-Alder Polymer Networks

Polymers ◽  
2021 ◽  
Vol 13 (8) ◽  
pp. 1189
Author(s):  
Merlina Thiessen ◽  
Volker Abetz
Keyword(s):  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Radical Polymerization ◽  
Polymer Networks ◽  
Alder Reaction ◽  
Diels Alder ◽  
Self Healing ◽  
Scanning Calorimetry ◽  
Diels Alder Reaction

The interest in self-healing, recyclable, and adaptable polymers is growing. This work addresses the reversibility of crosslink formation based on Diels-Alder reaction in copolymer networks containing furfuryl and maleimide groups, which represent the “diene” and the “dienophile,” respectively. The copolymers are synthesized by atom transfer radical polymerization (ATRP) and free radical polymerization. The diene bearing copolymers are crosslinked either with a small molecule containing two dienophiles or with a dienophile bearing copolymer. The influence of the crosslinking temperature on the Diels-Alder reaction is analyzed. Furthermore, the influence of the glass transition temperature and the influence of the density of crosslinking groups on the thermo-reversibility of crosslinking are investigated by temperature dependent infrared spectroscopy and differential scanning calorimetry. It is shown that the reversibility of crosslinking is strongly influenced by the glass transition temperature of the system.

scholarly journals Self-Healing in Mobility-Restricted Conditions Maintaining Mechanical Robustness: Furan–Maleimide Diels–Alder Cycloadditions in Polymer Networks for Ambient Applications

Polymers ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 2543 ◽  
Author(s):  
Dorothee Ehrhardt ◽  
Jessica Mangialetto ◽  
Jolien Bertouille ◽  
Kurt Van Durme ◽  
Bruno Van Mele ◽  
...  
Keyword(s):  
Structural Integrity ◽  
Network Formation ◽  
Polymer Networks ◽  
Mechanical Analysis ◽  
Diels Alder ◽  
Self Healing ◽  
Ambient Conditions ◽  
Scanning Calorimetry ◽  
Diffusion Controlled ◽  
Cure Temperature

Two reversible polymer networks, based on Diels–Alder cycloadditions, are selected to discuss the opportunities of mobility-controlled self-healing in ambient conditions for which information is lacking in literature. The main methods for this study are (modulated temperature) differential scanning calorimetry, microcalorimetry, dynamic rheometry, dynamic mechanical analysis, and kinetic simulations. The reversible network 3M-3F630 is chosen to study the conceptual aspects of diffusion-controlled Diels–Alder reactions from 20 to 65 °C. Network formation by gelation is proven and above 30 °C gelled glasses are formed, while cure below 30 °C gives ungelled glasses. The slow progress of Diels–Alder reactions in mobility-restricted conditions is proven by the further increase of the system’s glass transition temperature by 24 °C beyond the cure temperature of 20 °C. These findings are employed in the reversible network 3M-F375PMA, which is UV-polymerized, starting from a Diels–Alder methacrylate pre-polymer. Self-healing of microcracks in diffusion-controlled conditions is demonstrated at 20 °C. De-gelation measurements show the structural integrity of both networks up to at least 150 °C. Moreover, mechanical robustness in 3M-F375PMA is maintained by the poly(methacrylate) chains to at least 120 °C. The self-healing capacity is simulated in an ambient temperature window between −40 and 85 °C, supporting its applicability as self-healing encapsulant in photovoltaics.

scholarly journals The Effect of POSS Type on the Shape Memory Properties of Epoxy-Based Nanocomposites

Molecules ◽  
2020 ◽  
Vol 25 (18) ◽  
pp. 4203
Author(s):  
Avraham I. Bram ◽  
Irina Gouzman ◽  
Asaf Bolker ◽  
Noam Eliaz ◽  
Ronen Verker
Keyword(s):  
Transition Temperature ◽  
Shape Memory ◽  
Crosslinking Density ◽  
Mechanical Analysis ◽  
Thermomechanical Properties ◽  
Space Environment ◽  
Scanning Calorimetry ◽  
Space Applications ◽  
Curing Conditions ◽  
Oligomeric Silsesquioxane

Thermally activated shape memory polymers (SMPs) can memorize a temporary shape at low temperature and return to their permanent shape at higher temperature. These materials can be used for light and compact space deployment mechanisms. The control of transition temperature and thermomechanical properties of epoxy-based SMPs can be done using functionalized polyhedral oligomeric silsesquioxane (POSS) additives, which are also known to improve the durability to atomic oxygen in the space environment. In this study, the influence of varying amounts of two types of POSS added to epoxy-based SMPs on the shape memory effect (SME) were studied. The first type contained amine groups, whereas the second type contained epoxide groups. The curing conditions were defined using differential scanning calorimetry and glass transition temperature (Tg) measurements. Thermomechanical and SME properties were characterized using dynamic mechanical analysis. It was found that SMPs containing amine-based POSS show higher Tg, better shape fixity and faster recovery speed, while SMPs containing epoxide-based POSS have higher crosslinking density and show superior thermomechanical properties above Tg. This work demonstrates how the Tg and SME of SMPs can be controlled by the type and amount of POSS in an epoxy-based SMP nanocomposite for future space applications.

scholarly journals Self-Healable and Recyclable Biomass-Derived Polyurethane Networks through Carbon Dioxide Immobilization

Polymers ◽  
2021 ◽  
Vol 13 (24) ◽  
pp. 4381
Author(s):  
Seohyun Baek ◽  
Juhyen Lee ◽  
Hyunwoo Kim ◽  
Inhwan Cha ◽  
Changsik Song
Keyword(s):  
Carbon Dioxide ◽  
Mechanical Analysis ◽  
Thermomechanical Properties ◽  
Polymer Materials ◽  
Self Healing ◽  
Scanning Calorimetry ◽  
Covalent Bonds ◽  
Thermal Mechanical Analysis ◽  
Carbon Dioxide Co2 ◽  
Combined Strategy

Due to growing environmental issues, research on carbon dioxide (CO2) use is widely conducted and efforts are being made to produce useful materials from biomass-derived resources. However, polymer materials developed by a combined strategy (i.e., both CO2-immobilized and biomass-derived) are rare. In this study, we synthesized biomass-derived poly(carbonate-co-urethane) (PCU) networks using CO2-immobilized furan carbonate diols (FCDs) via an ecofriendly method. The synthesis of FCDs was performed by directly introducing CO2 into a biomass-derived 2,5-bis(hydroxymethyl)furan. Using mechanochemical synthesis (ball-milling), the PCU networks were effortlessly prepared from FCDs, erythritol, and diisocyanate, which were then hot-pressed into films. The thermal and thermomechanical properties of the PCU networks were thoroughly characterized by thermogravimetric analysis, differential scanning calorimetry, dynamic (thermal) mechanical analysis, and using a rheometer. The self-healing and recyclable properties of the PCU films were successfully demonstrated using dynamic covalent bonds. Interestingly, transcarbamoylation (urethane exchange) occurred preferentially as opposed to transcarbonation (carbonate exchange). We believe our approach presents an efficient means for producing sustainable polyurethane copolymers using biomass-derived and CO2-immobilized diols.

Effect of C12-14 Alcohols on the Thermomechanical Properties of Epoxy Shape-Memory Polymer

2014 ◽  
Vol 787 ◽  
pp. 275-280
Author(s):  
Li Min Zhao ◽  
Xue Feng ◽  
Xu Jun Mi ◽  
Yan Feng Li ◽  
Hao Feng Xie ◽  
...  
Keyword(s):  
Transition Temperature ◽  
Shape Memory ◽  
Room Temperature ◽  
Aliphatic Alcohol ◽  
Shape Memory Polymer ◽  
Mechanical Analysis ◽  
Thermomechanical Properties ◽  
Epoxy System ◽  
Scanning Calorimetry ◽  
Epoxy Polymers

A critical parameter for a shape memory polymer (SMP) lies in its shape memory transition temperature. For an amorphous SMP polymer, it is highly desirable to develop methods to tailor its Tg, which corresponds to its shape memory transition temperature. Starting with an amine cured aromatic epoxy system, epoxy polymers were synthesized by introducing flexible aliphatic alcohol. The thermal and thermomechanical properties of these epoxy polymers were characterized by differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). All the crosslinked epoxy polymers with Tg’s above room temperature were found to possess shape memory properties.

scholarly journals Influence of 1D and 2D Carbon Fillers and Their Functionalisation on Crystallisation and Thermomechanical Properties of Injection Moulded Nylon 6,6 Nanocomposites

2014 ◽  
Vol 2014 ◽  
pp. 1-13 ◽  
Author(s):  
Fabiola Navarro-Pardo ◽  
Ana L. Martínez-Hernández ◽  
Victor M. Castaño ◽  
José L. Rivera-Armenta ◽  
Francisco J. Medellín-Rodríguez ◽  
...  
Keyword(s):  
Mechanical Analysis ◽  
Thermomechanical Properties ◽  
Reduced Form ◽  
Scanning Calorimetry ◽  
Graphene Nanocomposites ◽  
Moulding Process ◽  
Nylon 6,6 ◽  
Injection Moulding Process ◽  
The One ◽  
Carbon Fillers

Carbon nanotubes (CNTs) and graphene were used as reinforcing fillers in nylon 6,6 in order to obtain nanocomposites by using an injection moulding process. The two differently structured nanofillers were used in their pristine or reduced form, after oxidation treatment and after amino functionalisation. Three low nanofiller contents were employed. Crystallisation behaviour and perfection of nylon 6,6 crystals were determined by differential scanning calorimetry and wide angle X-ray diffraction, respectively. Crystallinity was slightly enhanced in most samples as the content of the nanofillers was increased. The dimensionality of the materials was found to provide different interfaces and therefore different features in the nylon 6,6 crystal growth resulting in improved crystal perfection. Dynamical, mechanical analysis showed the maximum increases provided by the two nanostructures correspond to the addition of 0.1 wt.% amino functionalised CNTs, enhancing in 30% the storage modulus and the incorporation of 0.5 wt.% of graphene oxide caused an increase of 44% in this property. The latter also provided better thermal stability when compared to pure nylon 6,6 under inert conditions. The superior properties of graphene nanocomposites were attributed to the larger surface area of the two-dimensional graphene compared to the one-dimensional CNTs.

Viscoelastic behavior of an epoxy resin during cure below the glass transition temperature: Characterization and modeling

2018 ◽  
Vol 53 (2) ◽  
pp. 155-171 ◽  
Author(s):  
Alice Courtois ◽  
Martin Hirsekorn ◽  
Maria Benavente ◽  
Agathe Jaillon ◽  
Lionel Marcin ◽  
...  
Keyword(s):  
Glass Transition ◽  
Transition Temperature ◽  
Glass Transition Temperature ◽  
Epoxy Resin ◽  
Viscoelastic Behavior ◽  
Mechanical Analysis ◽  
Strain History ◽  
Model Parameters ◽  
Degree Of Cure ◽  
Model Predictions

This paper presents a viscoelastic temperature- and degree-of-cure-dependent constitutive model for an epoxy resin. Multi-temperature relaxation tests on fully and partially cured rectangular epoxy specimens were conducted in a dynamic mechanical analysis apparatus with a three-point bending clamp. Master curves were constructed from the relaxation test results based on the time–temperature superposition hypothesis. The influence of the degree of cure was included through the cure-dependent glass transition temperature which was used as reference temperature for the shift factors. The model parameters were optimized by minimization of the differences between the model predictions and the experimental data. The model predictions were successfully validated against an independent creep-like strain history over which the temperature varied.

Thermal and Thermomechanical Properties of Poly(butylene succinate) Nanocomposites

2008 ◽  
Vol 8 (4) ◽  
pp. 1679-1689 ◽  
Author(s):  
Mamookho E. Makhatha ◽  
Suprakas Sinha Ray ◽  
Joseph Hato ◽  
Adriaan S. Luyt
Keyword(s):  
Thermal Stability ◽  
Tensile Modulus ◽  
Melting Behavior ◽  
Mechanical Analysis ◽  
Thermomechanical Properties ◽  
Scanning Calorimetry ◽  
Melt Mixing ◽  
Butylene Succinate ◽  
Modulated Differential Scanning Calorimetry ◽  
Thermal Stability Of

This article describes the thermal and thermomechanical properties of poly(butylene succinate) (PBS) and its nanocomposites. PBS nanocomposites with three different weight ratios of organically modified synthetic fluorine mica (OMSFM) have been prepared by melt-mixing in a batch mixer at 140 °C. The structure and morphology of the nanocomposites were characterized by X-ray diffraction (XRD) analyses and transmission electron microscopy (TEM) observations that reveal the homogeneous dispersion of the intercalated silicate layers into the PBS matrix. The thermal properties of pure PBS and the nanocomposite samples were studied by both conventional and temperature modulated differential scanning calorimetry (DSC) analyses, which show multiple melting behavior of the PBS matrix. The investigation of the thermomechanical properties was performed by dynamic mechanical analysis. Results reveal significant improvement in the storage modulus of neat PBS upon addition of OMSFM. The tensile modulus of neat PBS is also increased substantially with the addition of OMSFM, however, the strength at yield and elongation at break of neat PBS systematically decreases with the loading of OMSFM. The thermal stability of the nanocomposites compared to that of the pure polymer sample was examined under both pyrolytic and thermooxidative environments. It is shown that the thermal stability of PBS is increased moderately in the presence of 3 wt% of OMSFM, but there is no significant effect on further silicate loading in the oxidative environment. In the nitrogen environment, however, the thermal stability systematically decreases with increasing clay loading.

Thermomechanical Characterization of Bismuth Telluride Based Thermoelectric Materials

2001 ◽  
Vol 691 ◽  
Author(s):  
Witold Brostow ◽  
Kevin P. Menard ◽  
John B. White
Keyword(s):  
Bismuth Telluride ◽  
Van Der Waals ◽  
Mechanical Analysis ◽  
Thermomechanical Properties ◽  
Thermal Transitions ◽  
Scanning Calorimetry ◽  
Direction Parallel ◽  
Crystalline Polymers ◽  
Structural Metals ◽  
P Type

ABSTRACTThe thermoelectric properties of bismuth telluride based thermoelectric (TE) materials are well-characterized, but comparatively little has been published on the mechanical and thermomechanical properties of these materials. In this paper, we present the initial dynamic mechanical analysis (DMA) data for n-type and p-type bismuth telluride based TE materials. The materials' tan δ values, indicative of viscoelastic energy dissipation modes, approach that of glassy or crystalline polymers and are greater than ten times the tan delta of structural metals. TE samples measured perpendicular to the van der Waals planes have higher tan δ values. Thermal scans in the DMA compressive mode showed changes in mechanical properties versus temperature with clear hysteresis effects. These changes were correlated to differential scanning calorimetry (DSC) thermal transitions. The expected anisotropy was shown in flexural 3-point bending results for one n-type material that showed a storage modulus of 0.10 to 0.45 GPa in the direction parallel to the van der Waals planes and 0.07 to 0.2 GPa in the perpendicular direction.

Application of dynamic mechanical analysis techniques to bismuth telluride based thermoelectric materials

e-Polymers ◽  
2004 ◽  
Vol 4 (1) ◽  
Author(s):  
Witold Brostow ◽  
Kevin P. Menard ◽  
John B. White
Keyword(s):  
Dynamic Mechanical Analysis ◽  
Bismuth Telluride ◽  
Polymeric Materials ◽  
Mechanical Analysis ◽  
Thermomechanical Properties ◽  
Thermal Transitions ◽  
Scanning Calorimetry ◽  
Dynamic Mechanical ◽  
Tan Δ ◽  
Te Material

Abstract Dynamic mechanical analysis (DMA) techniques are commonly applied to characterize polymer-based materials - but little if at all to characterize semiconductor thermoelectric (TE) materials. TE materials may be coupled with polymeric materials in advanced thermoelectric devices, and the knowledge of TE material properties will be useful in the choice of materials for future applications. We have obtained DMA results for both n-type and p-type bismuth telluride based TE materials. We find that tan δ values, indicative of viscoelastic energy dissipation modes, approach the values for glassy or semi-crystalline polymers, and are larger by more than a whole order of magnitude than the tan δ of structural metals. DMA thermal scans show clear hysteresis-type effects and a correlation with differential scanning calorimetry thermal transitions. DMA properties as a function of frequency are briefly discussed. Our results show that DMA techniques are useful in the evaluation of thermophysical and thermomechanical properties of these TE materials and of assembled coolers. The viscoelastic effects we report may provide a damping mechanism for severe stresses inherent to service conditions of the TE coolers.

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