scholarly journals Hydrothermal Carbon as Reactive Fillers to Produce Sustainable Biocomposites with Aromatic Bio-Based Epoxy Resins

Polymers ◽  
2021 ◽  
Vol 13 (2) ◽  
pp. 240
Author(s):  
Iuliana Bejenari ◽  
Roxana Dinu ◽  
Sarah Montes ◽  
Irina Volf ◽  
Alice Mija

Thiswork is focused on the development of sustainable biocomposites based on epoxy bioresin reinforced with a natural porous material (hydrochar, HC) that is the product of spruce bark wastes subjected to hydrothermal decomposition. To identify the influence of hydrochar as a reinforcing material on the designed composites, seven formulations were prepared and tested. An aromatic epoxy monomer derived from wood biomass was used to generate the polymeric matrix, and the formulations were prepared varying the filler concentration from 0 to 30 wt %. The reactivity of these formulations, together with the structural, thermal, and mechanical properties of bio-based resin and biocomposites, are investigated. Surprisingly, the reactivity study performed by differential scanning calorimetry (DSC) revealed that HC has a strong impact on polymerization, leading to an important increase in reaction enthalpy and to a decrease of temperature range. The Fourier Transform Infrared Spectroscopy (FT-IR) investigations confirmed the chemical bonding between the resin and the HC, while the dynamic mechanical analysis (DMA) showed increased values of crosslink density and of storage moduli in the biocomposites products compared to the neat bioresin. Thermogravimetric analysis (TGA) points out that the addition of hydrochar led to an improvement of the thermal stability of the biocomposites compared with the neat resorcinol diglycidyl ether (RDGE)-based resin (T5% = 337 °C) by ≈2–7 °C. Significantly, the biocomposites with 15–20 wt % hydrochar showed a higher stiffness value compared to neat epoxy resin, 92SD vs. 82SD, respectively.

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).


Author(s):  
Abbas Hassan Faris

In this work, appropriate alternative for diglycidyl ether bisphenol A (DGEBA) was found to avoid the destructive effects of bisphenol A. Lignin, an aromatic compound from palm tree leaves, was used as a renewable material to synthesize a bio-based epoxy resin. Lignin extracted using Kraft pulping process. Kraft Lignin was epoxidized with epichlorohydrin in alkaline medium. Nano-titanium dioxide was used as filler with ratio of 10% to prepare the green epoxy composite. The structure of the Kraft lignin and lignin-based epoxy resin was proven via Infrared spectra (FT-IR) were recorded using solid KBr disk by testing Shimadzu (FT-IR-8300) spectrophotometer. The thermal properties of the curing process of lignin-based epoxy resin and composite were investigate using Differential scanning calorimetry (DSC) analysis. Potentiodynamic measurements data revealed that the anti-corrosion performance of the lignin based epoxy resin. The study demonstrates successful of epoxidation of Kraft lignin. In addition, lignin based eopxy resin showed effective inhibitor for carbon steel in 3.5 wt. % NaCl electrolyte solutions


Polymers ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 542 ◽  
Author(s):  
David Santiago ◽  
Dailyn Guzmán ◽  
Francesc Ferrando ◽  
Àngels Serra ◽  
Silvia De la Flor

A series of bio-based epoxy shape-memory thermosetting polymers were synthesized starting from a triglycidyl phloroglucinol (3EPOPh) and trimethylolpropane triglycidyl ether (TPTE) as epoxy monomers and a polyetheramine (JEF) as crosslinking agent. The evolution of the curing process was studied by differential scanning calorimetry (DSC) and the materials obtained were characterized by means of DSC, thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), stress-strain tests, and microindentation. Shape-memory properties were evaluated under free and totally constrained conditions. All results were compared with an industrial epoxy thermoset prepared from standard diglycidyl ether of Bisphenol A (DGEBA). Results revealed that materials prepared from 3EPOPh were more reactive and showed a tighter network with higher crosslinking density and glass transition temperatures than the prepared from DGEBA. The partial substitution of 3EPOPh by TPTE as epoxy comonomer caused an increase in the molecular mobility of the materials but without worsening the thermal stability. The shape-memory polymers (SMPs) prepared from 3EPOPh showed good mechanical properties as well as an excellent shape-memory performance. They showed almost complete shape-recovery and shape-fixation, fast shape-recovery rates, and recovery stress up to 7 MPa. The results obtained in this study allow us to conclude that the triglycidyl phloroglucinol derivative of eugenol is a safe and environmentally friendly alternative to DGEBA for preparing thermosetting shape-memory polymers.


Materials ◽  
2020 ◽  
Vol 13 (22) ◽  
pp. 5184
Author(s):  
Mariusz Tryznowski ◽  
Zuzanna Żołek-Tryznowska

Poly(hydroxyurethane)s (PHU) are alternatives for conventional polyurethanes due to the use of bis-cyclic dicarbonates and diamines instead of harmful and toxic isocyanates. However, the surface properties of poly(hydroxyurethane)s are not well known. In this work, we focus on the analysis of the surface properties of poly(hydroxyurethane) coatings. Poly(hydroxyurethane)s were obtained by a catalyst-free method from commercially available carbonated diglycidyl ether of bisphenol A (Epidian 6 epoxy resins) and various diamines: ethylenediamine, trimethylenediamine, putrescine, hexamethylenediamine, 2,2,4(2,4,4)-trimethyl-1,6-hexanediamine, m-xylylenediamine, 1,8-diamino-3,6-dioxaoctane, 4,7,10-trioxa-1,13-tridecanediamine, and isophorone diamine, using a non-isocyanate route. The structures of the obtained polymers were confirmed by FT-IR, 1H NMR and 13C NMR spectroscopy, and thermogravimetric (TGA) and differential scanning calorimetry (DSC) analyses were performed. The rheological characteristic of the obtained polymers is presented. The static contact angles of water, diidomethane, and formamide, deposited on PHU coatings, were measured. From the measured contact angles, the surface free energy was calculated using two different approaches: Owens–Wendt and van Oss–Chaudhury–Good. Moreover, the wetting envelopes of PHU coatings were plotted, which enables the prediction of the wetting effect of various solvents. The results show that in the investigated coatings, a mainly dispersive interaction occurs.


Polymers ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 591 ◽  
Author(s):  
Mirjana Rodošek ◽  
Mohor Mihelčič ◽  
Marija Čolović ◽  
Ervin Šest ◽  
Matic Šobak ◽  
...  

Versatile product protective coatings that deliver faster drying times and shorter minimum overcoat intervals that enable curing at faster line speeds and though lower energy consumption are often desired by coating manufacturers. Product protective coatings, based on silsesquioxane-modified diglycidyl ether of bisphenol-A (DGEBA) epoxy resin, are prepared through a glycidyl ring-opening polymerization using dicyandiamide (DICY) as a curing agent. As silsesquioxane modifier serves the octaglycidyl-polyhedral oligomeric silsesquioxane (GlyPOSS). To decrease the operational temperature of the curing processes, three different accelerators for crosslinking are tested, i.e., N,N-benzyl dimethylamine, 2-methylimidazole, and commercial Curezol 2MZ-A. Differential scanning calorimetry, temperature-dependent FT-IR spectroscopy, and rheology allow differentiation among accelerators’ effectiveness according to their structure. The former only contributed to epoxy ring-opening, while the latter two, besides participate in crosslinking. The surface roughness of the protective coatings on aluminum alloy substrate decreases when the accelerators are applied. The scanning electron microscopy (SEM) confirms that coatings with accelerators are more homogeneous. The protective efficiency is tested with a potentiodynamic polarization technique in 0.5 M NaCl electrolyte. All coatings containing GlyPOSS, either without or with accelerators, reveal superior protective efficiency compared to neat DGEBA/DICY coating.


2017 ◽  
Vol 30 (7) ◽  
pp. 767-775 ◽  
Author(s):  
An-ran Wang ◽  
Abdul Qadeer Dayo ◽  
Dan Lv ◽  
Yi-le Xu ◽  
Jun Wang ◽  
...  

A series of amino-containing fluorene-based bisphthalonitrile (AFPN) monomers with alkyl or alkoxy groups were successfully produced by the reaction of 4-nitrophthalonitrile with 9, 9-bis (3-alkyl (or alkoxy)-4-aminophenyl)-2, 7-dihydroxylfluorene in the presence of potassium carbonate by a nucleophilic substitution reaction. The chemical structures of the synthesized monomers were confirmed by the Fourier transform infrared (FTIR), proton nuclear magnetic resonance, and carbon-13 nuclear magnetic resonance analyses. The synthesized monomers’ curing behaviors were evaluated by FTIR and differential scanning calorimetry, and a rheological analysis was performed to evaluate their respective processabilities. Moreover, dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) were performed for the thermomechanical, thermal, and thermo-oxidative analyses of the polymers. The results confirmed that the newly prepared phthalonitrile (PN) monomers with alkyl or alkoxy groups exhibited a self-promoted curing behavior. The rheological analysis suggested that the processing windows of the synthesized monomers were wider than that of APFN monomer bearing no flexible group. DMA and TGA revealed that the cured polymers exhibited high glass transition temperature (358–416°C) and the char yields at 800°C under nitrogen were between 70% and 77%. Moreover, the introduction of alkyl or alkoxy groups into the PN monomers’ backbones slightly reduced the thermal stability of the resulting polymers.


Materials ◽  
2020 ◽  
Vol 13 (13) ◽  
pp. 2901 ◽  
Author(s):  
Stefan Cichosz ◽  
Anna Masek

The following article debates on the properties of cellulose-filled ethylene-norbornene copolymer (EN) composites. Natural fibers employed in this study have been modified via two different approaches: solvent-involving (S) and newly developed non-solvent (NS). The second type of the treatment is fully eco-friendly and was carried out in the planetary mill without incorporation of any additional, waste-generating substances. Composite samples have been investigated with the use of spectroscopic methods (FT-IR), differential scanning calorimetry (DSC), static mechanical analysis, and surface-free energy measurements. It has been proved that the possible filler-polymer matrix interaction changes may occur due to the performed modifications. The highest reinforcement was evidenced for the composite sample filled with cellulose treated via a NS approach—TS = (34 ± 2) MPa, Eb = (380 ± 20)%. Additionally, a surface free energy polar part exhibited a significant increase for the same type of modification. Consequently, this could indicate easier wetting of the material which may contribute to the degradation process enhancement. Successfully developed cellulose-filled ethylene-norbornene copolymer composite compromises the rules of green chemistry and sustainable development by taking an advantage of renewable natural resources. This bio-inspired material may become an eco-friendly alternative for commonly used polymer blends.


2019 ◽  
Vol 3 (1) ◽  
pp. 6 ◽  
Author(s):  
Mohd Radzi Mohd Hafiezal ◽  
Abdan Khalina ◽  
Zainal Abidin Zurina ◽  
Md Deros Mohd Azaman ◽  
Zin Mohd Hanafee

This purpose of this paper was to reveal characteristics of a composite structure containing carbon fiber as a reinforcement and blended synthetic epoxy/bio-epoxy derived from crude jatropha oil as resin and compared with fully synthetic epoxy. The composite structure was prepared by the vacuum-assisted resin transfer molding technique and was left to cure for 24 h at room temperature. Both were characterized for their thermal, chemical, and flammable characteristics. The incorporation of jatropha bio-epoxy into the matrix significantly improved the thermal stability between 288–365 °C as obtained by thermogravimetric analysis (TGA) test. Dynamic mechanical analysis (DMA) curves showed slight diminution of performances and Tg from DMA tests confirmed well with the trend of Tg obtain by differential scanning calorimetry (DSC) curves. On the other hand, the flammability property was rated horizontal burning (HB) which was the same as the fully synthetic composite, but the duration to self-extinguish was halved for the composite with jatropha bio-epoxy. Fourier transform infrared attenuated total reflectance (FT-IR/ATR) was conducted to determine the difference of functional groups’ spectrum due to bonding type existing on both specimens. Overall, the composite specimen with blended bio-epoxy exhibited better thermal stability, comparable flammability characteristics, and performances. The aim of this paper was to introduce bio-based epoxy as a potential alternative epoxy and to compete with synthetic epoxy so as to minimize the footprint of non-renewable composite.


2013 ◽  
Vol 470 ◽  
pp. 53-57
Author(s):  
Xiao Yi Geng ◽  
Zhi You Hu ◽  
Fei Yang ◽  
Li Juan Zhang ◽  
Meng Qian Li ◽  
...  

Aqueous polyurethane(PU) polyols were synthesized from polyester polyol, toluene diisocyanate(TDI), dimethylolbutyric acid (DMBA) and diethanolamine(DEA). The structure of PU polyol and resulting polyurethane film were confirmed by the Fourier Transform Infrared Spectroscopy (FT-IR). The effects of NCO/OH and DMBA content on the particle size of PU polyol and resulting polyurethane films, which formed by the mixture of PU polyol and water-dispersible polyisocyanate, was investigated by dynamic light scattering analysis, dynamic mechanical analysis and measurement of the mechanical properties.The results show the increase in DMBA content or NCO:OH ratio may be used to decrease the particle size of aqueous polyurethane polyol, increase the Tg for two-component aqueous PU film and maybe adjust the mechanical properties of resulting film.


Materials ◽  
2018 ◽  
Vol 11 (11) ◽  
pp. 2330 ◽  
Author(s):  
Yufei Liu ◽  
Min He ◽  
Daohai Zhang ◽  
Qian Zhao ◽  
Yang Li ◽  
...  

P(N-phenylmaleimide-alt-styrene) (P(NPMI-alt-St)) and P(N-(4-carboxyphenyl)maleimide-alt-styrene) (P(CPMI-alt-St)) were designed and synthesized via free radical copolymerization. Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance spectroscopy (1H NMR and 13C NMR), gel permeation chromatography (GPC), and differential scanning calorimetry (DSC) were used to confirm the structure of P(NPMI-alt-St) and P(CPMI-alt-St). Next, the effect of P(CPMI-alt-St) on the heat deflection temperature (HDT) of nylon 6 was studied. In comparison to the PA6/P(NPMI-alt-St) blend, with the addition of 10 wt %, the HDT value of the PA6/P(CPMI-alt-St) blend increased by 15.7 °C, and the glass transition temperature (Tg) by Dynamic mechanical analysis (DMA) increased 2.3 °C. According to the analysis of DMA, dynamic viscosity, and the SEM of PA6 and its blends, P(CPMI-alt-St) promoted its compatibility with PA6, and promoted the storage modulus and dynamic viscosity of the blends. Thus, the introduction of 4-carboxyl can significantly improve the effect of P(CPMI-alt-St) on the heat resistance modification of nylon 6.


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