Search results for: bio-based monomers
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 133

Search results for: bio-based monomers

103 Effects of Auxetic Antibacterial Zwitterion Carboxylate and Sulfate Copolymer Hydrogels for Diabetic Wound Healing Application

Authors: Udayakumar Vee, Franck Quero

Abstract:

Zwitterionic polymers generally have been viewed as a new class of antimicrobial and non-fouling materials. They offer a broad versatility for chemical modification and hence great freedom for accurate molecular design, which bear an equimolar number of homogenously distributed anionic and cationic groups along their polymer chains. This study explores the effectiveness of the auxetic zwitterion carboxylate/sulfonate hydrogel in the diabetic-induced mouse model. A series of silver metal-doped auxetic zwitterion carboxylate/sulfonate/vinylaniline copolymer hydrogels is designed via a 3D printer. Zwitterion monomers have been characterized by FT-IR and NMR techniques. The effect of changing the monomers and different loading ratios of Ag over zwitterion on the final hydrogel materials' antimicrobial properties and biocompatibility will be investigated in detail. The synthesized auxetic hydrogel has been characterized using a wide range of techniques to help establish the relationship between molecular level and macroscopic properties of these materials, including mechanical and antibacterial and biocompatibility and wound healing ability. This work's comparative studies and results provide new insights and guide us in choosing a better auxetic structured material for a broad spectrum of wound healing applications in the animal model. We expect this approach to provide a versatile and robust platform for biomaterial design that could lead to promising treatments for wound healing applications.

Keywords: auxetic, zwitterion, carboxylate, sulfonate, polymer, wound healing

Procedia PDF Downloads 104
102 Antibacterial Zwitterion Carboxylate and Sulfonate Copolymer Auxetic Hydrogels for Diabetic Wound Healing Application

Authors: Udayakumar Veerabagu, Franck Quero

Abstract:

Zwitterion carboxylate and sulfonate polymers generally have been viewed as a new class of antimicrobial and non-fouling materials. They offer a broad versatility for chemical modification and hence great freedom for accurate molecular design, which bear an equimolar number of homogenously distributed anionic and cationic groups along their polymer chains. This study explores the effectiveness of the auxetic zwitterion carboxylate/sulfonate hydrogel in the diabetic-induced mouse model. A series of silver metal-doped auxetic zwitterion carboxylate/sulfonate/vinylaniline copolymer hydrogels is designed via a 3D printer. Zwitterion monomers have been characterized by FT-IR and NMR techniques. The effect of changing the monomers and different loading ratios of Ag over zwitterion on the final hydrogel materials' antimicrobial properties and biocompatibility will be investigated in detail. The synthesized auxetic hydrogel has been characterized using a wide range of techniques to help establish the relationship between molecular level and macroscopic properties of these materials, including mechanical and antibacterial and biocompatibility and wound healing ability. This work's comparative studies and results provide new insights and guide us in choosing a better auxetic structured material for a broad spectrum of wound healing applications in the animal model. We expect this approach to provide a versatile and robust platform for biomaterial design that could lead to promising treatments for wound healing applications.

Keywords: auxetic, zwitterion, carboxylate, sulfonate, polymer, wound healing

Procedia PDF Downloads 123
101 Correlation Volumic Shrinkage, Conversion Degree of Dental Composites

Authors: A. Amirouche, M. Mouzali, D. C. Watts

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During polymerization of dental composites, the volumic shrinkage is related to the conversion degree. The variation of the volumic shrinkage (S max according to the degree of conversion CD.), was examined for the experimental composites: (BisGMA/TEGDMA): (50/50), (75/25), (25/75) mixed with seven radiopac fillers: La2O3, BaO, BaSO4, SrO, ZrO2 , SrZrO3 and BaZrO 3 with different contents in weight, from 0 to 80%. We notice that whatever the filler and the composition in monomers, Smax increases with the increase in CD. This variation is, linear in particular in the case of the fillers containing only one heavy metal, and that whatever the composition in monomers. For a given salt, the increase of BisGMA composition leads to significant increase of S max more pronounced than the increase in CD. The variation of ratio (S max / CD.) with the increase of filler content is negligible. However the fillers containing two types of heavy metals have more effect on the volumic shrinkage than on the degree of conversion. Whatever the composition in monomer, and the content of filler containing only one heavy atom, S max increases with the increase in CD. Nevertheless, S max is affected by the viscosity of the medium compared with CD. For high percentages of mineral fillers (≥ 70% in weight), the diagrams S max according to CD are deviated of the linearity, owing to the fact that S max is affected by the high percentage of fillers compared with CD. The number of heavy atoms influences directly correlation (S max / CD.). In the case of the two mineral fillers: SrZrO3 and BaZrO3 ratio (S max / CD) moves away from the proportionality. The linearity of the diagrams Smax according to CD is less regular, due to the viscosity of high content of BisGMA. The study of Smax and DC of four commercial composites are presented and compared to elaborate experimental composites.

Keywords: Dental composites, degree of conversion, volumic shrinkage, photopolymerization

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100 Numerical Study of Homogeneous Nanodroplet Growth

Authors: S. B. Q. Tran

Abstract:

Drop condensation is the phenomenon that the tiny drops form when the oversaturated vapour present in the environment condenses on a substrate and makes the droplet growth. Recently, this subject has received much attention due to its applications in many fields such as thin film growth, heat transfer, recovery of atmospheric water and polymer templating. In literature, many papers investigated theoretically and experimentally in macro droplet growth with the size of millimeter scale of radius. However few papers about nanodroplet condensation are found in the literature especially theoretical work. In order to understand the droplet growth in nanoscale, we perform the numerical simulation work to study nanodroplet growth. We investigate and discuss the role of the droplet shape and monomer diffusion on drop growth and their effect on growth law. The effect of droplet shape is studied by doing parametric studies of contact angle and disjoining pressure magnitude. Besides, the effect of pinning and de-pinning behaviours is also studied. We investigate the axisymmetric homogeneous growth of 10–100 nm single water nanodroplet on a substrate surface. The main mechanism of droplet growth is attributed to the accumulation of laterally diffusing water monomers, formed by the absorption of water vapour in the environment onto the substrate. Under assumptions of quasi-steady thermodynamic equilibrium, the nanodroplet evolves according to the augmented Young–Laplace equation. Using continuum theory, we model the dynamics of nanodroplet growth including the coupled effects of disjoining pressure, contact angle and monomer diffusion with the assumption of constant flux of water monomers at the far field. The simulation result is validated by comparing with the published experimental result. For the case of nanodroplet growth with constant contact angle, our numerical results show that the initial droplet growth is transient by monomer diffusion. When the flux at the far field is small, at the beginning, the droplet grows by the diffusion of initially available water monomers on the substrate and after that by the flux at the far field. In the steady late growth rate of droplet radius and droplet height follow a power law of 1/3, which is unaffected by the substrate disjoining pressure and contact angle. However, it is found that the droplet grows faster in radial direction than high direction when disjoining pressure and contact angle increase. The simulation also shows the information of computational domain effect in the transient growth period. When the computational domain size is larger, the mass coming in the free substrate domain is higher. So the mass coming in the droplet is also higher. The droplet grows and reaches the steady state faster. For the case of pinning and de-pinning droplet growth, the simulation shows that the disjoining pressure does not affect the droplet radius growth law 1/3 in steady state. However the disjoining pressure modifies the growth rate of the droplet height, which then follows a power law of 1/4. We demonstrate how spatial depletion of monomers could lead to a growth arrest of the nanodroplet, as observed experimentally.

Keywords: augmented young-laplace equation, contact angle, disjoining pressure, nanodroplet growth

Procedia PDF Downloads 240
99 Carbon Aerogel Spheres from Resorcinol/Phenol and Formaldehyde for CO₂ Adsorption

Authors: Jessica Carolina Hernandez Galeano, Juan Carlos Moreno Pirajan, Liliana Giraldo

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Carbon gels are materials whose structure and porous texture can be designed and controlled on a nanoscale. Among their characteristics it is found their low density, large surface area and high degree of porosity. These materials are produced by a sol-gel polymerization of organic monomers using basic or acid catalysts, followed by drying and controlled carbonization. In this work, the synthesis and characterization of carbon aerogels from resorcinol, phenol and formaldehyde in ethanol is described. The aim of this study is obtaining different carbonaceous materials in the form of spheres using the Stöber method to perform a further evaluation of CO₂ adsorption of each material. In general, the synthesis consisted of a sol-gel polymerization process that generates a cluster (cross-linked organic monomers) from the precursors in the presence of NH₃ as a catalyst. This cluster was subjected to specific conditions of gelling and curing (30°C for 24 hours and 100°C for 24 hours, respectively) and CO₂ supercritical drying. Finally, the dry material was subjected to a process of carbonization or pyrolysis, in N₂ atmosphere at 350°C (1° C / min) for 2 h and 600°C (1°C / min) for 4 hours, to obtain porous solids that retain the structure initially desired. For this work, both the concentrations of the precursors and the proportion of ammonia in the medium where modify to describe the effect of the use of phenol and the amount of catalyst in the resulting material. Carbon aerogels were characterized by Scanning Electron Microscope (SEM), N₂ isotherms, infrared spectroscopy (IR) and X-ray Powder Diffraction (XRD) showing the obtention of carbon spheres in the nanometric scale with BET areas around 500 m2g-1.

Keywords: carbon aerogels, carbon spheres, CO₂ adsorption, Stöber method

Procedia PDF Downloads 108
98 Organic Co-Polymer Monolithic Columns for Liquid Chromatography Mixed Mode Protein Separations

Authors: Ahmed Alkarimi, Kevin Welham

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Organic mixed mode monolithic columns were fabricated from; glycidyl methacrylate-co-ethylene dimethacrylate-co-stearyl methacrylate, using glycidyl methacrylate and stearyl methacrylate as co monomers representing 30% and 70% respectively of the liquid volume with ethylene dimethacrylate crosslinker and 2,2-dimethoxy-2-phenylacetophenone as the free radical initiator. The monomers were mixed with a binary porogenic solvent, comprising propan-1-ol, and methanol (0.825 mL each). The monolith was formed by photo polymerization (365 nm) inside a borosilicate glass tube (1.5 mm ID and 3 mm OD x 50 mm length). The monolith was observed to have formed correctly by optical examination and generated reasonable backpressure, approximately 650 psi at a flow rate of 0.2 mL min⁻¹ 50:50 acetonitrile: water. The morphological properties of the monolithic columns were investigated using scanning electron microscopy images, and Brunauer-Emmett-Teller analysis, the results showed that the monolith was formed properly with 19.98 ± 0.01 mm² surface area, 0.0205 ± 0.01 cm³ g⁻¹ pore volume and 6.93 ± 0.01 nm average pore size. The polymer monolith formed was further investigated using proton nuclear magnetic resonance, and Fourier transform infrared spectroscopy. The monolithic columns were investigated using high-performance liquid chromatography to test their ability to separate different samples with a range of properties. The columns displayed both hydrophobic/hydrophilic and hydrophobic/ion exchange interactions with the compounds tested indicating that true mixed mode separations. The mixed mode monolithic columns exhibited significant separation of proteins.

Keywords: LC separation, proteins separation, monolithic column, mixed mode

Procedia PDF Downloads 134
97 Bio-Guided of Active New Alkaloids from Alstonia Brassi Toxicity Antitumour Activity in Silico and Molecular Modeling

Authors: Mesbah Khaled, Bouraoui Ouissal, Benkiniouar Rachid, Belkhiri Lotfi

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Alstonia, which are tropical plants with a wide geographical distribution, have been divided into different sections by different authors based on previous studies of several species within the genus. Monachino divides Alstonia into 5 sections, while Pichon divides it into 3 sections. Several plants belonging to this genus, such as Alstonia brassii, have been used in traditional folk medicine to treat ailments such as fever, malaria and dysentery]. Previous studies focusing on the chemical composition of these plants have successfully identified indol alkaloids with cytotoxic, anti-diabetic and anti-inflammatory properties. The newly discovered monomers are structurally similar to the backbones of picralin, affinisin and macrolin. On the other hand, all recently isolated dimeric compounds have a macrolin moiety. In this study, a computational analysis was performed on a series of novel molecules, including both monomeric and dimeric compounds with different structural frameworks. This investigation represents the first computational study of these molecules using an in silico approach incorporating 2D-QSAR data. The analysis involved various computational techniques, including 2D-QSAR modelling, molecular docking studies and subsequent validation by molecular dynamics simulation and assessment of ADMET properties. The chemical composition was identified by 1D and 2D NMR. Eight new alkaloids were isolated, 5 monomers and 3 dimers. In this section, we focus on the biological activity of 4 new alkaloids belonging to two different skeletons, the affinisine skeleton.

Keywords: affinisine, talcarpine, macroline, cytotoxicity, alkaloids

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96 Biobased Sustainable Films from the Algerian Opuntia Ficus-Indica Cladodes Powder: Effect of Plasticizer Content

Authors: Nadia Chougui, Nawal Makhloufi, Farouk Rezgui, Elias Benramdane, Carmen S. R. Freire, Carla Vilela, Armando J. D. Silvestre

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Native to Mexico, Opuntia ficus-indica was introduced in southern Spain, and thereafter, it was spread throughout the Mediterranean Basin by the Spanish conquerors in the 16th and 17th centuries. O. ficus-indica is a tropical and subtropical plant able to grow in arid and semi-arid regions, such as the Mediterranean and Central America regions. The culture of Opuntia covers about 200,000 ha in North Africa. This tree is used against soil erosion and desertification for fruit production and is encouraged to promote the livestock sector. It has recently received ever-increasing attention from researchers worldwide for the multivalent pharmaceutical and cosmetical potential of its different compartments (fruits, seeds, cladodes). The present study investigated the elaboration by casting method and characterization of new biodegradable films composed of cladodes powder (CP) of the plant raw material mentioned above, and a marine seaweed derivative, namely agar (A). The effect of glycerol concentration on the properties of the films was evaluated at four different contents (30, 40, 50 and 60 wt.%). The films present UV-blocking properties, thermal stability as well as moderate mechanical performance and water vapor transmission rate (WVTR). The results point to an increase in thickness, elongation at break, moisture content, water solubility, and WVTR with increasing glycerol content. On the contrary, Young’s modulus, tensile strength and contact angle decreased as glycerol concentration increased. The best combination is obtained for the film with 30% glycerol, based on an intermediate compromise between physical, mechanical, thermal and barrier properties. All these outcomes express the potentiality of the powder obtained from grinding the OFI cladodes as raw material to produce low-cost films for the development of sustainable packaging materials.

Keywords: Opuntia ficus-indica cladodes powder, agar, biobased films, effect of plasticizer, sustainable packaging

Procedia PDF Downloads 39
95 Liquid Tin(II) Alkoxide Initiators for Use in the Ring-Opening Polymerisation of Cyclic Ester Monomers

Authors: Sujitra Ruengdechawiwat, Robert Molloy, Jintana Siripitayananon, Runglawan Somsunan, Paul D. Topham, Brian J. Tighe

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The main aim of this research has been to design and synthesize some completely soluble liquid tin(II) alkoxide initiators for use in the ring-opening polymerisation (ROP) of cyclic ester monomers. This is in contrast to conventional tin(II) alkoxides in solid form which tend to be molecular aggregates and difficult to dissolve. The liquid initiators prepared were bis(tin(II) monooctoate) diethylene glycol ([Sn(Oct)]2DEG) and bis(tin(II) monooctoate) ethylene glycol ([Sn(Oct)]2EG). Their efficiencies as initiators in the bulk ROP of ε-caprolactone (CL) at 130oC were studied kinetically by dilatometry. Kinetic data over the 20-70% conversion range was used to construct both first-order and zero-order rate plots. It was found that the rate data fitted more closely to first-order kinetics with respect to the monomer concentration and gave higher first-order rate constants than the corresponding tin(II) octoate/diol initiating systems normally used to generate the tin(II) alkoxide in situ. Since the ultimate objective of this work is to produce copolymers suitable for biomedical use as absorbable monofilament surgical sutures, poly(L-lactide-co-ε-caprolactone) 75:25 mol %, P(LL-co-CL), copolymers were synthesized using both solid and liquid tin(II) alkoxide initiators at 130°C for 48 hrs. The statistical copolymers were obtained in near-quantitative yields with compositions (from 1H-NMR) close to the initial comonomer feed ratios. The monomer sequencing (from 13C-NMR) was partly random and partly blocky (gradient-type) due to the much differing monomer reactivity ratios (rLL >> rCL). From GPC, the copolymers obtained using the soluble liquid tin(II) alkoxides were found to have higher molecular weights (Mn = 40,000-100,000) than those from the only partially soluble solid initiators (Mn = 30,000-52,000).

Keywords: biodegradable polyesters, poly(L-lactide-co-ε-caprolactone), ring-opening polymerisation, tin(II) alkoxide

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94 Chromatographic Preparation and Performance on Zinc Ion Imprinted Monolithic Column and Its Adsorption Property

Authors: X. Han, S. Duan, C. Liu, C. Zhou, W. Zhu, L. Kong

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The ionic imprinting technique refers to the three-dimensional rigid structure with the fixed pore sizes, which was formed by the binding interactions of ions and functional monomers and used ions as the template, it has a high level of recognition to the ionic template. The preparation of monolithic column by the in-situ polymerization need to put the compound of template, functional monomers, cross-linking agent and initiating agent into the solution, dissolve it and inject to the column tube, and then the compound will have a polymerization reaction at a certain temperature, after the synthetic reaction, we washed out the unread template and solution. The monolithic columns are easy to prepare, low consumption and cost-effective with fast mass transfer, besides, they have many chemical functions. But the monolithic columns have some problems in the practical application, such as low-efficiency, quantitative analysis cannot be performed accurately because of the peak shape is wide and has tailing phenomena; the choice of polymerization systems is limited and the lack of theoretical foundations. Thus the optimization of components and preparation methods is an important research direction. During the preparation of ionic imprinted monolithic columns, pore-forming agent can make the polymer generate the porous structure, which can influence the physical properties of polymer, what’ s more, it can directly decide the stability and selectivity of polymerization reaction. The compounds generated in the pre-polymerization reaction could directly decide the identification and screening capabilities of imprinted polymer; thus the choice of pore-forming agent is quite critical in the preparation of imprinted monolithic columns. This article mainly focuses on the research that when using different pore-forming agents, the impact of zinc ion imprinted monolithic column on the enrichment performance of zinc ion.

Keywords: high performance liquid chromatography (HPLC), ionic imprinting, monolithic column, pore-forming agent

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93 Distribution of Antioxidants between Sour Cherry Juice and Pomace

Authors: Sonja Djilas, Gordana Ćetković, Jasna Čanadanović-Brunet, Vesna Tumbas Šaponjac, Slađana Stajčić, Jelena Vulić, Milica Vinčić

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In recent years, interest in food rich in bioactive compounds, such as polyphenols, increased the advantages of the functional food products. Bioactive components help to maintain health and prevention of diseases such as cancer, cardiovascular and many other degenerative diseases. Recent research has shown that the fruit pomace, a byproduct generated from the production of juice, can be a potential source of valuable bioactive compounds. The use of fruit industrial waste in the processing of functional foods represents an important new step for the food industry. Sour cherries have considerable nutritional, medicinal, dietetic and technological value. According to the production volume of cherries, Serbia ranks seventh in the world, with a share of 7% of the total production. The use of sour cherry pomace has so far been limited to animal feed, even though it can be potentially a good source of polyphenols. For this study, local variety of sour cherry cv. ‘Feketićka’ was chosen for its more intensive taste and deeper red color, indicating high anthocyanin content. The contents of total polyphenols, flavonoids and anthocyanins, as well as radical scavenging activity on DPPH radicals and reducing power of sour cherry juice and pomace were compared using spectrophotometrical assays. According to the results obtained, 66.91% of total polyphenols, 46.77% of flavonoids, 46.77% of total anthocyanins and 47.88% of anthocyanin monomers from sour cherry fruits have been transferred to juice. On the other hand, 29.85% of total polyphenols, 33.09% of flavonoids, 53.23% of total anthocyanins and 52.12% of anthocyanin monomers remained in pomace. Regarding radical scavenging activity, 65.51% of Trolox equivalents from sour cherries were exported to juice, while 34.49% was left in pomace. However, reducing power of sour cherry juice was much stronger than pomace (91.28% and 8.72% of Trolox equivalents from sour cherry fruits, respectively). Based on our results it can be concluded that sour cherry pomace is still a rich source of natural antioxidants, especially anthocyanins with coloring capacity, therefore it can be used for dietary supplements development and food fortification.

Keywords: antioxidants, polyphenols, pomace, sour cherry

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92 Effect of Primer on Bonding between Resin Cement and Zirconia Ceramic

Authors: Deog-Gyu Seo, Jin-Soo Ahn

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Objectives: Recently, the development of adhesive primers on stable bonding between zirconia and resin cement has been on the increase. The bond strength of zirconia-resin cement can be effectively increased with the treatment of primer composed of the adhesive monomer that can chemically bond with the oxide layer, which forms on the surface of zirconia. 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP) that contains phosphate ester and acidic monomer 4-methacryloxyethyl trimellitic anhydride(4-META) have been suggested as monomers that can form chemical bond with the surface oxide layer of zirconia. Also, these suggested monomers have proved to be effective zirconia surface treatment for bonding to resin cement. The purpose of this study is to evaluate the effects of primer treatment on the bond strength of Zirconia-resin cement by using three different kinds of primers on the market. Methods: Zirconia blocks were prepared into 60 disk-shaped specimens by using a diamond saw. Specimens were divided into four different groups: first three groups were treated with zirconiaLiner(Sun Medical Co., Ltd., Furutaka-cho, Moriyama, Shiga, Japan), Alloy primer (Kuraray Noritake Dental Inc., Sakaju, Kurashiki, Okayama, Japan), and Universal primer (Tokuyama dental Corp., Taitou, Taitou-ku, Tokyo, Japan) respectively. The last group was the control with no surface treatment. Dual cured resin cement (Biscem, Bisco Inc., Schaumburg, IL, USA) was luted to each group of specimens. And then, shear bond strengths were measured by universal tesing machine. The significance of the result was statistically analyzed by one-way ANOVA and Tukey test. The failure sites in each group were inspected under a magnifier. Results: Mean shear bond strength were 0.60, 1.39, 1.03, 1.38 MPa for control, Zirconia Liner (ZL), Alloy primer (AP), Universal primer (UP), respectively. Groups with application of each of the three primers showed significantly higher shear bond strength compared to the control group (p < 0.05). Among the three groups with the treatment, ZL and UP showed significantly higher shear bond strength than AP (p < 0.05), and there were no significant differences in mean shear bond strength between ZL and UP (p < 0.05). While the most specimens of control groups showed adhesive failure (80%), the most specimens of three primer-treated groups showed cohesive or mixed failure (80%).

Keywords: primer, resin cement, shear bond strength, zirconia

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91 Crosslinking of Unsaturated Elastomers in Presence of Aromatic Chlorine-Containing Compounds

Authors: Shiraz M. Mammadov, Elvin M. Aliyev, Adil A. Garibov

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The role of the disulfochloride benzene in unsaturated rubbers (SKIN, SKN-26) which is in the systems of SKIN+disulfochloride benzene and SKN-26+disulfochloride benzene was studied by the radiation exposure. By the usage of physical, chemical and spectral methods the changes in the molecular structure of the rubber were shown after irradiation by y-rays at 300 kGy. The outputs and the emergence of the crosslinking in the elastomers for each system depending on absorbed dose were defined. It is suggested that the mechanism of radiation occurs by the heterogeneous transformation of elastomers in the presence of disulfochloride benzene.

Keywords: acrylonitrile-butadiene rubber, crosslinking, polyfunctional monomers, radiation, sensitizier, vulcanization

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90 Eco-Friendly Natural Filler Based Epoxy Composites

Authors: Suheyla Kocaman, Gulnare Ahmetli

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In this study, acrylated soybean oil (AESO) was used as modifying agent for DGEBF-type epoxy resin (ER). AESO was used as a co-matrix in 50 wt % with ER. Composites with eco-friendly natural fillers-banana bark and seashell were prepared. MNA was used as a hardener. Effect of banana peel (BP) and seashell (SSh) fillers on mechanical properties, such as tensile strength, elongation at break, and hardness of M-ERs were investigated. The structure epoxy resins (M-ERs) cured with MNA and sebacic acid (SAc) hardeners were characterized by Fourier transform infrared spectroscopy (FTIR). Tensile test results show that Young’s (elastic) modulus, tensile strength and hardness of SSh particles reinforced with M-ERs were higher than the M-ERs reinforced with banana bark.

Keywords: biobased composite, epoxy resin, mechanical properties, natural fillers

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89 Synthesis and Charaterization of Nanocomposite Poly (4,4' Methylenedianiline) Catalyzed by Maghnite-H+

Authors: A. Belmokhtar, A. Yahiaoui, A. Benyoucef, M. Belbachir

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We reported the synthesis and characterization of nanocomposite poly (4,4’ methylenedianiline) via chemical polymerization of monomers 4,4’ methylenedianiline by ammonium persulfate (APS) at room temperature catalyzed by Maghnite-H+. A facile method was demonstrated to grow poly (4,4’ methylenedianiline) nanocomposite, which was carried out by mixing Ammonium Persulfate (APS) aqueous and 4,4’ methylenedianiline solution in the presence of Maghnite-H+ at room temperature The effect of amount of catalyst and time on the polymerization yield of the polymers was studied. Structure was confirmed by elemental analysis, UV vis, RMN-1H, and voltammetry cyclique.

Keywords: charaterization, maghnite-h+, polymerization, poly (4, 4’ methylenedianiline)

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88 Comparison of Non-destructive Devices to Quantify the Moisture Content of Bio-Based Insulation Materials on Construction Sites

Authors: Léa Caban, Lucile Soudani, Julien Berger, Armelle Nouviaire, Emilio Bastidas-Arteaga

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Improvement of the thermal performance of buildings is a high concern for the construction industry. With the increase in environmental issues, new types of construction materials are being developed. These include bio-based insulation materials. They capture carbon dioxide, can be produced locally, and have good thermal performance. However, their behavior with respect to moisture transfer is still facing some issues. With a high porosity, the mass transfer is more important in those materials than in mineral insulation ones. Therefore, they can be more sensitive to moisture disorders such as mold growth, condensation risks or decrease of the wall energy efficiency. For this reason, the initial moisture content on the construction site is a piece of crucial knowledge. Measuring moisture content in a laboratory is a mastered task. Diverse methods exist but the easiest and the reference one is gravimetric. A material is weighed dry and wet, and its moisture content is mathematically deduced. Non-destructive methods (NDT) are promising tools to determine in an easy and fast way the moisture content in a laboratory or on construction sites. However, the quality and reliability of the measures are influenced by several factors. Classical NDT portable devices usable on-site measure the capacity or the resistivity of materials. Water’s electrical properties are very different from those of construction materials, which is why the water content can be deduced from these measurements. However, most moisture meters are made to measure wooden materials, and some of them can be adapted for construction materials with calibration curves. Anyway, these devices are almost never calibrated for insulation materials. The main objective of this study is to determine the reliability of moisture meters in the measurement of biobased insulation materials. The determination of which one of the capacitive or resistive methods is the most accurate and which device gives the best result is made. Several biobased insulation materials are tested. Recycled cotton, two types of wood fibers of different densities (53 and 158 kg/m3) and a mix of linen, cotton, and hemp. It seems important to assess the behavior of a mineral material, so glass wool is also measured. An experimental campaign is performed in a laboratory. A gravimetric measurement of the materials is carried out for every level of moisture content. These levels are set using a climatic chamber and by setting the relative humidity level for a constant temperature. The mass-based moisture contents measured are considered as references values, and the results given by moisture meters are compared to them. A complete analysis of the uncertainty measurement is also done. These results are used to analyze the reliability of moisture meters depending on the materials and their water content. This makes it possible to determine whether the moisture meters are reliable, and which one is the most accurate. It will then be used for future measurements on construction sites to assess the initial hygrothermal state of insulation materials, on both new-build and renovation projects.

Keywords: capacitance method, electrical resistance method, insulation materials, moisture transfer, non-destructive testing

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87 Effect of Catalyst on Castor Oil Based Polyurethane with Different Hard/Soft Segment Ratio

Authors: Swarnalata Sahoo, Smita Mohanty, S. K. Nayak

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Environmentally friendly Polyurethane(PU) synthesis from Castor oil(CO) has been studied extensively. Probably due to high proportion of fatty hydroxy acids and unsaturated bond, CO showed better performance than other oil, can be easily utilized as commercial applications. In this work, cured PU polymers having different –NCO/OH ratio with and without catalyst were synthesized by using partially biobased Isocyanate with castor oil (CO). Curing time has been studied by observing at the time of reaction, which can be confirmed by AT-FTIR. DSC has been studied to monitor the reaction between CO & Isocyanates using non Isothermal process. Curing kinetics have also been studied to investigate the catalytic effect of the NCO / OH ratio of Polyurethane. Adhesion properties were evaluated from Lapshear test. Tg of the PU polymer was evaluated by DSC which can be compared by DMA. Surface Properties were studied by contact angle measurement. Improvement of the interfacial adhesion between the nonpolar surface of Aluminum substrate and the polar adhesive has been studied by modifying surface.

Keywords: polyurethane, partially bio-based isocyanate, castor oil, catalyst

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86 Comparative Dielectric Properties of 1,2-Dichloroethane with n-Methylformamide and n,n-Dimethylformamide Using Time Domain Reflectometry Technique in Microwave Frequency

Authors: Shagufta Tabassum, V. P. Pawar, jr., G. N. Shinde

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The study of dielectric relaxation properties of polar liquids in the binary mixture has been carried out at 10, 15, 20 and 25 ºC temperatures for 11 different concentrations using time domain reflectometry technique. The dielectric properties of a solute-solvent mixture of polar liquids in the frequency range of 10 MHz to 30 GHz gives the information regarding formation of monomers and multimers and also an interaction between the molecules of the liquid mixture under study. The dielectric parameters have been obtained by the least squares fit method using the Debye equation characterized by a single relaxation time without relaxation time distribution.

Keywords: excess properties, relaxation time, static dielectric constant, and time domain reflectometry technique

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85 Bis-Azlactone Based Biodegradable Poly(Ester Amide)s: Design, Synthesis and Study

Authors: Kobauri Sophio, Kantaria Tengiz, Tugushi David, Puiggali Jordi, Katsarava Ramaz

Abstract:

Biodegradable biomaterials (BB) are of high interest for numerous applications in modern medicine as resorbable surgical materials and drug delivery systems. This kind of materials can be cleared from the body after the fulfillment of their function that excludes a surgical intervention for their removal. One of the most promising BBare amino acids based biodegradable poly(ester amide)s (PEAs) which are composed of naturally occurring (α-amino acids) and non-toxic building blocks such as fatty diols and dicarboxylic acids. Key bis-nucleophilic monomers for synthesizing the PEAs are diamine-diesters-di-p-toluenesulfonic acid salts of bis-(α-amino acid)-alkylenediesters (TAADs) which form the PEAs after step-growth polymerization (polycondensation) with bis-electrophilic counter-partners - activated diesters of dicarboxylic acids. The PEAs combine all advantages of the 'parent polymers' – polyesters (PEs) and polyamides (PAs): Ability of biodegradation (PEs), a high affinity with tissues and a wide range of desired mechanical properties (PAs). The scopes of applications of thePEAs can substantially be expanded by their functionalization, e.g. through the incorporation of hydrophobic fragments into the polymeric backbones. Hydrophobically modified PEAs can form non-covalent adducts with various compounds that make them attractive as drug carriers. For hydrophobic modification of the PEAs, we selected so-called 'Azlactone Method' based on the application of p-phenylene-bis-oxazolinons (bis-azlactones, BALs) as active bis-electrophilic monomers in step-growth polymerization with TAADs. Interaction of BALs with TAADs resulted in the PEAs with low MWs (Mw2,800-19,600 Da) and poor material properties. The high-molecular-weight PEAs (Mw up to 100,000) with desirable material properties were synthesized after replacement of a part of BALs with activated diester - di-p-nitrophenylsebacate, or a part of TAAD with alkylenediamine – 1,6-hexamethylenediamine. The new hydrophobically modified PEAs were characterized by FTIR, NMR, GPC, and DSC. It was shown that after the hydrophobic modification the PEAs retain the biodegradability (in vitro study catalyzed by α-chymptrypsin and lipase), and are of interest for constructing resorbable surgical and pharmaceutical devices including drug delivering containers such as microspheres. The new PEAs are insoluble in hydrophobic organic solvents such as chloroform or dichloromethane (swell only) that allowed elaborating a new technology of fabricating microspheres.

Keywords: amino acids, biodegradable polymers, bis-azlactones, microspheres

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84 Molecularly Imprinted Polymer and Computational Study of (E)-2-Cyano-3-(Dimethylamino)-N-(2,4-Dioxo-1,2,3,4-Tetrahydropyrimidin-5-Yl)Acrylam-Ide and Its Applications in Industrial Applications

Authors: Asmaa M. Fahim

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In this investigation, the (E)-2-cyano-3-(dimethylamino)-N-(2,4-dioxo-1,2,3,4-tetrahydropyrimidin-5-yl)acrylam-ide (4) which used TAM as a template which interacts with Methacrylic Acid (MAA) monomer, in the presence of CH₃CN as progen. The TAM-MMA complex interactions are dependent on stable hydrogen bonding interaction between the carboxylic acid group of TAM(Template) and the hydroxyl group of MMA(methyl methacrylate) with minimal interference of porogen CH₃CN. The physical computational studies were used to optimize their structures and frequency calculations. The binding energies between TAM with different monomers showed the most stable molar ratio of 1:4, which was confirmed through experimental analysis. The optimized polymers were investigated in industrial applications.

Keywords: molecular imprinted polymer, computational studies, SEM, spectral analysis, industrial applications

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83 In situ Polymerization and Properties of Biobased Polyurethane/Epoxy Interpenetrating Network Nanocomposites

Authors: Aiswarea Mathew, Smita Mohanty, Jr., S. K. Nayak

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Polyurethane networks based on castor oil (CO) as a renewable resource polyol were synthesized. Polyurethane/epoxy resin interpenetrating network nanocomposites containing modified montmorillonite organoclay (C30B-PU/EP nanocomposites) were prepared by an in situ intercalation method. The conventional spectroscopic characterization of the synthesized samples using FT-IR confirms the existence of the proposed castor oil based PU structure and also showed that strong interactions existed between C30B and EP/PU matrix. The dispersion degree of C30B in EP/PU matrix was characterized by X-Ray diffraction (XRD) method. Scanning electronic microscopy analysis showed that the interpenetrating process of PU and EP increases the exfoliation degree of C30B, and it improves the compatibility and the phase structure of polyurethane/epoxy resin interpenetrating polymer networks (PU/EP IPNs). The thermal stability improves compared to the polyurethane when the PU/EP IPN is formed. Mechanical properties including the Young’s modulus and tensile strength reflected marked improvement with addition of C30B.

Keywords: castor oil, epoxy, montmorillonite, polyurethane

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82 Synthesis and Characterization of New Polyesters Based on Diarylidene-1-Methyl-4-Piperidone

Authors: Tareg M. Elsunaki, Suleiman A. Arafa, Mohamed A. Abd-Alla

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New interesting thermal stable polyesters containing 1-methyl-4-piperidone moiety in the main chain have been synthesized. These polyesters were synthesized by interfacial polycondensation technique of 3,5-bis(4-hydroxybenzylidene)-1-methyl-4-piperidone (I) and 3,5-bis(4-hydroxy-3-methoxy benzyli-dene)-1-methyl-4-piperidone (II) with terphthaloyl, isophthaloyl, 4,4'-diphenic, adipoyl and sebacoyl dichlorides. The yield and the values of the reduced viscosity of the produced polyesters were found to be affected by the type of an organic phase. In order to characterize these polymers, the necessary model compounds (A), (B) were prepared from (I), (II) respectively and benzoyl chloride. The structure of monomers (I), (II), model compounds and resulting polyesters were confirmed by IR, elemental analysis and 1HNMR spectroscopy. The various characteristic of the resulting polymers including solubility, thermal properties, viscosity and X-ray analysis were also studied.

Keywords: synthesis, characterization, new polyesters, chemistry

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81 Poly(propylene fumarate) Copolymers with Phosphonic Acid-based Monomers Designed as Bone Tissue Engineering Scaffolds

Authors: Görkem Cemali̇, Avram Aruh, Gamze Torun Köse, Erde Can ŞAfak

Abstract:

In order to heal bone disorders, the conventional methods which involve the use of autologous and allogenous bone grafts or permanent implants have certain disadvantages such as limited supply, disease transmission, or adverse immune response. A biodegradable material that acts as structural support to the damaged bone area and serves as a scaffold that enhances bone regeneration and guides bone formation is one desirable solution. Poly(propylene fumarate) (PPF) which is an unsaturated polyester that can be copolymerized with appropriate vinyl monomers to give biodegradable network structures, is a promising candidate polymer to prepare bone tissue engineering scaffolds. In this study, hydroxyl-terminated PPF was synthesized and thermally cured with vinyl phosphonic acid (VPA) and diethyl vinyl phosphonate (VPES) in the presence of radical initiator benzoyl peroxide (BP), with changing co-monomer weight ratios (10-40wt%). In addition, the synthesized PPF was cured with VPES comonomer at body temperature (37oC) in the presence of BP initiator, N, N-Dimethyl para-toluidine catalyst and varying amounts of Beta-tricalcium phosphate (0-20 wt% ß-TCP) as filler via radical polymerization to prepare composite materials that can be used in injectable forms. Thermomechanical properties, compressive properties, hydrophilicity and biodegradability of the PPF/VPA and PPF/VPES copolymers were determined and analyzed with respect to the copolymer composition. Biocompatibility of the resulting polymers and their composites was determined by the MTS assay and osteoblast activity was explored with von kossa, alkaline phosphatase and osteocalcin activity analysis and the effects of VPA and VPES comonomer composition on these properties were investigated. Thermally cured PPF/VPA and PPF/VPES copolymers with different compositions exhibited compressive modulus and strength values in the wide range of 10–836 MPa and 14–119 MPa, respectively. MTS assay studies showed that the majority of the tested compositions were biocompatible and the overall results indicated that PPF/VPA and PPF/VPES network polymers show significant potential for applications as bone tissue engineering scaffolds where varying PPF and co-monomer ratio provides adjustable and controllable properties of the end product. The body temperature cured PPF/VPES/ß-TCP composites exhibited significantly lower compressive modulus and strength values than the thermal cured PPF/VPES copolymers and were therefore found to be useful as scaffolds for cartilage tissue engineering applications.

Keywords: biodegradable, bone tissue, copolymer, poly(propylene fumarate), scaffold

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80 Structural Properties of Polar Liquids in Binary Mixture Using Microwave Technique

Authors: Shagufta Tabassum, V. P. Pawar

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The study of static dielectric properties in a binary mixture of 1,2 dichloroethane (DE) and n,n dimethylformamide (DMF) polar liquids has been carried out in the frequency range of 10 MHz to 30 GHz for 11 different concentration using time domain reflectometry technique at 10ºC temperature. The dielectric relaxation study of solute-solvent mixture at microwave frequencies gives information regarding the creation of monomers and multimers as well as interaction between the molecules of the binary mixture. The least squares fit method is used to determine the values of dielectric parameters such as static dielectric constant (ε0), dielectric constant at high frequency (ε) and relaxation time (τ).

Keywords: shagufta shaikhexcess parameters, relaxation time, static dielectric constant, time domain reflectometry

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79 The Potential Use of Flavin Mononucleotide for Photoluminescent and Bioluminescent Textile

Authors: Sweta Iyer, Nemeshwaree Behary, Jinping Guan, Guoqiang Chen, Vincent Nierstrasz

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Flavin mononucleotide widely known as 'FMN' is a biobased resource derived from riboflavin. The isoalloxazine ring present in the FMN molecule attributes the photoluminescence phenomenon, whereas FMN molecule in the presence of bacterial luciferase enzyme and co-factors such as NADH, long chain aldehyde leads to bioluminescence reaction. In this study, the FMN molecule was treated on cellulosic textile using chromojet technique and the photoluminescence property was characterized using spectroscopy technique. Further, the FMN was used as a substrate along with enzymes and co-factors to treat the non-woven textile, and the bioluminescence property was explored using luminometer equipment. The investigation revealed photoluminescence property on cellulosic textile, and the emission peak was observed at a wavelength around 530 nm with an average corrected spectral intensity of 10×106 CPS/Microamps. In addition, the measurement of nonwoven textile using bioluminescence reaction system exhibited light intensity measured in the form of relative light units (RLU). The study enabled to explore the use of FMN as both photoluminescent and bioluminescent textile. Further investigation would require for stability study of the same to provide an eco-efficient approach to obtain luminescent textile.

Keywords: flavin mononucleotide, photoluminescence, bioluminescence, luminescent textile

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78 Biomimetic Luminescent Textile Using Biobased Products

Authors: Sweta Iyer, Nemeshwaree Behary, Vincent Nierstrasz

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Various organisms involve bioluminescence for their particular biological function. The bio-based molecules responsible for bioluminescence vary from one species to another, research has been done to identify the chemistry and different mechanisms involved in light production in living organisms. The light emitting chemical systems such as firefly and bacterial luminous mostly involves enzyme-catalyzed reactions and is widely used for ATP measurement, bioluminescence imaging, environmental biosensors etc. Our strategy is to design bioluminescent textiles using such bioluminescent systems. Hence, a detailed literature work was carried out to study on how to mimic bioluminescence effect seen in nature. Reaction mechanisms in various bioluminescent living organisms were studied and the components or molecules responsible for luminescence were identified. However, the challenge is to obtain the same effect on textiles by immobilizing enzymes responsible for light creation. Another challenge is also to regenerate substrates involved in the reaction system to create a longer lasting illumination in bioluminescent textiles. Natural film-forming polymers were used to immobilize the reactive components including enzymes on textile materials to design a biomimetic luminescent textile.

Keywords: bioluminescence, biomimetic, immobilize, luminescent textile

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77 Synthesis and Characterization of Renewable Resource Based Green Epoxy Coating

Authors: Sukanya Pradhan, Smita Mohanty, S. K Nayak

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Plant oils are a great renewable source for being a reliable starting material to access new products with a wide spectrum of structural and functional variations. Even though petroleum products might also render the same, but it would also impose a high risk factor of environmental and health hazard. Since epoxidized vegetable oils are easily available, eco-compatible, non-toxic and renewable, hence these have drawn much of the attentions in the polymer industrial sector especially for the development of eco-friendly coating materials. In this study a waterborne epoxy coating was prepared from epoxidized soyabean oil by using triethanolamine. Because of its hydrophobic nature, it was a tough and tedius task to make it hydrophilic. The hydrophobic biobased epoxy was modified into waterborne epoxy by the help of a plant based anhydride as curing agent. Physico-mechanical, chemical resistance tests and thermal analysis of the green coating material were carried out which showed good physic-mechanical, chemical resistance properties as well as environment friendly. The complete characterization of the final material was done in terms of scratch hardness, gloss test, impact resistance, adhesion and bend test.

Keywords: epoxidized soybean oil, waterborne, curing agent, green coating

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76 Preparation of Polylactide Nanoparticles by Supercritical Fluid Technology

Authors: Jakub Zágora, Daniela Plachá, Karla Čech Barabaszová, Sylva Holešová, Roman Gábor, Alexandra Muñoz Bonilla, Marta Fernández García

Abstract:

The development of new antimicrobial materials that are not toxic to higher living organisms is a major challenge today. Newly developed materials can have high application potential in biomedicine, coatings, packaging, etc. A combination of commonly used biopolymer polylactide with cationic polymers seems to be very successful in the fight against antimicrobial resistance [1].PLA will play a key role in fulfilling the intention set out in the New Deal announced by the EU commission, as it is a bioplastic that is easily degradable, recyclable, and mass-produced. Also, the development of 3D printing in the context of this initiative, and the actual use of PLA as one of the main materials used for this printing, make the technology around the preparation and modification of PLA quite logical. Moreover, theenvironmentally friendly and energy saving technology like supercritical fluid process (SFP) will be used for their preparation. In a first approach, polylactide nano- and microparticles and structures were prepared by supercritical fluid extraction. The RESS (rapid expansion supercritical fluid solution) method is easier to optimize and shows better particle size control. On the contrary, a highly porous structure was obtained using the SAS (supercritical antisolvent) method. In a second part, the antimicrobial biobased polymer was introduced by SFP.

Keywords: polylactide, antimicrobial polymers, supercritical fluid technology, micronization

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75 Chemical Functionalization of Graphene Oxide for Improving Mechanical and Thermal Properties of Polyurethane Composites

Authors: Qifei Jing, Vadim V. Silberschmidt, Lin Li, ZhiLi Dong

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Graphene oxide (GO) was chemically functionalized to prepare polyurethane (PU) composites with improved mechanical and thermal properties. In order to achieve a well exfoliated and stable GO suspension in an organic solvent (dimethylformamide, DMF), 4, 4′- methylenebis(phenyl isocyanate) and polycaprolactone diol, which were the two monomers for synthesizing PU, were selectively used to functionalize GO. The obtained functionalized GO (FGO) could form homogeneous dispersions in DMF solvent and the PU matrix, as well as provide a good compatibility with the PU matrix. The most efficient improvement of mechanical properties was achieved when 0.4 wt% FGO was added into the PU matrix, showing increases in the tensile stress, elongation at break and toughness by 34.2%, 27.6% and 64.5%, respectively, compared with those of PU. Regarding the thermal stability, PU filled with 1 wt% FGO showed the largest extent of improvement with T2% and T50% (the temperatures at which 2% and 50% weight-loss happened) 16 °C and 21 °C higher than those of PU, respectively. The significant improvement in both mechanical properties and thermal stability of FGO/PU composites should be attributed to the homogeneous dispersion of FGO in the PU matrix and strong interfacial interaction between them.

Keywords: composite, dispersion, graphene oxide, polyurethane

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74 Starch Valorization: Biorefinery Concept for the Circular Bioeconomy

Authors: Maider Gómez Palmero, Ana Carrasco Pérez, Paula de la Sen de la Cruz, Francisco Javier Royo Herrer, Sonia Ascaso Malo

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The production of bio-based products for different purposes is one of the strategies that has grown the most at European and even global levels, seeking to contribute to mitigating the impacts associated with climate change and to achieve the ambitious objectives set in this regard. However, the substitution of fossil-based products for bio-based products requires a challenging and deep transformation and adaptation of the secondary and primary sectors and, more specifically, in the latter, the agro-industries. The first step to developing a bio-based value chain focuses on the availability of a resource with the right characteristics for the substitution sought. This, in turn, requires a significant reshaping of the forestry/agricultural sector but also of the agro-industry, which has a relevant potential to be deployed as a supplier and develop a robust logistical supply chain and to market a biobased raw material at a competitive price. However, this transformation may involve a profound restructuring of its traditional business model to incorporate biorefinery concepts. In this sense, agro-industries that generate by-products in their processes that are currently not valorized, such as potato processing rejects or the starch found in washing water, constitute a potential raw material that can be used for different bio-applications. This article aims to explore this potential to evaluate the most suitable bio applications to target and identify opportunities and challenges.

Keywords: starch valorisation, biorefinery, bio-based raw materials, bio-applications

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