Search results for: polycaprolactone/clay nanocomposites

Authors: Amine Harrane, Mahmoud Belalia

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During the last decade, polymer layered silicate nanocomposites have received increasing attention from scientists and industrial researchers because they generally exhibit greatly improved mechanical, thermal, barrier and flame-retardant properties at low clay content in comparison with unfilled polymers or more conventional micro composites. Poly(ε-caprolactone) (PCL)-layered silicate nanocomposites have the advantage of adding biocompatibility and biodegradability to the traditional properties of nanocomposites. They can be prepared by in situ ring-opening polymerization of ε-caprolactone using a conventional initiator to induce polymerization in the presence of an organophilic clay, such as organomodified montmorillonite. Messersmith and Giannelis used montmorillonite exchanged with protonated 12-amino dodecanoic acid and Cr3+ exchanged fluorohectorite, a synthetic mica type of silicate. Sn-based catalysts such as tin (II) octoate and dibutyltin (IV) dimethoxide have been reported to efficiently promote the polymerization of ε-caprolactone in the presence of organomodified clays. In this work, we have used an alternative method to prepare PCL/montmorillonite nanocomposites. The cationic polymerization of ε-caprolactone was initiated directly by Maghnite-TOA, organomodified montmorillonite clay, to produce nanocomposites (Scheme 1). Resulted from nanocomposites were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), force atomic microscopy (AFM) and thermogravimetry.

Keywords: polycaprolactone, polycaprolactone/clay nanocomposites, biodegradables nanocomposites, Maghnite, Insitu polymeriation

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Authors: Nagi Greesh

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This study highlights a new method to obtain multiphase composites particles containing hydrophobic (wax) and inorganic (clay) compounds. Multiphase polystyrene-clay-wax nanocomposites were successfully synthesized. Styrene monomer were polymerized in the presence of different wax-clay nanocomposites concentrations in miniemulsion. Wax-clay nanocomposites were firstly obtained through ultrasonic mixing at a temperature above the melting point of the wax at different clay loadings. The obtained wax-clay nanocomposites were then used as filler in the preparation of polystyrene-wax-clay nanocomposites via miniemulsion polymerization. The particles morphology of PS/wax-clay nanocomposites latexes was mainly determined by Transmission Electron Microscopy ( TEM) , core/shell morphology was clearly observed, with the encapsulation of most wax-clay nanocomposites inside the PS particles. On the other hand, the morphology of the PS/wax-clay nanocomposites (after film formation) ranged from exfoliated to intercalated structures, depending on the percentage of wax-clay nanocomposites loading. This strategy will allow the preparation materials with tailored properties for specific applications such as paint coatings and adhesives.

Keywords: polymer-wax, paraffin wax, miniemulsion, core/shell, nanocomposites

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Authors: Fatima Zohra Zeggai, Benjamin Carbonnier, Aïcha Hachemaoui, Ahmed Yahiaoui, Samia Mahouche-Chergui, Zakaria Salmi

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A series of polyaniline (PANI)/modified Montmorillonite (MMT) Clay nanocomposite materials have been successfully prepared by In-Situ polymerization in the presence of modified MMT-Clay or Diazonium-MMT-Clay. The obtained nanocomposites were characterized and compared by various physicochemical techniques. The presence of physicochemical interaction, probably hydrogen bonding, between clay and polyaniline, which was confirmed by FTIR, UV-Vis Spectroscopy. The electrical conductivity of neat PANI and a series of the obtained nanocomposites were also studied by cyclic voltammograms.

Keywords: polyaniline, clay, nanocomposites, in-situ polymerization, polymers conductors, diazonium salt

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Authors: Emad A. Jaffar Al-Mulla

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In this study, a biopolymer-based nanocomposite was successfully prepared through melt blending technique. Two biodegradable polymers, polycaprolactone and starch, environmental friendly and obtained from renewable, easily available raw materials, have been chosen. Fatty hydrazide, synthesized from palm oil, has been used as a surfactant to modify montmorillonite (natural clay) for preparation of polycaprolactone/starch nanocomposite. X-ray diffraction and transmission electron microscopy were used to characterize nanocomposite formation. Compatibility of the blend was improved by adding 3% weight modified clay. Higher biodegradability and thermal stability of nanocomopeite were also observed compared to those of the polycaprolactone/starch blend. This product will solve the problem of plastic waste, especially disposable packaging, and reduce the dependence on petroleum-based polymers and surfactants.

Keywords: polycaprolactone, starch, biodegradable, nanocomposite

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Authors: Danila Merino, Leandro N. Ludueña, Vera A. Alvarez

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Clays are commonly used to reinforce polymeric materials. In order to modify them, long-chain quaternary-alkylammonium salts have been widely employed. However, the application of these clays in biological fields is limited by the toxicity and poor biocompatibility presented by these modifiers. Meanwhile, soy lecithin, acts as a natural biosurfactant and environment-friendly biomodifier. In this report, we analyse the effect of content of soy lecithin-modified bentonite on the properties of polycaprolactone (PCL) nanocomposites. Commercial grade PCL (CAPA FB 100) was supplied by Perstorp, with Mw = 100000 g/mol. Minarmco S.A. and Melar S.A supplied bentonite and soy lecithin, respectively. Clays with 18, 30 and 45 wt% of organic content were prepared by exchanging 4 g of Na-Bent with 1, 2 and 4 g of soy lecithin aqueous and acid solution (pH=1, with HCl) at 75ºC for 2 h. Then, they were washed and lyophilized for 72 h. Samples were labeled A, B and C. Nanocomposites with 1 and 2 wt.% of each clay were prepared by melt-intercalation followed by compression-moulding. An intensive Brabender type mixer with two counter-rotating roller rotors was used. Mixing temperature was 100 ºC; speed of rotation was 100 rpm. and mixing time was 10 min. Compression moulding was carried out in a hydraulic press under 75 Kg/mm2 for 10 minutes at 100 ºC. The thickness of the samples was about 1 mm. Thermal and mechanical properties were analysed. PCL nanocomposites with 1 and 2% of B presented the best mechanical properties. It was observed that an excessive organic content produced an increment on the rigidity of PCL, but caused a detrimental effect on the tensile strength and elongation at break of the nanocomposites. Thermogravimetrical analyses suggest that all reinforced samples have higher resistance to degradation than neat PCL.

Keywords: chemical modification, clay, nanocomposite, characterization

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Authors: Mohamed Amine Zenasni, Bahia Meroufel, André Merlin, Said Benfarhi, Stéphane Molina, Béatrice George

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The introduction of nano-fillers into polymers field lead to the creation of the nano composites. This creation is starting up a new revolution into the world of materials. Nano composites are similar to traditional composite of a polymer blend and filler with at least one nano-scopic dimension. In our project, we worked with nano composites of biodegradable polymer: polycaprolactone, combined with nano-clay (Maghnite) and with different nano-organo-clays. These nano composites have been prepared by melt mixture method. The advantage of this polymer is its degradability and bio compatibility. A study of the relationship between development, micro structure and physico chemical properties of nano composites, clays modified with 3-aminopropyltriethoxysilane (APTES) and Hexadecyltriméthy ammonium bromide (CTAB) and untreated clays were made. Melt mixture method is most suitable methods to get a better dispersion named exfoliation.

Keywords: nanocomposite, biodegradable, polycaprolactone, maghnite, melt mixture, APTES, CTAB

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Authors: O. I. H. Dimitry, N. A. Mansour, A. L. G. Saad

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Natural sodium montmorillonite (NaMMT), Cloisite Na⁺ and two organophilic montmorillonites (OMMTs), Cloisites 20A and 15A were used. Polycaprolactone (PCL)/MMT composites containing 1, 3, 5, and 10 wt% of Cloisite Na⁺ and PCL/OMMT nanocomposites containing 5 and 10 wt% of Cloisites 20A and 15A were prepared via solution intercalation technique to study the influence of organic modifier loading on particle dispersion of PCL/ NaMMT composites. Thermal stabilities of the obtained composites were characterized by thermal analysis using the thermogravimetric analyzer (TGA) which showed that in the presence of nitrogen flow the incorporation of 5 and 10 wt% of filler brings some decrease in PCL thermal stability in the sequence: Cloisite Na+>Cloisite 15A > Cloisite 20A, while in the presence of air flow these fillers scarcely influenced the thermoxidative stability of PCL by slightly accelerating the process. The interaction between PCL and silicate layers was studied by Fourier transform infrared (FTIR) spectroscopy which confirmed moderate interactions between nanometric silicate layers and PCL segments. The electrical conductivity (σ) which describes the ionic mobility of the systems was studied as a function of temperature and showed that σ of PCL was enhanced on increasing the modifier loading at filler content of 5 wt%, especially at higher temperatures in the sequence: Cloisite Na⁺<Cloisite 20A<Cloisite 15A, and was then decreased to some extent with a further increase to 10 wt%. The activation energy E_σ obtained from the dependency of σ on temperature using Arrhenius equation was found to be lowest for the nanocomposite containing 5 wt% of Cloisite 15A. The dispersed behavior of clay in PCL matrix was evaluated by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses which revealed partial intercalated structures in PCL/NaMMT composites and semi-intercalated/semi-exfoliated structures in PCL/OMMT nanocomposites containing 5 wt% of Cloisite 20A or Cloisite 15A.

Keywords: electrical conductivity, montmorillonite, nanocomposite, organoclay, polycaprolactone

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Authors: F. Zouai, F. Z. Benabid, S. Bouhelal, D. Benachour

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A method for the exfoliation of polyethylene terephtalate (PET) - clay nanocomposites has been reported in this study. Montmorillonite clay based polyethylene terephtalate nanocomposites were prepared by reactive melt-mixing. To achieve this, untreated clay was first functionalized with the crosslinking agent compound based mainly on peroxide/sulphur and TMTD as accelerator or activator for sulphur. Furthermore, the different blends composition of PET/clay were directly mixed in melt state in closed chamber of plastograph at given working conditions for short time and in one step process. To investigate the microstructure modification and thermal, mechanical and rheological properties the DSC, WAXS, microhardness, FTIR and tensile properties were performed. The resulting structure of the modified samples shows that total exfoliation appears at 4% w/w of clay to PET matrices. The crystallinity and tensile modulus were correlated by the H microhardness and the DSC shows no significant effect on the cristallinity degree. The mechanical properties were improved significantly. The viscosity decreases for 4% clay and the activation energy is the minimum. The WAXS measurement shows a partial exfoliation without any intercalation which is the most relevant point. The grafting of organic to inorganic nanolayers was observed by Si—O—C and Si—C bonds by FTIR.

Keywords: PET, montmorillonite, nanocomposites, exfoliation, reactive melt-mixing

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Authors: F. Zouai, F. Z. Benabid, S. Bouhelal, D. Benachour

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Reinforced plastics or nanocomposites have attracted considerable attention in scientific and industrial fields because a very small amount of clay can significantly improve the properties of the polymer. The polymeric matrices used in this work are two saturated polyesters, i.e., polyethylene terephthalate (PET) and polyethylene naphthalate (PEN). The success of processing compatible blends, based on poly(ethylene terephthalate) (PET)/poly(ethylene naphthalene) (PEN)/clay nanocomposites in one step by reactive melt extrusion is described. Untreated clay was first purified and functionalized ‘in situ’ with a compound based on an organic peroxide/ sulfur mixture and (tetramethylthiuram disulfide) as the activator for sulfur. The PET and PEN materials were first separately mixed in the molten state with functionalized clay. The PET/4 wt% clay and PEN/7.5 wt% clay compositions showed total exfoliation. These compositions, denoted nPET and nPEN, respectively, were used to prepare new n(PET/PEN) nanoblends in the same mixing batch. The n(PET/PEN) nanoblends were compared to neat PET/PEN blends. The blends and nanocomposites were characterized using various techniques. Microstructural and nanostructural properties were investigated. Fourier transform infrared spectroscopy (FTIR) results showed that the exfoliation of tetrahedral clay nanolayers is complete, and the octahedral structure totally disappears. It was shown that total exfoliation, confirmed by wide-angle X-ray scattering (WAXS) measurements, contributes to the enhancement of impact strength and tensile modulus. In addition, WAXS results indicated that all samples are amorphous. The differential scanning calorimetry (DSC) study indicated the occurrence of one glass transition temperature Tg, one crystallization temperature Tc and one melting temperature Tm for every composition.

Keywords: exfoliation, DRX, DSC, montmorillonite, nanocomposites, PEN, PET, plastograph, reactive melt-mixing

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Authors: Habib Shaban

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Nanocomposites of isotactic polypropylene (iPP) and date wood fiber were prepared after modification of the host matrix by reactive extrusion grafting of maleic anhydride. Chemical and mechanical treatment of date wood flour (WF) was conducted to obtain nanocrystalline cellulose. Layered silicates (clay) were partially intercalated with date wood fiber, and the modified layered silicate was used as filler in the PP matrix via a melt-blending process. The tensile strength of composites prepared from wood fiber modified clay was greater than that of the iPP-clay and iPP-WF composites at a 6% filler concentration, whereas deterioration of mechanical properties was observed when clay and WF were used alone for reinforcement. The dispersion of the filler in the matrix significantly decreased after clay modification with cellulose at higher concentrations, as shown by X-ray diffraction (XRD) data.

Keywords: nanocomposites, isotactic polypropylene, date wood flour, intercalated, melt-blending

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Authors: Kumar Sankaran, Santanu Chattopadhyay, Golok Behari Nando, Sujith Nair, Sreejesh Arayambath, Unnikrishnan Govindan

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Rubber nanocomposites based on Bromobutyl rubber (BIIR), Polyepichlorohydrin rubber (CO), Carbon black (CB) and organically modified montmorillonite clay (NC) were prepared via melt compounding technique. The developed quaternary nanocomposites were characterized analytically and their properties were compared against the standard BIIR compound. BIIR-CO nanocomposites showed improved physico-mechanical properties as compared to that of the standard BIIR compound. Hybrid microstructure (NC-CB) development, clay exfoliation and better filler dispersion in the quaternary nanocomposite significantly contributed to the overall enhancement of properties. Introduction of CO in the system increased the specific gravity and hardness of the compound as compared to that of the standard compound. XRD analysis, AFM imaging and HR-TEM measurements confirmed exfoliation and a good level of dispersion of the NC in the composites. Permeability of developed BIIR-CO nanocomposites decreases significantly as compared to that of the standard BIIR compound.

Keywords: rubber nanocomposites, morphology, permeability, BIIR

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Authors: F. Zouai, F. Z. Benabid, S. Bouhelal, D. Benachoura

Abstract:

A (PET)/clay nano composites has been successfully performed in one step by reactive melt extrusion. The PEN was first mixed in the melt state with different amounts of functionalized clay. It was observed that the composition PET/4 wt% clay showed total exfoliation. These completely exfoliated composition called nPET, was used to prepare new nPET nano composites in the same mixing batch. The nPEN was compared to neat PET. The nanocomposites were characterized by different techniques: differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). The micro and nanostructure/properties relationships were investigated. From the different WAXS patterns, it is seen that all samples are amorphous phase. In addition, nPET blends present lower Tc values and higher Tm values than the corresponding neat PET. The present study allowed establishing good correlations between the different measured properties.

Keywords: PET, montmorillonite, nanocomposites, exfoliation, reactive melt-mixing

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Authors: R. Kamarudzaman, A. Kalam, N. A. Mohd Fadzil

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Oil Palm Fruit Bunch Fiber (OPEFB) was used as secondary filler in HDPE/clay nanocomposites. The composites were prepared by melt compounding which contains High Density Polyethylene (HDPE), OPEFB fibers, Maleic Anhydride Graft Polyethylene (MAPE) and four different clay loading (3, 5, 7 and 10 PE nanoclay pellets per hundred of HDPE pellets). Four OPEFB sizes (180 µm, 250 µm, 300 µm and 355 µm) were added in the composites to investigate their effects on fracture toughness. Fracture toughness of the composites were determined according to ASTM D5045 and Single Edge Notch Bending (SENB) been employed during the test. The effects of alkali treatment were also investigated in this study. The results indicate that the fracture toughness slightly increased as clay loading increased. The highest value of fracture toughness was 0.47 and 1.06 MPa.m1/2 at 5 phr for both types of clay loading. The presence of filler as reinforcement with the matrix indicates the enhancement of composites compared to those without the filler.

Keywords: oil palm empty fruit bunch, fiber, polyethylene, polymer nanocomposite, impact strength

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Authors: Samir Al-Zobaidi

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This study attempts to understand the effect of different UV irradiation methods on the intercalation of LDPE/MMT nanocomposites, and its molecular behavior at certain isothermal crystallization temperature. Three different methods of UV exposure were employed using single composition of LDPE/MMT nanocomposites. All samples were annealed for 5 hours at a crystallization temperature of 100°C. The crystallization temperature was chosen to be at large supercooling temperature to ensure quick and complete crystallization. The raw material of LDPE consisted of two stable monoclinic and orthorhombic phases according to XRD results. The thermal behavior of both phases acted differently when UV exposure method was changed. The monoclinic phase was more dependent on the method used compared to the orthorhombic phase. The intercalation of clay, as well as, the non-isothermal crystallization temperature, has also shown a clear dependency on the type of UV exposure. A third phase that is thermally less stable was also observed. Its respond to UV irradiation was greater since it contains low molecular weight entities which make it more vulnerable to any UV exposure.

Keywords: LDPE/MMt nanocomposites, crystallization, UV irradiation, intercalation

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Authors: D. E. Abulyazied, S. M. Mokhtar, A. M. Motawie

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Polymer blends represent an important class of materials in engineering applications. The incorporation of clay nanofiller may provide new opportunities for this type of materials to enhance their applications. This article reports on the effects of clay on the structure and properties of polymer blends nanocomposites, based on Polyvinyl chloride PVC and styrene co-maleic anhydride SMA blend. Modification of the Egyptian Bentonite EB was carried out using organo-modifier namely; octadecylamine ODA. Before the modification, the cation exchange capacity CEC of the EB was measured. The octadecylamine bentonite ODA-B was characterized using Fourier transform infrared Spectroscopy FTIR, X-Ray Diffraction XRD, and Transition Electron Microscope TEM. A blend of Polyvinyl chloride PVC and styrene co-maleic anhydride SMA (50:50) was prepared in Tetra Hydro Furan (THF). Then nanocomposites of PVC/SMA/ODA-B were prepared by solution intercalation polymerization from 0.50% up to 5% by weight of ODA-B. The nanocomposites are characterized by XRD, TEM. Thermal, nanoindentation, swelling and electrical properties of the nanocomposites were measured. The morphology of the nanocomposites showed that ODA-B achieved good dispersion in the PVC/SMA matrix. Incorporation of 0.5 %, 1%, 3% and 5% by weight nanoclay into the PVC/SMA blends results in an improvement in nanohardness of 16%, 76%, 92%, and 68% respectively. The elastic modulus increased from 4.59 GPa for unreinforced PVC/SMA blend to 6.30 GPa (37% increase) with the introduction of 3% by weight nanoclay. The cross-link density of the nanocomposites increases with increasing the content of ODA-B.

Keywords: PVC, SMA, nanocomposites, nanoindentation, organo-bentonite

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Authors: F. Zouai, F. Z. Benabid, S. Bouhelal, D. Benachour

Abstract:

Nanocomposite polymer / clay are relatively important area of research. These reinforced plastics have attracted considerable attention in scientific and industrial fields because a very small amount of clay can significantly improve the properties of the polymer. The polymeric matrices used in this work are two saturated polyesters ie polyethylene terephthalate (PET) and polyethylene naphthalate (PEN).The success of processing compatible blends, based on poly(ethylene terephthalate) (PET)/ poly(ethylene naphthalene) (PEN)/clay nanocomposites in one step by reactive melt extrusion is described. Untreated clay was first purified and functionalized ‘in situ’ with a compound based on an organic peroxide/ sulfur mixture and (tetramethylthiuram disulfide) as the activator for sulfur. The PET and PEN materials were first separately mixed in the molten state with functionalized clay. The PET/4 wt% clay and PEN/7.5 wt% clay compositions showed total exfoliation. These compositions, denoted nPET and nPEN, respectively, were used to prepare new n(PET/PEN) nanoblends in the same mixing batch. The n(PET/PEN) nanoblends were compared to neat PET/PEN blends. The blends and nanocomposites were characterized using various techniques. Microstructural and nanostructural properties were investigated. Fourier transform infrared spectroscopy (FTIR) results showed that the exfoliation of tetrahedral clay nanolayers is complete and the octahedral structure totally disappears. It was shown that total exfoliation, confirmed by wide angle X-ray scattering (WAXS) measurements, contributes to the enhancement of impact strength and tensile modulus. In addition, WAXS results indicated that all samples are amorphous. The differential scanning calorimetry (DSC) study indicated the occurrence of one glass transition temperature Tg, one crystallization temperature Tc and one melting temperature Tm for every composition. This was evidence that both PET/PEN and nPET/nPEN blends are compatible in the entire range of compositions. In addition, the nPET/nPEN blends showed lower Tc and higher Tm values than the corresponding neat PET/PEN blends. In conclusion, the results obtained indicate that n(PET/PEN) blends are different from the pure ones in nanostructure and physical behavior.

Keywords: blends, exfoliation, DRX, DSC, montmorillonite, nanocomposites, PEN, PET, plastograph, reactive melt-mixing

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Authors: Pooria Pasbakhsh, Rangika T. De Silva, Vahdat Vahedi, Hanafi Ismail

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The influence of three different types of halloysite nanotubes (HNTs) with different dimensions, namely as camel lake (CLA), Jarrahdale (JA) and Matauri Bay (MB), on their reinforcing ability of ethylene propylene dine monomer (EPDM) were investigated by varying the HNTs loading (from 0-15 phr). Mechanical properties of the nanocomposites improved with addition of all three HNTs, but CLA based nanocomposites exhibited a significant enhancement compared to the other HNTs. For instance, tensile properties of EPDM nanocomposites increased by 120%, 256% and 340% for MB, JA, and CLA, respectively with addition of 15 phr of HNTs. This could be due to the higher aspect ratio and higher surface area of CLA compared to others. Scanning electron microscopy (SEM) of nanocomposites at 15 phr of HNT loadings showed low amounts of pulled-out nanotubes which confirmed the presence of more embedded nanotubes inside the EPDM matrix, as well as aggregates within the fracture surface of EPDM/HNT nanocomposites.

Keywords: aspect ratio, halloysite nanotubes (HNTs), mechanical properties, rubber/clay nanocomposites

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Authors: Emi Govorčin Bajsića, Vesna Ocelić Bulatović, Miroslav Slouf, Ana Šitum

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Composites based on a biodegradable polycaprolactone (PCL) containing 0.5, 1.0 and 2.0 wt % of titanium dioxide (TiO2) micro and nanoparticles were prepared by melt mixing and the effect of filler type and contents on the thermal properties, dynamic-mechanical behaviour and morphology were investigated. Measurements of storage modulus and loss modulus by dynamic mechanical analysis (DMA) showed better results for microfilled PCL/TiO2 composites than nanofilled composites, with the same filler content. DSC analysis showed that the Tg and Tc of micro and nanocomposites were slightly lower than those of neat PCL. The crystallinity of the PCL increased with the addition of TiO2 micro and nanoparticles; however, the c for the PCL was unchanged with micro TiO2 content. The thermal stability of PCL/TiO2 composites were characterized using thermogravimetric analysis (TGA). The initial weight loss (5 wt %) occurs at slightly higher temperature with micro and nano TiO2 addition and with increasing TiO2 content.

Keywords: polycaprolactone, titanium dioxide, thermal properties, morphology

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Authors: K. Khouzami, J. Brassinne, C. Branca, E. Van Ruymbeke, B. Nysten, G. D’Angelo

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The development of hybrid organic-inorganic nanocomposites has recently attracted great interest. Typically, polymer silicates represent an emerging class of polymeric nanocomposites that offer superior material properties compared to each compound alone. Among these materials, complexes based on silicate clay and polysaccharides are one of the most promising nanocomposites. The strong electrostatic interaction between chitosan and montmorillonite can induce what is called physical hydrogel, where the coordination bonds or physical crosslinks may associate and dissociate reversibly and in a short time. These mechanisms could be the main origin of the uniqueness of their rheological behavior. However, owing to their structure intrinsically heterogeneous and/or the lack of dissipated energy, they are usually brittle, possess a poor toughness and may not have sufficient mechanical strength. Consequently, the properties of these nanocomposites cannot respond to some requirements of many applications in several fields. To address the issue of weak mechanical properties, covalent chemical crosslink bonds can be introduced to the physical hydrogel. In this way, quite homogeneous dually crosslinked microstructures with high dissipated energy and enhanced mechanical strength can be engineered. In this work, we have prepared a series of chitosan-montmorillonite nanocomposites chemically crosslinked by addition of poly (ethylene glycol) diglycidyl ether. This study aims to provide a better understanding of the mechanical behavior of dually crosslinked chitosan-based nanocomposites by relating it to their microstructures. In these systems, the variety of microstructures is obtained by modifying the number of cross-links. Subsequently, a superior uniqueness of the rheological properties of chemically crosslinked chitosan-montmorillonite nanocomposites is achieved, especially at the highest percentage of clay. Their rheological behaviors depend on the clay/chitosan ratio and the crosslinking. All specimens exhibit a viscous rheological behavior over the frequency range investigated. The flow curves of the nanocomposites show a Newtonian plateau at very low shear rates accompanied by a quite complicated nonlinear decrease with increasing the shear rate. Crosslinking induces a shear thinning behavior revealing the formation of network-like structures. Fitting shear viscosity curves via Ostward-De Waele equation disclosed that crosslinking and clay addition strongly affect the pseudoplasticity of the nanocomposites for shear rates γ ̇>20.

Keywords: chitosan, crossliking, nanocomposites, rheological properties

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Authors: D. Önen, N. Kızılcan, B. Yıldız, A. Akar

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In situ modified cyclohexanone-formaldehyde resins were prepared by addition of alendronic acid during resin preparation. Clay nanocomposites in ketonic resins were achieved by adding clay into the flask at the beginning of the resin preparation. The prepared resins were used for the synthesis of fire resistant polyurethanes foam. Both phosphorous containing modifier compound alendronic acid and nanoclay increases fire resistance of the cyclohexanone-formaldehyde resin thus polyurethane produced from these resins. The effect of the concentrations of alendronic acid and clay on the fire resistance and physical properties of polyurethanes was studied.

Keywords: alendronic acid, clay, ketonic resin, polyurethane

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Authors: H. Ferfera-Harrar, T. Benhalima, D. Lerari

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Contamination of water, due to the discharge of untreated industrial wastewaters into the ecosystem, has become a serious problem for many countries. In this study, bioadsorbents based on chitosan-g-poly(acrylamide) and montmorillonite (MMt) clay (CTS-g-PAAm/MMt) hydrogel nanocomposites were prepared via free‐radical grafting copolymerization and crosslinking of acrylamide monomer (AAm) onto natural polysaccharide chitosan (CTS) as backbone, in presence of various contents of MMt clay as nanofiller. Then, they were hydrolyzed to obtain highly functionalized pH‐sensitive nanomaterials with uppermost swelling properties. Their structure characterization was conducted by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. The adsorption performances of the developed nanohybrids were examined for removal of methylene blue (MB) cationic dye from aqueous solutions. The factors affecting the removal of MB, such as clay content, pH medium, adsorbent dose, initial dye concentration and temperature were explored. The adsorption process was found to be highly pH dependent. From adsorption kinetic results, the prepared adsorbents showed remarkable adsorption capacity and fast adsorption rate, mainly more than 88% of MB removal efficiency was reached after 50 min in 200 mg L^-1 of dye solution. In addition, the incorporating of various content of clay has enhanced adsorption capacity of CTS-g-PAAm matrix from 1685 to a highest value of 1749 mg g^-1 for the optimized nanocomposite containing 2 wt.% of MMt. The experimental kinetic data were well described by the pseudo-second-order model, while the equilibrium data were represented perfectly by Langmuir isotherm model. The maximum Langmuir equilibrium adsorption capacity (q_m) was found to increase from 2173 mg g⁻¹ until 2221 mg g⁻¹ by adding 2 wt.% of clay nanofiller. Thermodynamic parameters revealed the spontaneous and endothermic nature of the process. In addition, the reusability study revealed that these bioadsorbents could be well regenerated with desorption efficiency overhead 87% and without any obvious decrease of removal efficiency as compared to starting ones even after four consecutive adsorption/desorption cycles, which exceeded 64%. These results suggest that the optimized nanocomposites are promising as low cost bioadsorbents.

Keywords: chitosan, clay, dye adsorption, hydrogels nanocomposites

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Authors: F. Zouai, F. Z. Benabid, S. Bouhelal, D. Benachour

Abstract:

A new route of preparation of compatible blends, based on poly(ethylene terephthalate)(PET)/poly(ethylenenaphthalene2,6-dicarboxylate) (PEN)/clay nanocomposites has been successfully performed in one step by reactive melt extrusion. To achieve this, untreated clay was first purified and functionalized “in situ” with a compound based on an organic peroxide/sulfur mixture and (tetra methyl thiuram disulfide) TMTD as accelerator or activator for sulfur. The PET and PEN materials were first mixed separately in the melt state with different amounts of functionalized clay. It was observed that the compositions PET/4 wt% clay and PEN/7.5 wt% clay showed total exfoliation. These completely exfoliated compositions, called nPET and nPEN, respectively, were used to prepare new nPET/nPEN nanoblends in the same mixing batch. The nPET/nPEN nanoblends were compared to neat blends of PET/PEN. The blends and the nanocomposites were characterized by different techniques: differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). The micro and nanostructure/properties relationships were investigated. The results of the WAXS measurements study showed that the exfoliation of tetrahedral nanolayers of clay was complete and the octahedral structure disappeared totally. From the different WAXS patterns, it is seen that all samples are amorphous phase. The thermal study showed that there are only one glass transition temperature Tg, one crystallization temperature Tc and one melting temperature Tm for every composition. This indicated that both PET/PEN blends and nPET/nPEN blends were compatible in the entire range of compositions. In addition, nPET/nPEN blends present lower Tc values and higher Tm values than the corresponding neat PET/PEN blends. The obtained results indicate that nPET/nPEN blends are somewhat different from the pure ones in nanostructure and behavior, thus showing the additional effect of nanolayers. The present study allowed establishing good correlations between the different measured properties.

Keywords: PET, PEN, montmorillonite, nanocomposites, exfoliation, reactive melt-mixing

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Authors: Gulcan Sahal, Behzad Nasseri, Ali Akbar Ebrahimi, Isil Seyis Bilkay

Abstract:

Proteus mirabilis strains which are natural colonizers of healthy individuals’ gastrointestinal tract are also known as common causes of catheter-associated urinary tract infections. Nowadays, as a result of an increased resistance to various antimicrobial drugs, there has been a growing interest in natural products. Therefore, the aim of this study is to investigate biofilm formation of P. mirabilis strains on lemongrass oil containing polycaprolactone nanofibers. Polycaprolactone nanofibers with different lemongrass oil concentrations were successfully prepared by electrospinning and biofilm formation of P. mirabilis on these nanofibers were determined by ‘Crystal Violet Staining Assay’. According to our results, polycaprolactone nanofibers with some lemongrass oil concentrations, decreased biofilm formation of P. mirabilis and this effect increased in parallel with the increase in lemongrass oil concentration. Our results indicate that, polycaprolactone nanofibers with some concentrations of lemongrass oil may provide a treatment against catheter-associated urinary tract infections by means of causing an inhibition on biofilm formation of P. mirabilis.

Keywords: anti-biofilm, biofilm formation, essential oils, nanofibers, proteus mirabilis

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Authors: Sayed Mansour, Mohammad Aldoasri, Nagib Elmarzugi, Nadia A. Al-Mouallimi

Abstract:

The archaeological large stone used in construction of ancient Pharaonic tombs, temples, obelisks and other sculptures, always subject to physicomechanical deterioration and destructive forces, leading to their partial or total broken. The task of reassembling this type of artifact represent a big challenge for the conservators. Recently, the researchers are turning to new technologies to improve the properties of traditional adhesive materials and techniques used in re-assembly of broken large stone. The epoxy resins are used extensively in stone conservation and re-assembly of broken stone because of their outstanding mechanical properties. The introduction of nanoparticles to polymeric adhesives at low percentages may lead to substantial improvements of their mechanical performances in structural joints and large objects. The aim of this study is to evaluate the effectiveness of clay nanoparticles in enhancing the performances of epoxy adhesives used in re-assembly of archaeological massive stone by adding proper amounts of those nanoparticles. The nanoparticles reinforced epoxy nanocomposite was prepared by direct melt mixing with a nanoparticles content of 3% (w/v), and then mould forming in the form of rectangular samples, and used as adhesive for experimental stone samples. Scanning electron microscopy (SEM) was employed to investigate the morphology of the prepared nanocomposites, and the distribution of nanoparticles inside the composites. The stability and efficiency of the prepared epoxy-nanocomposites and stone block assemblies with new formulated adhesives were tested by aging artificially the samples under different environmental conditions. The effect of incorporating clay nanoparticles on the mechanical properties of epoxy adhesives was evaluated comparatively before and after aging by measuring the tensile, compressive, and Elongation strength tests. The morphological studies revealed that the mixture process between epoxy and nanoparticles has succeeded with a relatively homogeneous morphology and good dispersion in low nano-particles loadings in epoxy matrix was obtained. The results show that the epoxy-clay nanocomposites exhibited superior tensile, compressive, and Elongation strength. Moreover, a marked improvement of the mechanical properties of stone joints increased in all states by adding nano-clay to epoxy in comparison with pure epoxy resin.

Keywords: epoxy resins, nanocomposites, clay nanoparticles, re-assembly, archaeological massive stones, mechanical properties

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Authors: I. Yalcin Enis, J. Vojtech, T. Gok Sadikoglu

Abstract:

In this study, polycaprolactone (PCL) was dissolved in chloroform: ethanol solvent system at a concentration of 18 w/v %. 1, 2, 4, and 6 droplets of formic acid were added to the prepared 10ml PCL-chloroform:ethanol solutions separately. Fibrous webs were produced by electrospinning technique. Morphology of the webs was investigated by using scanning electron microscopy (SEM) whereas fiber diameters were measured by Image J Software System. The effect of formic acid addition to the mostly used chloroform solvent on fiber morphology was examined.

Keywords: chloroform, electrospinning, formic acid polycaprolactone, fiber

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Authors: Rasha S. Kamal, Reham I. El-Shazly, Reem K. Farag

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Green nano-branched structural compounds were synthesized by adding 1% by weight of clay nanoparticle to different moles ratios of either dodecyl acrylate or triethylenetetramine using a simple one-pot method. The synthesized nano polymers were provided with different terminations. In order to confirm the chemical structure of the produced nanocomposites, FTIR and 1HNMR spectroscopy were performed. Additionally, Dynamic Light Scattering (DLS) analysis was used to assess the size and dispersion of the produced branching nano polymers. Using a Gel-permeation chromatograph, the molecular weights of the produced modified green nano hyperbranched polymer with various terminations were determined. the prepared nano samples with different molar feed ratios dodecyl acrylate: triethylenetetramine (DDA: TETA) was designed as An, Bn, Cn, Dn and En. Moreover, the synthesized compounds are expressed as viscosity index improvers (VII); The VI rises when prepared additive concentrations in the solution improve, as does the VI as prepared hyperbranched polymers' triethylenetetramine content rises, and the most effective VI is (E). All of the synthesized green hyperbranched nanocomposites have Newtonian rheological behavior as their rheological behavior.

Keywords: green hyperbranched polymer, DLS, viscosity index improver, Michael addition, nano clay

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Authors: Evgen Prokhorov, Gabriel Luna-Barcenas

Abstract:

The polysaccharide chitosan (CS) is an attractive biopolymer for the stabilization of several nanoparticles in acidic aqueous media. This is due in part to the presence of abundant primary NH2 and OH groups which may lead to steric or chemical stabilization. Applications of most CS nanocomposites are based upon the interaction of high surface area nanoparticles (NPs) with different substance. Therefore, agglomeration of NPs leads to decreasing effective surface area such that it may decrease the efficiency of nanocomposites. The aim of this work is to measure nanocomposite’s electrical conductivity phenomena that will allow one to formulate optimal concentrations of conductivity NPs in CS-based nanocomposites. Additionally, by comparing the efficiency of such nanocomposites, one can guide applications in the biomedical (antibacterial properties and tissue regeneration) and sensor fields (detection of copper and nitrate ions in aqueous solutions). It was shown that the best antibacterial (CS-AgNPs, CS-AgNPs-carbon nanotubes) and would healing properties (CS-AuNPs) are observed in nanocomposites with concentrations of NPs near the percolation threshold. In this regard, the best detection limit in potentiometric and impedimetric sensors for detection of copper ions (using CS-AuNPs membrane) and nitrate ions (using CS-clay membrane) in aqueous solutions have been observed for membranes with concentrations of NPs near percolation threshold. It is well known that at the percolation concentration of NPs an abrupt increasing of conductivity is observed due to the presence of physical contacts between NPs; above this concentration, agglomeration of NPs takes place such that a decrease in the effective surface and performance of nanocomposite appear. The obtained relationship between electrical percolation threshold and performance of polymer nanocomposites with conductivity NPs is important for the design and optimization of polymer-based nanocomposites for different applications.

Keywords: chitosan, conductivity nanoparticles, percolation threshold, polymer nanocomposites

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Authors: Benalia Kouini, Aicha Serier

Abstract:

Nanocomposites based on polypropylene/polyamide 66 (PP/PA66) nanoblends containing organophilic montmorillonite (OMMT) and maleic anhydride grafted polypropylene (PP-g-MAH) were prepared by melt compounding method followed by injection molding. Two different types of nanoclays were used in this work. DELLITE LVF is the untreated nanoclay and DELLITE 67G is the treated one. The morphology of the nanocomposites was studied using the XR diffraction (XRD). The results indicate that the incorporation of treated nanoclay has a significant effect on the impact strength of PP/PA66 nanocomposites. Furthermore, it was found that XRD results revealed the intercalation, exfoliation of nanaclays of nanocomposites.

Keywords: nNanoclay, Nanocomposites, Polypropylene, Polyamide, melt processing, mechanical properties.

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Authors: Ouaaz Oum Essaad, Melbouci Bachir

Abstract:

The experimental study conducted has a dual purpose: to valorize the clay material in the road domain and improve the lift of the shape layers by strengthening with plastic waste (in the form of aggregates). To do this, six mixtures of Clay and sand of different percentages were studied: 100% Clay, 95% Clay + 05% Sand, 90% Clay + 10% Sand, 85% Clay + 15% Sand, 80% Clay + 20% Sand, 75% Clay + 25% Sand. Proctor compaction and simple compression tests have been carried out on mixtures (sand + clay + plastic waste). The results obtained show a clear evolution of the characteristics of the Proctor test and the compressive strength of the mixtures according to the different types and percentages of the recycled plastic Plasticity and consistency index are important parameters that play a role in the toughness of plastic soil.

Keywords: valorization, recycling, soil mixture, mechanical tests

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Authors: Payal Mazumdar, Sunita Rattan, Monalisa Mukherjee

Abstract:

Polymer nanocomposites are a special class of materials having unique properties and wide application in diverse areas such as EMI shielding, sensors, photovoltaic cells, membrane separation properties, drug delivery etc. Recently the nanocomposites are being investigated for their use in biomedical fields as biosensors. Though nanocomposites with carbon nanoparticles have received worldwide attention in the past few years, comparatively less work has been done on nanographite although it has in-plane electrical, thermal and mechanical properties comparable to that of carbon nanotubes. The main challenge in the fabrication of these nanocomposites lies in the establishment of homogeneous dispersion of nanographite in polymer matrix. In the present work, attempts have been made to synthesize the nanocomposites of polystyrene and nanographite using click chemistry. The polymer and the nanographite are functionalized prior to the formation of nanocomposites. The polymer, polystyrene, was functionalized with alkyne moeity and nanographite with azide moiety. The fabricating of the nanocomposites was accomplished through click chemistry using Cu (I)-catalyzed Huisgen dipolar cycloaddition. The functionalization of filler and polymer was confirmed by NMR and FTIR. The nanocomposites formed by the click chemistry exhibit better electrical properties and the sensors are evaluated for their application as biosensors.

Keywords: nanocomposites, click chemistry, nanographite, biosensor

Procedia PDF Downloads 306