Search results for: polyamide copolymers

Authors: Krasimira N. Zhilkova, Mariya K. Kyulavska, Roza P. Mateva

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The anionic polymerization of -caprolactam (CL) with bifunctional activators has been extensively studied as an effective and beneficial method of improving chemical and impact resistances, elasticity and other mechanical properties of polyamide (PA6). In presence of activators or macroactivators (MAs) also called polymeric activators (PACs) the anionic polymerization of lactams proceeds rapidly at a temperature range of 130-180C, well below the melting point of PA-6 (220C) permitting thus the direct manufacturing of copolymer product together with desired modifications of polyamide properties. Copolymers of PA6 with an elastic polypropylene glycol (PPG) middle block into main chain were successfully synthesized via activated anionic ring opening polymerization (ROP) of CL. Using novel PACs based on PPG polyols (with differ molecular weight) the anionic ROP of CL was realized and investigated in the presence of a basic initiator sodium salt of CL (NaCL). The PACs were synthesized as N-carbamoyllactam derivatives of hydroxyl terminated PPG functionalized with isophorone diisocyanate [IPh, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane] and blocked then with CL units via an addition reaction. The block copolymers were analyzed and proved with 1H-NMR and FT-IR spectroscopy. The influence of the CL/PACs ratio in feed, the length of the PPG segments and polymerization conditions on the kinetics of anionic ROP, on average molecular weight, and on the structure of the obtained block copolymers were investigated. The structure and phase behaviour of the copolymers were explored with differential scanning calorimetry, wide-angle X-ray diffraction, thermogravimetric analysis and dynamic mechanical thermal analysis. The crystallinity dependence of PPG content incorporated into copolymers main backbone was estimate. Additionally, the mechanical properties of the obtained copolymers were studied by notched impact test. From the performed investigation in this study could be concluded that using PPG based PACs at the chosen ROP conditions leads to obtaining well-defined PA6-b-PPG-b-PA6 copolymers with improved impact resistance.

Keywords: anionic ring opening polymerization, caprolactam, polyamide copolymers, polypropylene glycol

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Authors: Nesrin Köken, Esin A. Güvel, Nilgün Kızılcan

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This work presents synthesis of α,ω-dithienyl terminated poly(ethylene glycol) (PEGTh) capable for further chain extension by either chemical or electrochemical polymerization. PEGTh was characterized by FTIR and 1H-NMR. Further, copolymerization of PEGTh and pyrrole (Py) was performed by chemical oxidative polymerization using ceric (IV) salt as an oxidant (PPy-PEGTh). PEG without end group modification was used directly to prepare copolymers with Py by Ce (IV) salt (PPy-PEG). Block copolymers with mole ratio of pyrrole to PEGTh (PEG) 50:1 and 10:1 were synthesized. The electrical conductivities of copolymers PPy-PEGTh and PPy-PEG were determined by four-point probe technique. Influence of the synthetic route and content of the insulating segment on conductivity and yield of the copolymers were investigated.

Keywords: chemical oxidative polymerization, conducting polymer, poly(ethylene glycol), polypyrrole

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Authors: A. Al-Sayyad, P. Lama, J. Bardon, P. Hirchenhahn, L. Houssiau, P. Plapper

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Composite metal–polymer materials, in particular titanium alloy (Ti-6Al-4V) to polyamide (PA6.6), fabricated by laser joining, have gained cogent interest among industries and researchers concerned with aerospace and biomedical applications. This work adopts infrared (IR) thermography technique to investigate effects of laser parameters used in the welding process on the three-dimensional temperature profile at the rear-side of titanium, at the region to be welded with polyamide. Cross sectional analysis of welded joints showed correlations between the morphology of titanium and polyamide at the weld zone with the corresponding temperature profile. In particular, spatial temperature profile was found to be correlated with the laser beam energy density, titanium molten pool width and depth, and polyamide heat affected zone depth.

Keywords: laser welding, metals to polymers joining, process monitoring, temperature profile, thermography

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Authors: Mohamed H. El-Newehy, Sameh M. Osman, Moamen S. Refat, Salem S. Al-Deyab, Ayman El-Faham

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The two copolymers itaconic acid-methyl methacrylate and itaconic acid-acrylamide have been prepared in different ratio by radical copolymerization in the presence of azobisisobutyronitrile (AIBN) as initiator and using 2-butanone as reaction medium using microwave irradiation. The microwave technique is safe, fast, and gives high yield of the products with high purity in an optimum time, comparing to the traditional conventional heating. All the prepared copolymers were characterized by FT-IR, thermal analysis and elemental microanalysis. The itaconic acid-based copolymers showed a good sensitivity in alkaline media for scavenging Cu (II) and Pb (II). The chelation behavior of both Cu (II) and Pb (II) complexes were checked using FT-IR, thermogravimetric analysis (TGA), and differential scanning calorimetery (DSC). The infrared data are in a good agreement with the coordination through carboxylate-to-metal, in which the copolymers acting as a bidentate ligand.

Keywords: microwave synthesis, itaconic acid, copolymerization, scavenging, thermal stability

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Authors: M. N. Abu Seman, L. M. Kei, M. A. Yusoff

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Forward Osmosis (FO) polyamide thin-film composite membranes have been prepared by inter facial polymerization using commercial UF polyethersulfone as membrane support. Different inter facial polymerization times (10s, 30s and 60s) in the organic solution containing trimesoyl chloride (TMC) at constant m-phenylenediamine (MPD) concentration (2% w/v) were studied. The synthesized polyamide membranes then tested for treatment of natural organic matter (NOM) and compared to commercial Cellulose TriAcetate (CTA) membrane. It was found that membrane prepared with higher reaction time (30 s and 60 s) exhibited better membrane performance (flux and humic acid removal) over commercial CTA membrane.

Keywords: cellulose triacetate, forward osmosis, humic acid, polyamide

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Authors: Benalia Kouini, Aicha Serier

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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: Sameh M. Osman, El-Refaie Kenawy, Zeid A. Al-Othman, Mohamed H. El-Newehy, El-Saied A. Aly, Sherine N. Khattab, Ayman El-Faham

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Recently, there has been a huge interest in using cyanuric chloride in a wide range of functional group transformations, as Cyanuric chloride has temperature-dependent differential reactivity for displacement of chlorides with various nucleophiles In the present work, some copolymers based on s-triazine Unit were prepared by microwave-assisted synthesis. For comparison study, the copolymers were synthesized by the conventional method. Synthesized Copolymers were characterized by MP, IR, TGA, DSC and GPC. The result indicated that copolymers are thermally stable and in good in composition and yield. Further studies that involve the test for selected removal of transition elements such as Cu (II), Zn (II) and Mn (II). Moreover, the effects of the polymeric triazine derivatives containing different functional groups which expected to have a good thermal stability and char formation ability on thermal degradation and flame retardancy.

Keywords: flame retardants, heavy metals, microwave-assisted synthesis, s-triazine

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Authors: Chih-Chi Cheng, Ji-Yu Lin, I-Ming Chu

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In this study, we synthesized a thermosensitive polypeptide hydrogel by copolymerizing poloxamer (PLX) and poly(ʟ-alanine) with ʟ-lysine segments at the both ends to form PLX-b-poly(ʟ-alanine-lysine) (Lys-Ala-PLX-Ala-Lys) copolymers. Poly(ʟ-alanine) is the hydrophobic chain of Lys-Ala-PLX-Ala-Lys copolymers which was designed to capture the hydrophobic agents. The synthesis was examined by 1H NMR and showed that Lys-Ala-PLX-Ala-Lys copolymers were successfully synthesized. At the concentration range of 3-7 wt%, the aqueous copolymer solution underwent sol-gel transition near the physiological temperature and exhibited changes in its secondary structure content, as evidenced by FTIR. The excellent viability of cells cultured within the scaffold was observed after 72 hr of incubation. Also, negatively charged bovine serum albumin was incorporated into the hydrogel without diminishing material integrity and shows good release profile. In the animal study, the results also indicated that Lys-Ala-PLX-Ala-Lys hydrogel has high potential in wound dressing.

Keywords: polypeptide thermosensitive hydrogel, tacrolimus, vascularized composite allotransplantation, sustain release

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Authors: El-Sayed Negim, Ainakulova D. T., Puteri S. M., Khaldun M. Azzam, Bekbayeva L. K., Arpit Goyal, Ganjian E.

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Anticorrosion coatings protect metal surfaces from environmental factors including moisture, oxygen, and gases that caused corrosion to the metal. Various types of anticorrosion coatings are available, with different properties and application methods. Many researchers have been developing methods to prevent corrosion, and epoxy polymers are one of the wide methods due to their excellent adhesion, chemical resistance, and durability. In this study, synthesis reactive dilute based on glycidyl methacrylate (GMA) with each of 2-ethylhexyl acrylate (2-EHA) and butyl acrylate (BuA) to improve the performance of epoxy resin and anticorrosion coating. The copolymers were synthesized with composition ratio (5/5) by bulk polymerization technique using benzoyl peroxide as a catalyst and temperature at 85 oC for 2 hours and at 90 oC for 30 minutes to complete the polymerization process. The obtained copolymers were characterized by FTIR, viscosity and thixotropic index. The effect of copolymers as reactive dilute on the physical and mechanical properties of epoxy resin was investigated. Metal plates coated by the modified epoxy resins with different contents of copolymers were tested using alkali and salt test methods, and the copolymer based on GMA and BUA showed the best protection efficiency due to the barrier effect of the polymer layer.

Keywords: epoxy, coating, dilute, corrosion, reactive

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Authors: Maria Bercea, Bernhard A. Wolf

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The thermodynamic behavior for solutions of poly (methyl methacrylate-ran-t-butyl methacrylate) of variable composition as compared with the corresponding homopolymers was investigated by light scattering measurements carried out for dilute solutions and vapor pressure measurements of concentrated solutions. The complex dependencies of the Flory Huggins interaction parameter on concentration and copolymer composition in solvents of different polarity (toluene and chloroform) can be understood by taking into account the ability of the polymers to rearrange in a response to changes in their molecular surrounding. A recent unified thermodynamic approach was used for modeling the experimental data, being able to describe the behavior of the different solutions by means of two adjustable parameters, one representing the effective number of solvent segments and another one accounting for the interactions between the components. Thus, it was investigated how the solvent quality changes with the composition of the copolymers through the Gibbs energy of mixing as a function of polymer concentration. The largest reduction of the Gibbs energy at a given composition of the system was observed for the best solvent. The present investigation proves that the new unified thermodynamic approach is a general concept applicable to homo- and copolymers, independent of the chain conformation or shape, molecular and chemical architecture of the components and of other dissimilarities, such as electrical charges.

Keywords: random copolymers, Flory Huggins interaction parameter, Gibbs energy of mixing, chemical architecture

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Authors: Nora A. Hamad, Ayman M. Atta, Adel A. H. Abdel-Rahman

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Two malice anhydride esters were prepared using long chain aliphatic alcohols (C8H17OH and C12H25OH, 1:1 mole ratio). Three series of crosslinked homo and copolymers of maleate esters with octadecyl acrylate and acrylic acid were prepared respectively through suspension copolymerization. The monomers were mixed with 0.02 Wt% of BP initiator, PVA 1% (170 ml for each 100g of monomers) and different weight ratios of DVB crosslinked (1% and 4%) in cyclohexane. The prepared crosslinked homo and copolymers were characterized by SEM, TGA and FTIR spectroscopic analyses. The prepared polymers were coated onto poly (ethylene terephethalate) nonwoven fiber (NWPET). The effect of copolymerization feed composition, crosslinker wt% and reaction media or solvent on swelling properties of crosslinked polymers were studied through the oil absorption tests in toluene and 10% of diluted crude oil with toluene.

Keywords: acrylic acid, crosslinked copolymers, maleate ester, poly(ethylene terephethalate) nonwoven fiber (NWPET), oil absorbency, octadecyl acrylat

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Authors: A. Sezai Sarac

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Acrylonitrile (AN) copolymers with typical comonomers of vinyl acetate (VAc) or methyl acrylate (MA) exhibit better mechanical behaviors than its homopolymer. To increase processability of conjugated polymer, and to obtain a hybrid nano-structure multi-stepped emulsion polymerization was applied. Such products could be used in, i.e., drug-delivery systems, biosensors, gas-sensors, electronic compounds, etc. Incorporation of a number of flexible comonomers weakens the dipolar interactions among CN and thereby decreases melting point or increases decomposition temperatures of the PAN based copolymers. Hence, it is important to consider the effect of comonomer on the properties of PAN-based copolymers. Acrylonitrile vinylacetate (AN–VAc ) copolymers have the significant effect to their thermal behavior and are also of interest as precursors in the production of high strength carbon fibers. AN is copolymerized with one or two comonomers, particularly with vinyl acetate The copolymer of AN and VAc can be used either as a plastic (VAc > 15 wt %) or as microfibers (VAc < 15 wt %). AN provides the copolymer with good processability, electrochemical and thermal stability; VAc provides the mechanical stability. The free radical copolymerization of AN and VAc copolymer and core Shell structure of polyprrole composites,and nanofibers of poly(m-anthranilic acid)/polyacrylonitrile blends were recently studied. Free radical copolymerization of acrylonitrile (AN) – with different comonomers, i.e. acrylates, and styrene was realized using ammonium persulfate (APS) in the presence of a surfactant and in-situ polymerization of conjugated polymers was performed in this reaction medium to obtain core-shell nano particles. Nanofibers of such nanoparticles were obtained by electrospinning. Morphological properties of nanofibers are investigated by scanning electron microscopy (SEM) and atomic force spectroscopy (AFM). Nanofibers are characterized using Fourier Transform Infrared - Attenuated Total Reflectance spectrometer (FTIR-ATR), Nuclear Magnetic Resonance Spectroscopy (1H-NMR), differential scanning calorimeter (DSC), thermal gravimetric analysis (TGA), and Electrochemical Impedance Spectroscopy. The electrochemical Impedance results of the nanofibers were fitted to an equivalent curcuit by modelling (ECM).

Keywords: core shell nanoparticles, nanofibers, ascrylonitile copolymers, hybrid nanostructures

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Authors: Ramita Vongrat, Pornsri Sapsrithong, Manit Nithitanakul

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In this work, blends of polyamide 6 (PA6) and polybutylene terephthalate (PBT) were successfully prepared. The effect of epoxidized natural rubber (ENR-25) and n butyl acrylate glycidyl methacrylate ethylene (EBa-GMA) as a compatibilizer on properties of PA6/PBT blends was also investigated by varying amount of ENR-50 and EBa-GMA, i.e., 0, 0.1, 0.5, 5 and 10 phr. All blends were prepared and shaped by using twin-screw extruder at 230 °C and injection molding machine, respectively. All test specimens were characterized by phase morphology, impact strength, tensile, flexural properties, and hardness. The results exhibited that phase morphology of PA6/PBT blend without compatibilizer was incompatible. This could be attributed to poor interfacial adhesion between the two polymers. SEM micrographs showed that the addition of ENR-25 and EBa-GMA improved the compatibility of PA6/PBT blends. With the addition of ENR-50 as a compatibilizer, the uniformity and the maximum reduction of dispersed phase size were observed. Additionally, the results indicate that, as the amount of ENR-25 increased, and EBa-GMA increased, the mechanical properties, including stress at the peak, tensile modulus, and izod impact strength, were also improved.

Keywords: EBa-GMA, epoxidized natural rubber-25, polyamide 6, polybutylene terephthalate

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Authors: Hamed Rajabzadeh Gatabi, Soroush Dastgheibifard, Mahsa Asnafi

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There is no doubt that reinforced concrete is known as one of the most significant materials which is used in construction industry for many years. Although, some natural elements in dealing with environment can contribute to its corrosion or failure. One of which is bar or so-called reinforcement failure. So as to combat this problem, one of the oxidization prevention methods investigated was the barrier protection method implemented over the application of an organic coating, specifically fusion-bonded epoxy. In this study comparative method is prepared on two different kinds of covered bars (zinc-riches epoxy and polyamide epoxy coated bars) and also uncoated bar. With the aim of evaluate these reinforced concretes, the stickiness, toughness, thickness and corrosion performance of coatings were compared by some tools like Cu/CuSo4 electrodes, EIS and etc. Different types of concretes were exposed to the salty environment (NaCl 3.5%) and their durability was measured. As stated by the experiments in research and investigations, thick coatings (named epoxies) have acceptable stickiness and strength. Polyamide epoxy coatings stickiness to the bars was a bit better than that of zinc-rich epoxy coatings; nonetheless it was stiffer than the zinc rich epoxy coatings. Conversely, coated bars with zinc-rich epoxy showed more negative oxidization potentials, which take revenge protection of bars by zinc particles. On the whole, zinc-rich epoxy coverings is more corrosion-proof than polyamide epoxy coatings due to consuming zinc elements and some other parameters, additionally if the epoxy coatings without surface defects are applied on the rebar surface carefully, it can be said that the life of steel structures is subjected to increase dramatically.

Keywords: surface coating, epoxy polyamide, reinforce concrete bars, salty environment

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Authors: I. Irska, S. Paszkiewicz, D. Pawlikowska, E. Piesowicz, A. Linares, T. A. Ezquerra

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Due to the number of advantages such as high tensile strength, sensitivity to hydrolytic degradation, and biocompatibility poly(lactic acid) (PLA) is one of the most common polyesters for biomedical and pharmaceutical applications. However, PLA is a rigid, brittle polymer with low heat distortion temperature and slow crystallization rate. In order to broaden the range of PLA applications, it is necessary to improve these properties. In recent years a number of new strategies have been evolved to obtain PLA-based materials with improved characteristics, including manipulation of crystallinity, plasticization, blending, and incorporation into block copolymers. Among the other methods, synthesis of aliphatic-aromatic copolyesters has been attracting considerable attention as they may combine the mechanical performance of aromatic polyesters with biodegradability known from aliphatic ones. Given the need for highly flexible biodegradable polymers, in this contribution, a series of aromatic-aliphatic based on poly(butylene terephthalate) and poly(lactic acid) (PBT-b-PLA) copolyesters exhibiting superior mechanical properties were copolymerized with an additional poly(tetramethylene oxide) (PTMO) soft block. The structure and properties of both series were characterized by means of attenuated total reflectance – Fourier transform infrared spectroscopy (ATR-FTIR), nuclear magnetic resonance spectroscopy (¹H NMR), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and dynamic mechanical, thermal analysis (DMTA). Moreover, the related changes in tensile properties have been evaluated and discussed. Lastly, the viscoelastic properties of synthesized poly(ester-ether) copolymers were investigated in detail by step cycle tensile tests. The block lengths decreased with the advance of treatment, and the block-random diblock terpolymers of (PBT-ran-PLA)-b-PTMO were obtained. DSC and DMTA analysis confirmed unambiguously that synthesized poly(ester-ether) copolymers are microphase-separated systems. The introduction of polyether co-units resulted in a decrease in crystallinity degree and melting temperature. X-ray diffraction patterns revealed that only PBT blocks are able to crystallize. The mechanical properties of (PBT-ran-PLA)-b-PTMO copolymers are a result of a unique arrangement of immiscible hard and soft blocks, providing both strength and elasticity.

Keywords: aliphatic-aromatic copolymers, multiblock copolymers, phase behavior, thermoplastic elastomers

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Authors: Nasser A. M. Barakat

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Membrane technology is the most promising process for oil-water separation operation if the hydrophilicity, fouling and reusability properties could be improved. In this study, novel effective and reusable membrane for oil-water separation process is introduced based on modification of polysulfone (PSF) electrospun nanofiber mats. The modification process was achieved by incorporation of NaOH nanoparticles inside the PSF nanofibers, and formation of a thin layer from a polyamide polymer on the surface of the electrospun mat. Typically, solutions composed of PSF and NaOH (twelve solutions were prepared based on different PSF concentrations; 15, 18 and 20 wt%, and various NaOH content; 1.5, 1.7 and 2.5 wt%) have been electrospun, then the dried nanofiber mats were treated by m-phenylenediamine and 1,3,5-benzenetricarbonyl chloride to form polyamide thin layer on the surface of the mats. The results indicated that incorporation of NaOH and the formed polyamide could decrease the water contact angle from ~ 130˚ to 13˚ for the nanofiber mats obtained from 20 wt% PSF solutions containing 1.7 wt% sodium hydroxide powders. Interestingly, the membrane having the lowest contact angle could separate oil-water mixture for three successive cycles and 100% removal of the oil with relatively high water flux; 5.5 m3/m2.day. Overall, simplicity of the manufacturing technique, and effectiveness and reusability of the produced nanofiber mats open new avenue for the introduced as promising membranes for the oil-water separation process.

Keywords: electrospinning, oil-water separation, hydrophilic membrane, nanofibers

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Authors: Nandhini Ravi, Muthukumaran Shanmugam

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Metals are being replaced by thermoplastic polymer composites in automotive industries because of their low density, easiness to fabricate, low cost and good wear resistance. Complex polymer components consist of assemblies of smaller parts which can be joined by friction stir welding. This study deals with the additive friction stir welding of 15 wt.% glass fiber reinforced polyamide 66 composite which is a modified technique of the conventional friction stir welding by the addition of a filler plate for the heating of the composite work piece through the tool during the welding process. Welding at different combinations of tool rotational speed, travel speed and tool plunge depth was done after which the tensile strength of the respective experiments was determined. The maximum tensile strength obtained was 77 MPa which was 80% of the strength of the base material. The process parameters were optimized using the L9 orthogonal array and also the effect of individual welding parameter on the tensile strength was studied. The optimum parameter combination was determined with the help of ANOVA studies. The hardness of the welded joints was studied with the help of Shore Durometer which yielded the maximum of D 75.

Keywords: additive friction stir welding, polyamide 66, process parameters, thermoplastic polymer composite

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Authors: Marco Soto-Arriaza, Eduardo Cena-Ahumada, Jaime Melendez-Rojel

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Background: Liposomes have been widely used as a model of lipid bilayer to study the physicochemical properties of biological membrane, encapsulation, transport and release of different molecules. Furthermore, extensive research has focused on improving the efficiency in the transport of drugs, developing tools that improve the release of the encapsulated drug from liposomes. In this context, the enzymatic activity of PLA₂, despite having been shown to be an effective tool to promote the release of drugs from liposomes, is still an open field of research. Aim: The aim of the present study is to explore the effect of cholesterol (Cho) and amphipathic di- and tri-block copolymers, on calcein release mediated by enzymatic activity of PLA2 in Dipalmitoylphosphatidylcholine (DPPC) liposomes under physiological conditions. Methods: Different dispersions of DPPC, cholesterol, di-block POE₄₅-PCL₅₂ or tri-block PCL₁₂-POE₄₅-PCL₁₂ were prepared by the extrusion method after five freezing/thawing cycles; in Phosphate buffer 10mM pH 7.4 in presence of calcein. DPPC liposomes/Calcein were centrifuged at 15000rpm 10 min to separate free calcein. Enzymatic activity assays of PLA₂ were performed at 37°C using the TBS buffer pH 7.4. The size distribution, polydispersity, Z-potential and Calcein encapsulation of DPPC liposomes was monitored. Results: PLA₂ activity showed a slower kinetic of calcein release up to 20 mol% of cholesterol, evidencing a minimum at 10 mol% and then a maximum at 18 mol%. Regardless of the percentage of cholesterol, up to 18 mol% a one-hundred percentage release of calcein was observed. At higher cholesterol concentrations, PLA₂ showed to be inefficient or not to be involved in calcein release. In assays where copolymers were added in a concentration lower than their cmc, a similar behavior to those showed in the presence of Cho was observed, that is a slower kinetic in calcein release. In both experimental approaches, a one-hundred percentage of calcein release was observed. PLA₂ was shown to be sensitive to the 4-(4-Octadecylphenyl)-4-oxobutenoic acid inhibitor and calcium, reducing the release of calcein to 0%. Cell viability of HeLa cells decreased 7% in the presence of DPPC liposomes after 3 hours of incubation and 17% and 23% at 5 and 15 hours, respectively. Conclusion: Calcein release from DPPC liposomes, mediated by PLA₂ activity, depends on the percentage of cholesterol and the presence of copolymers. Both, cholesterol up to 20 mol% and copolymers below it cmc could be applied to the regulation of the kinetics of antitumoral drugs release without inducing cell toxicity per se.

Keywords: amphipathic copolymers, calcein release, cholesterol, DPPC liposome, phospholipase A₂

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Authors: Soner Guler, Demet Yavuz, Fuat Korkut

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Synthetic fibers are commonly used in many civil engineering applications because of its some superior characteristics such as non-corrosive and cheapness. This study presents the results of experimental study on compressive strength of synthetic fiber reinforced concretes. Two types of polyamide (PA) synthetic fiber with the length of 12 and 54 mm are used for this study. The fiber volume ratio is kept as 0.25%, 0.75%, and 0.75% in all mixes. The plain concrete compressive strength is 36.2 MPa. The test results clearly show that the increase in compressive strength for synthetic fiber reinforced concretes is significant. The greatest increase in compressive strength is 23% for PA synthetic fiber reinforced concretes with 0.75% fiber volume.

Keywords: synthetic fibers, polyamide fibers, fiber volume, compressive strength

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Authors: Loredana Elena Nita, Maria Bercea, Aurica P. Chiriac, Iordana Neamtu

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The paper is devoted to the behavior of gels based on poly(itaconic anhydride-co-3, 9-divinyl-2, 4, 8, 10-tetraoxaspiro (5.5) undecane) copolymers, with different ratio between the comonomers, and hyaluronic acid (HA). The gel formation was investigated by small-amplitude oscillatory shear measurements following the viscoelastic behavior as a function of gel composition, temperature and shear conditions. Hyaluronic acid was investigated in the same conditions and its rheological behavior is typical to viscous fluids. In the case of the copolymers, the ratio between the two comonomers influences the viscoelastic behavior, a higher content of itaconic anhydride favoring the gel formation. Also, the sol-gel transition was evaluated according to Winter-Chambon criterion that identifies the gelation point when the viscoelastic moduli (G’ and G”) behave similarly as a function of oscillation frequency. From rheological measurements, an optimum composition was evidenced for which the system presents a typical gel-like behavior at 37 °C: the elastic modulus is higher than the viscous modulus and they are not dependent on the oscillation frequency. The formation of the 3D macroporous network was also evidenced by FTIR spectra, SEM microscopy and chemical imaging. These hydrogels present a high potential as drug delivery systems.

Keywords: copolymer, viscoelasticity, gelation, 3D network

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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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Authors: Karima Chergui, Hichem Amrani, Hammoudi Mazouz, Fatiha Mezaache

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Cemented femoral resurfacings have experienced a revival for younger and more active patients. Future developments have shown that the uncemented version eliminates failures related to cementing implants. A three-dimensional finite element method (FEM) simulation was carried out in order to exploit a new resurfacing prothesis design named MARMEL, proposed by a recent study with Co–Cr–Mo material, for comparing a hip uncemented resurfacing with a novel carbon fiber/polyamide 12 (CF/PA12) composite to other hip resurfacing implants with various bio materials. From FE analysis, the von Mises stress range for the Composite hip resurfacing was much lower than that in the other hip resurfacing implants used in this comparison. These outcomes showed that the biomimetic hip resurfacing had the potential to reduce stress shielding and prevent from bone fracture compared to conventional hip resurfacing implants.

Keywords: biomechanics, carbon–fibre polyamide 12, finite element analysis, hip resurfacing

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Authors: J. Klofac, P. Bazant, I. Kuritka

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This work is focused on the preparation of polymeric blend composed of polyamide (PA) and polyvinyl alcohol (PVA) with the intention to explore its basic characteristics important for potential use in medicine, especially for drug delivery systems. PA brings brilliant mechanical properties to the blend while PVA is inevitable due to its water solubility. Blend with different PA/PVA ratios were prepared and the release study of PVA into the water was carried out in a time interval 0-48 hours via the gravimetric method. The weight decrease is caused by the leaching of PVA domains what can be also followed by the optical and scanning electron microscopy. In addition, the thermal properties and the miscibility of blend components were evaluated by the differential scanning calorimeter. On the bases of performed experiments, it was found that the kinetics, continuity development and micro structure features of PA/PVA blends is strongly dependent on the blend composition and miscibility of its components.

Keywords: releas study, polyvinyl alcohol, polyamide morphology, polymeric blend

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Authors: Khodzhaberdi Allaberdiev

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In order to understand the interactions on the interface polyamide fibers and epoxy matrix in fiber- reinforced composites were investigated industrial aramid fibers: armos, svm, terlon using individual epoxy matrix components, epoxies: diglycidyl ether of bisphenol A (DGEBA), three- and diglycidyl derivatives of m, p-amino-, m, p-oxy-, o, m,p-carboxybenzoic acids, the models: curing agent, aniline and the compound, that depict of the structure the primary addition reaction the amine to the epoxy resin, N-di (oxyethylphenoxy) aniline. The chemical structure of the surface of untreated and treated polyamide fibers analyzed using Fourier transform infrared spectroscopy (FTIR). The impregnation of fibers with epoxy matrix components and N-di (oxyethylphenoxy) aniline has been carried out by heating 150˚C (6h). The optimum fiber loading is at 65%.The result a thermal treatment is the covalent bonds formation , derived from a combined of homopolymerization and crosslinking mechanisms in the interfacial region between the epoxy resin and the surface of fibers. The reactivity of epoxy resins on interface in microcomposites (MC) also depends from processing aids treated on surface of fiber and the absorbance moisture. The influences these factors as evidenced by the conversion of epoxy groups values in impregnated with DGEBA of the terlons: industrial, dried (in vacuum) and purified samples: 5.20 %, 4.65% and 14.10%, respectively. The same tendency for svm and armos fibers is observed. The changes in surface composition of these MC were monitored by X-ray photoelectron spectroscopy (XPS). In the case of the purified fibers, functional groups of fibers act as well as a catalyst and curing agent of epoxy resin. It is found that the value of the epoxy groups conversion for reinforced formulations depends on aromatic polyamides nature and decreases in the order: armos >svm> terlon. This difference is due of the structural characteristics of fibers. The interfacial interactions also examined between polyglycidyl esters substituted benzoic acids and polyamide fibers in the MC. It is found that on interfacial interactions these systems influences as well as the structure and the isomerism of epoxides. The IR-spectrum impregnated fibers with aniline showed that the polyamide fibers appreciably with aniline do not react. FTIR results of treated fibers with N-di (oxyethylphenoxy) aniline fibers revealed dramatically changes IR-characteristic of the OH groups of the amino alcohol. These observations indicated hydrogen bondings and covalent interactions between amino alcohol and functional groups of fibers. This result also confirms appearance of the exo peak on Differential Scanning Calorimetry (DSC) curve of the MC. Finally, the theoretical evaluation non-covalent interactions between individual epoxy matrix components and fibers has been performed using the benzanilide and its derivative contaning the benzimidazole moiety as a models of terlon and svm,armos, respectively. Quantum-topological analysis also demonstrated the existence hydrogen bond between amide group of models and epoxy matrix components.All the results indicated that on the interface polyamide fibers and epoxy matrix exist not only covalent, but and non-covalent the interactions during the preparation of MC.

Keywords: epoxies, interface, modeling, polyamide fibers

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Authors: Jifeng Zhang , Yongpeng Lei

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Continuous carbon fiber reinforced polyamide 6 (CF/PA6) composites are potential for application in the automotive industry due to their high specific strength and stiffness. However, PA6 resin is sensitive to the moisture in the hydrothermal environment and CF/PA6 composites might undergo several physical and chemical changes, such as plasticization, swelling, and hydrolysis, which induces a reduction of mechanical properties. So far, little research has been reported on the assessment of the effects of hydrothermal aging on the mechanical properties of continuous CF/PA6 composite. This study deals with the effects of hydrothermal aging on moisture absorption and mechanical properties of polyamide 6 (PA6) and polyamide 6 reinforced with continuous carbon fibers composites (CF/PA6) by immersion in distilled water at 30 ℃, 50 ℃, 70 ℃, and 90 ℃. Degradation of mechanical performance has been monitored, depending on the water absorption content and the aging temperature. The experimental results reveal that under the same aging condition, the PA6 resin absorbs more water than the CF/PA6 composite, while the water diffusion coefficient of CF/PA6 composite is higher than that of PA6 resin because of interfacial diffusion channel. In mechanical properties degradation process, an exponential reduction in tensile strength and elastic modulus are observed in PA6 resin as aging temperature and water absorption content increases. The degradation trend of flexural properties of CF/PA6 is the same as that of tensile properties of PA6 resin. Moreover, the water content plays a decisive role in mechanical degradation compared with aging temperature. In contrast, hydrothermal environment has mild effect on the tensile properties of CF/PA6 composites. The elongation at breakage of PA6 resin and CF/PA6 reaches the highest value when their water content reaches 6% and 4%, respectively. Dynamic mechanical analysis (DMA) and scanning electron microscope (SEM) were also used to explain the mechanism of mechanical properties alteration. After exposed to the hydrothermal environment, the Tg (glass transition temperature) of samples decreases dramatically with water content increase. This reduction can be ascribed to the plasticization effect of water. For the unaged specimens, the fibers surface is coated with resin and the main fracture mode is fiber breakage, indicating that a good adhesion between fiber and matrix. However, with absorbed water content increasing, the fracture mode transforms to fiber pullout. Finally, based on Arrhenius methodology, a predictive model with relate to the temperature and water content has been presented to estimate the retention of mechanical properties for PA6 and CF/PA6.

Keywords: continuous carbon fiber reinforced polyamide 6 composite, hydrothermal aging, Arrhenius methodology, interface

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Authors: Hussein M. Etmimi, Peter E. Mallon

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Electrospinning uses an electrical charge to draw very fine fibers (typically on the micro or nano scale) from a liquid or molten precursor. Over the years, this method has become a widely used and a successful technique to process polymer materials and their composites into nanofibers. The main focus of this work is to study the electrospinning of multi-phase amphiphilic copolymers and their nanocomposites, which contain graphene as the nanofiller material. In such amphiphilic materials, the constituents segments are incompatible and thus the solid state morphology will be determined by the composition of the various constituents as well as the method of preparation. In this study, amphiphilic block copolymers of poly(dimethyl siloxane) and poly(methyl methacrylate) (PDMS-b-PMMA) with well-defined structures were synthesized and the solution electrospinning of these materials and their properties were investigated. Atom transfer radical polymerization (ATRP) was used to obtain the controlled block copolymers with relatively high molar masses and narrow dispersity. First, PDMS macroinitiators with different chain length of 1000, 5000 and 10000 g/mol were synthesized by the reaction of monocarbinol terminated PDMS with α-bromoisobutyryl bromide initiator. The obtained macroinitiators were used for the polymerization of methyl methacrylate monomer to obtain the desired block copolymers using the ATRP process. Graphene oxide (GO) of different loading was then added to the copolymer solution and the resultant nanocomposites were successfully electrospun into nanofibers. The electrospinning was achieved using dimethylformamide/chloroform mixture (60:40 vl%) as electrospinning solution medium. Scanning electron microscopy (SEM) showed the successful formation of the electrospun fibers with dimensions in the nanometer range. X-ray diffraction indicated that the GO nanosheets were of an exfoliated structure, irrespective of the filler loading. Thermogravimetric analysis also showed that the thermal stability of the nanofibers was improved in the presence of GO, which was not a function of the filler loading. Differential scanning calorimetry also showed that the mechanical properties (measured as glass transition temperature) of the nanofibers was improved significantly in the presence of GO, which was a function of the filler loading.

Keywords: elctrospinning, graphene oxide, nanofibers, polymethyl methacrylate (PMMA)

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Authors: Irati Barandiaran, Xabier Velasco-Iza, Galder Kortaberria

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Hybrid inorganic/organic nanostructured materials based on block copolymers are of considerable interest in the field of Nanotechnology, taking into account that these nanocomposites combine the properties of polymer matrix and the unique properties of the added nanoparticles. The use of block copolymers as templates offers the opportunity to control the size and the distribution of inorganic nanoparticles. This research is focused on the surface modification of inorganic nanoparticles to reach a good interface between nanoparticles and polymer matrices which hinders the nanoparticle aggregation. The aim of this work is to obtain a good and selective dispersion of Fe3O4 magnetic nanoparticles into different types of block copolymers such us, poly(styrene-b-methyl methacrylate) (PS-b-PMMA), poly(styrene-b-ε-caprolactone) (PS-b-PCL) poly(isoprene-b-methyl methacrylate) (PI-b-PMMA) or poly(styrene-b-butadiene-b-methyl methacrylate) (SBM) by using different grafting strategies. Fe3O4 magnetic nanoparticles have been surface-modified with polymer or block copolymer brushes following different grafting methods (grafting to, grafting from and grafting through) to achieve a selective location of nanoparticles into desired domains of the block copolymers. Morphology of fabricated hybrid nanocomposites was studied by means of atomic force microscopy (AFM) and with the aim to reach well-ordered nanostructured composites different annealing methods were used. Additionally, nanoparticle amount has been also varied in order to investigate the effect of the nanoparticle content in the morphology of the block copolymer. Nowadays different characterization methods were using in order to investigate magnetic properties of nanometer-scale electronic devices. Particularly, two different techniques have been used with the aim of characterizing synthesized nanocomposites. First, magnetic force microscopy (MFM) was used to investigate qualitatively the magnetic properties taking into account that this technique allows distinguishing magnetic domains on the sample surface. On the other hand, magnetic characterization by vibrating sample magnetometer and superconducting quantum interference device. This technique demonstrated that magnetic properties of nanoparticles have been transferred to the nanocomposites, exhibiting superparamagnetic behavior similar to that of the maghemite nanoparticles at room temperature. Obtained advanced nanostructured materials could found possible applications in the field of dye-sensitized solar cells and electronic nanodevices.

Keywords: atomic force microscopy, block copolymers, grafting techniques, iron oxide nanoparticles

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Authors: S. Paszkiewicz, A. Zubkiewicz, A. Szymczyk, D. Pawlikowska, I. Irska, E. Piesowicz, A. Linares, T. A. Ezquerra

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Over the last century, the world has become increasingly dependent on oil as its main source of chemicals and energy. Driven largely by the strong economic growth of India and China, demand for oil is expected to increase significantly in the coming years. This growth in demand, combined with diminishing reserves, will require the development of new, sustainable sources for fuels and bulk chemicals. Biomass is an attractive alternative feedstock, as it is widely available carbon source apart from oil and coal. Nowadays, academic and industrial research in the field of polymer materials is strongly oriented towards bio-based alternatives to petroleum-derived plastics with enhanced properties for advanced applications. In this context, 2,5-furandicarboxylic acid (FDCA), a biomass-based chemical product derived from lignocellulose, is one of the most high-potential biobased building blocks for polymers and the first candidate to replace the petro-derived terephthalic acid. FDCA has been identified as one of the top 12 chemicals in the future, which may be used as a platform chemical for the synthesis of biomass-based polyester. The aim of this study is to synthesize and characterize the multiblock copolymers containing rigid segments of poly(trimethylene 2,5-furanoate) (PTF) and soft segments of poly(tetramethylene oxide) (PTMO) with excellent elastic properties or aliphatic polyesters of polycaprolactone (PCL). Two series of PTF based copolymers, i.e., PTF-block-PTMO-T and PTF-block-PCL-T, with different content of flexible segments were synthesized by means of a two-step melt polycondensation process and characterized by various methods. The rigid segments of PTF, as well as the flexible PTMO/or PCL ones, were randomly distributed along the chain. On the basis of 1H NMR, SAXS and WAXS, DSC an DMTA results, one can conclude that both phases were thermodynamically immiscible and the values of phase transition temperatures varied with the composition of the copolymer. The copolymers containing 25, 35 and 45wt.% of flexible segments (PTMO) exhibited elastomeric property characteristics. Moreover, with respect to the flexible segments content, the temperatures corresponding to 5%, 25%, 50% and 90% mass loss as well as the values of tensile modulus decrease with the increasing content of aliphatic polyether or aliphatic polyester in the composition.

Keywords: furan based polymers, multiblock copolymers, supramolecular structure, functional properties

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Authors: Bo Keun Lee, Doo Yeon Kwon, Ji Hoon Park, Gun Hee Lee, Ji Hye Baek, Heung Jae Chun, Young Joo Koh, Moon Suk Kim

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Thermo-responsive materials are viscoelastic materials that undergo a sol-to-gel phase transition at a specific temperature and many materials have been developed. MPEG-b-PCL (MPC) as a thermo-responsive material contained hydrophilic and hydrophobic segments and it formed an ordered crystalline structure of hydrophobic PCL segments in aqueous solutions. The ordered crystalline structure packed tightly or aggregated and finally induced an aggregated gel through intra- and inter-molecular interactions as a function of temperature. Thus, we introduced anionic and cationic groups into the end positions of the PCL chain to alter the hydrophobicity of the PCL segment. Introducing anionic and cationic groups into the PCL end position altered their solubility by changing the crystallinity and hydrophobicity of the PCL block domains. These results indicated that the properties of the end group in the hydrophobic PCL blockand the balance between hydrophobicity and hydrophilicity affect thermo-responsivebehavior of the copolymers in aqueous solutions. Thus, we concluded that determinant of the temperature-dependent thermo-responsive behavior of MPC depend on the ionic end group in the PCL block. So, we introduced zwitterionic end groups to investigate the thermo-responsive behavior of MPC. Methoxypoly(ethylene oxide) and ε-caprolactone (CL) were randomly copolymerized that introduced varying hydrophobic PCL lengths and an MPC featuring a zwitterionic sulfobetaine (MPC-ZW) at the chain end of the PCL segment. The MPC and MPC-ZW copolymers were obtained formed sol-state at room temperature when prepared as 20-wt% aqueous solutions. The solubility of MPC decreased when the PCL block was increased from molecular weight. The solubilization time of MPC-2.4k was around 20 min and MPC-2.8k, MPC-3.0k increased to 30 min and 1 h, respectively. MPC-3.6k was not solubilized. In case of MPC-ZW 3.6k, However, the zwitterion-modified MPC copolymers were solubilized in 3–5 min. This result indicates that the zwitterionic end group of the MPC-ZW diblock copolymer increased the aqueous solubility of the diblock copolymer even when the length of the hydrophobic PCL segment was increased. MPC and MPC-ZW diblock copolymers that featuring zwitterionic end groups were synthesized successfully. The sol-to-gel phase-transition was formed that specific temperature depend on the length of the PCL hydrophobic segments introduced and on the zwitterion groups attached to the MPC chain end. This result indicated that the zwitterionic end groups reduced the hydrophobicity in the PCL block and changed the solubilization. The MPC-ZW diblock copolymer can be utilized as a potential injectable drug and cell carrier.

Keywords: thermo-responsive material, zwitterionic, hydrophobic, crystallization, phase transition

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Authors: Victoria I. Michailova, Denitsa B. Momekova, Hristiana A. Velichkova, Evgeni H. Ivanov

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The aim of this work is to design and develop thermo-responsive nanosized drug delivery systems based on poly(N-isopropylacrylamide)-g-poly(ethylene oxide) (PNIPAM-g-PEO) double hydrophilic graft copolymers. The PNIPAM-g-PEO copolymers are able to self-assemble in water into nanoparticles above the LCST of the thermo-responsive PNIPAM backbone and to disassemble and rapidly release the entrapped drugs upon cooling. However, their drug delivery applications are often hindered by their low loading capacity as the drugs to be encapsulated do not dissolve in water. In order to overcome this limitation, here we applied a low-temperature procedure with ethanol as an alternative route to the formation and loading a model hydrophobic drug, Indomethacin (IMC), into PNIPAM-g-PEO nanoparticles. The rationale for this approach was that ethanol dissolves both IMC and the copolymer and its mixing with water may induce micellization of PNIPAM-g-PEO at temperatures lower than the LCST. The influence of the volume fraction of ethanol and the temperature on the aggregation characteristics of PNIPAM-g-PEO copolymers (2.7 mol% PEO) was investigated by means of DLS, TEM and rheological dynamic oscillatory tests. The studies showed rich phase behavior at T < LCST, incl. the formation of highly solvated 500-1000 nm complex structures, 30-70 nm micelles and polymersomes as well as giant polymersomes, as the fraction of added ethanol increased. We believe that the PNIPAM-g-PEO self-assembly is favored due to the different solvation of its constituting blocks in ethanol-water mixtures. The incorporation of IMC led to alteration of the physicochemical and morphological characteristics of the blank nanoparticles. In this case, only monodisperse polymersomes and micelles were observed in the solutions with an average diameter less than 65 nm and substantial drug loading (DLC ~117 – 146 wt%). Indomethacin release from the nanoparticles was responsive to temperature changes, being much faster at a temperature of 42oC compared to that of 37oC under otherwise the same conditions. The results obtained suggest that these PNIPAM-g-PEO nanoparticles could be potential in mild hyper-thermic delivery of nonsteroidal anti-inflammatory drugs.

Keywords: drug delivery, nanoparticles, poly(N-isopropylacryl amide)-g-poly(ethylene oxide), thermo-responsive

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