Search results for: methacrylate copolymer

Authors: Caroline Rocco, Feyza Karasu, Céline Croutxé-Barghorn, Xavier Allonas, Maxime Lecompère, Gérard Riess, Yujing Zhang, Catarina Esteves, Leendert van der Ven, Rolf van Benthem Gijsbertus de With

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Acrylates are widely used in UV-curing technology. Their high reactivity can, however, limit their conversion due to early vitrification. In addition, the free radical photopolymerization is known to be sensitive to oxygen inhibition leading to tacky surfaces. Although epoxides can lead to full polymerization, they are sensitive to humidity and exhibit low polymerization rate. To overcome the intrinsic limitations of both classes of monomers, Interpenetrating Polymer Networks (IPNs) can be synthesized. They consist of at least two cross linked polymers which are permanently entangled. They can be achieved under thermal and/or light induced polymerization in one or two steps approach. IPNs can display homogeneous to heterogeneous morphologies with various degrees of phase separation strongly linked to the monomer miscibility and also synthesis parameters. In this presentation, we synthesize UV-cured methacrylate - epoxide based IPNs with different chemical compositions in order to get a better understanding of their formation and phase separation. Miscibility before and during the photopolymerization, reaction kinetics, as well as mechanical properties and morphology have been investigated. The key parameters controlling the morphology and the phase separation, namely monomer miscibility and synthesis parameters have been identified. By monitoring the stiffness changes on the film surface, atomic force acoustic microscopy (AFAM) gave, in conjunction with polymerization kinetic profiles and thermomechanical properties, explanations and corroborated the miscibility predictions. When varying the methacrylate / epoxide ratio, it was possible to move from a miscible and highly-interpenetrated IPN to a totally immiscible and phase-separated one.

Keywords: investigation of properties and morphology, kinetics, phase separation, UV-cured IPNs

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Authors: Muhammad Zahid, Ilker S. Bayer, Athanassia Athanassiou

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Fluorinated polymers having C8 chemistry (chemicals with 8 fluorinated carbon atoms) are well renowned for their excellent low surface tension and water repelling properties. However, these polymers degrade into highly toxic heavy perfluoro acids in the environment. When the C8 chemistry is reduced to C6 chemistry, this environmental concern is eliminated at the expense of reduced liquid repellent performance. In order to circumvent this, in this study, we demonstrate pre-treatment of woven cotton fabrics with a fluorinated acrylic copolymer with C6 chemistry and subsequently with a silicone polymer to render them hydrophobic. A commercial fluorinated acrylic copolymer was blended with silica nanoparticles to form hydrophobic nano-roughness on cotton fibers and a second coating layer of polydimethylsiloxane (PDMS) was applied on the fabric. A static water contact angle (for 5µl) and rolling angle (for 12.5µl) of 147°±2° and 31° were observed, respectively. Hydrostatic head measurements were also performed to better understand the performance with 26±1 cm and 2.56kPa column height and static pressure respectively. Fabrication methods (with rod coater etc.) were kept simple, reproducible, and scalable and cost efficient. Moreover, the robustness of applied coatings was also evaluated by sonication cleaning and abrasion methods. Water contact angle (WCA), water shedding angle (WSA), hydrostatic head, droplet bouncing-rolling off and prolonged staining tests were used to characterize hydrophobicity of materials. For chemical and morphological analysis, various characterization methods were used such as attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), atomic force microscopy (AFM) and scanning electron microscopy (SEM).

Keywords: fluorinated polymer, hydrophobic, polydimethylsiloxane, water contact angle

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Authors: Shima Taheri, Simon Clark

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Concrete is an essential building material used in the majority of structures. Degradation of concrete over time increases the life-cycle cost of an asset with an estimated annual cost of billions of dollars to national economies. Most of the concrete failure occurs due to cracks, which propagate through a structure and cause weakening leading to failure. Stopping crack propagation is thus the key to protecting concrete structures from failure and is the best way to prevent inconveniences and catastrophes. Furthermore, the majority of cracks occur deep within the concrete in inaccessible areas and are invisible to normal inspection. Few materials intrinsically possess self-healing ability, but one that does is concrete. However, self-healing in concrete is limited to small dormant cracks in a moist environment and is difficult to control. In this project, we developed a method for self-healing of nascent fractures in concrete components through the automatic release of self-curing healing agents encapsulated in breakable nano- and micro-structures. The Poly(methyl methacrylate) (PMMA) based two-part adhesive is encapsulated in core-shell structures with brittle/weak inert shell, synthesized via miniemulsion/solvent evaporation polymerization. Stress fields associated with propagating cracks can break these capsules releasing the healing agents at the point where they are needed. The shell thickness is playing an important role in preserving the content until the final setting of concrete. The capsules can also be surface functionalized with carboxyl groups to overcome the homogenous mixing issues. Currently, this formulated self-healing system can replace up to 1% of cement in a concrete formulation. Increasing this amount to 5-7% in the concrete formulation without compromising compression strength and shrinkage properties, is still under investigation. This self-healing system will not only increase the durability of structures by stopping crack propagation but also allow the use of less cement in concrete construction, thereby adding to the global effort for CO2 emission reduction.

Keywords: self-healing concrete, concrete crack, concrete deterioration, durability

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Authors: Vishal Kumar, Soumitra Satapathi

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Föster Resonance Energy Transfer (FRET) is a powerful technique used to probe close-range molecular interactions. Physically, the FRET phenomenon manifests as a dipole–dipole interaction between closely juxtaposed fluorescent molecules (10–100 Å). Our effort is to employ this FRET technique to make a prototype device for highly sensitive detection of environment pollutant. Among the most common environmental pollutants, nitroaromatic compounds (NACs) are of particular interest because of their durability and toxicity. That’s why, sensitive and selective detection of small amounts of nitroaromatic explosives, in particular, 2,4,6-trinitrophenol (TNP), 2,4-dinitrotoluene (DNT) and 2,4,6-trinitrotoluene (TNT) has been a critical challenge due to the increasing threat of explosive-based terrorism and the need of environmental monitoring of drinking and waste water. In addition, the excessive utilization of TNP in several other areas such as burn ointment, pesticides, glass and the leather industry resulted in environmental accumulation, and is eventually contaminating the soil and aquatic systems. To the date, high number of elegant methods, including fluorimetry, gas chromatography, mass, ion-mobility and Raman spectrometry have been successfully applied for explosive detection. Among these efforts, fluorescence-quenching methods based on the mechanism of FRET show good assembly flexibility, high selectivity and sensitivity. Here, we report a FRET-based sensor system for the highly selective detection of NACs, such as TNP, DNT and TNT. The sensor system is composed of a copolymer Poly [(N,N-dimethylacrylamide)-co-(Boc-Trp-EMA)] (RP) bearing tryptophan derivative in the side chain as donor and dansyl tagged copolymer P(MMA-co-Dansyl-Ala-HEMA) (DCP) as an acceptor. Initially, the inherent fluorescence of RP copolymer is quenched by non-radiative energy transfer to DCP which only happens once the two molecules are within Förster critical distance (R0). The excellent spectral overlap (Jλ= 6.08×10¹⁴ nm⁴M⁻¹cm⁻¹) between donors’ (RP) emission profile and acceptors’ (DCP) absorption profile makes them an exciting and efficient FRET pair i.e. further confirmed by the high rate of energy transfer from RP to DCP i.e. 0.87 ns⁻¹ and lifetime measurement by time correlated single photon counting (TCSPC) to validate the 64% FRET efficiency. This FRET pair exhibited a specific fluorescence response to NACs such as DNT, TNT and TNP with 5.4, 2.3 and 0.4 µM LODs, respectively. The detection of NACs occurs with high sensitivity by photoluminescence quenching of FRET signal induced by photo-induced electron transfer (PET) from electron-rich FRET pair to electron-deficient NAC molecules. The estimated stern-volmer constant (KSV) values for DNT, TNT and TNP are 6.9 × 10³, 7.0 × 10³ and 1.6 × 104 M⁻¹, respectively. The mechanistic details of molecular interactions are established by time-resolved fluorescence, steady-state fluorescence and absorption spectroscopy confirmed that the sensing process is of mixed type, i.e. both dynamic and static quenching as lifetime of FRET system (0.73 ns) is reduced to 0.55, 0.57 and 0.61 ns DNT, TNT and TNP, respectively. In summary, the simplicity and sensitivity of this novel FRET sensor opens up the possibility of designing optical sensor of various NACs in one single platform for developing multimodal sensor for environmental monitoring and future field based study.

Keywords: FRET, nitroaromatic, stern-Volmer constant, tryptophan and dansyl tagged copolymer

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Authors: Mohammed Badereldien, Rezk Diab, Mohamoud Ali, Ayman Aboelkassem

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The stone surfaces of historical architectural heritage in Egypt are under threat from of various environmental factors such as temperature fluctuation, humidity, pollution, and microbes. Due to these factors, the facades of buildings are deteriorating deformation and disfiguration of external decoration and the formation of black accretion also often from the stone works. The aim of this study is to evaluate the effectiveness of CaCO₃ nano-particles as consolidation and protection material for calcareous stone monuments. Selected tests were carried out in order to estimate the superficial consolidating and protective effect of the treatment. When applied the nanoparticles dispersed in the acrylic copolymer; poly ethylmethacrylate (EMA)/methylacrylate (MA) (70/30, respectively) (EMA)/methylacrylate (MA) (70/30, respectively). The synthesis process of CaCO₃ nanoparticles/polymer nano-composite was prepared using in situ emulsion polymerization system. The consolidation and protection were characterized by TEM, while the penetration depth, re-aggregating effects of the deposited phase, and the surface morphology before and after treatment were examined by SEM (Scanning Electron Microscopy). Improvement of the stones' mechanical properties was evaluated by compressive strength tests. Changes in water-interaction properties were evaluated by water absorption capillarity measurements, and colorimetric measurements were used to evaluate the optical appearance. Together the results appear to demonstrate that CaCO₃/polymer nanocomposite is an efficient material for the consolidation of limestone architecture and monuments. As compared with samples treated with pure acrylic copolymer without Calcium carbonate nanoparticles, for example, CaCO₃ nanoparticles are completely compatible, strengthening limestone against thermal aging and improving its mechanical properties.

Keywords: calcium carbonate nanoparticles, consolidation, nanocomposites, calcareous stone, colorimetric measurements, compressive strength

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Authors: Lin Meng, Xi Lu, Haibo Wang, Yong Song, Lili Cao, Wenfang Song, Yong Hu

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China has abundant heavy oil resources, and thermal recovery is the main recovery method for heavy oil reservoirs. However, high energy consumption, high carbon emission and high production costs make heavy oil thermal recovery unsustainable. It is urgent to explore a replacement for developing technology. A low Carbon and cost technology of heavy oil recovery, chemical viscosity-reduction in layer (CVRL), is developed by the petroleum exploration and development research institute of Sinopec via investigated mechanisms, synthesized products, and improved oil production technologies, as follows: (1) Proposed a cascade viscous mechanism of heavy oil. Asphaltene and resin grow from free molecules to associative structures further to bulk aggregations by π - π stacking and hydrogen bonding, which causes the high viscosity of heavy oil. (2) Aimed at breaking the π - π stacking and hydrogen bond of heavy oil, the copolymer of N-(3,4-dihydroxyphenethyl) acryl amide and 2-Acrylamido-2-methylpropane sulfonic acid was synthesized as a viscosity reducer. It achieves a viscosity reduction rate of>80% without shearing for heavy oil (viscosity < 50000 mPa‧s), of which fluidity is evidently improved in the layer. (3) Synthesized hydroxymethyl acrylamide-maleic acid-decanol ternary copolymer self-assembly plugging agent. The particle size is 0.1 μm-2 mm adjustable, and the volume is 10-500 times controllable, which can achieve the efficient transportation of viscosity reducer to enriched oil areas. CVRL has applied 400 wells until now, increasing oil production by 470000 tons, saving 81000 tons of standard coal, reducing CO2 emissions by 174000 tons, and reducing production costs by 60%. It promotes the transformation of heavy oil towards low energy consumption, low carbon emissions, and low-cost development.

Keywords: heavy oil, chemical viscosity-reduction, low carbon, viscosity reducer, plugging agent

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Authors: Raquel Galante, Marina Braga, Daniela Ghisleni, Terezinha J. A. Pinto, Rogério Colaço, Ana Paula Serro

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The sensitive nature of soft biomaterials, such as hydrogels, renders their sterilization a particularly challenging task for the biomedical industry. Widely used contact lenses are now studied as promising platforms for topical corneal drug delivery. However, to the best of the authors knowledge, the influence of sterilization methods on these systems has yet to be evaluated. The main goal of this study was to understand how different pairs drug-hydrogel would interact under an ozone-based sterilization method in comparison with two conventional processes (steam heat and gamma irradiation). For that, Si-Hy containing hydroxylethyl methacrylate (HEMA) and [tris(trimethylsiloxy)silyl]propyl methacrylate (TRIS) was produced and soaked in different drug solutions, commonly used for the treatment of ocular diseases (levofloxacin, chlorhexidine, diclofenac and timolol maleate). The drug release profiles and main material properties were evaluated before and after the sterilization. Namely, swelling capacity was determined by water uptake studies, transparency was accessed by UV-Vis spectroscopy, surface topography/morphology by scanning electron microscopy (SEM) and mechanical properties by performing tensile tests. The drug released was quantified by high performance liquid chromatography (HPLC). The effectiveness of the sterilization procedures was assured by performing sterility tests. Ozone gas method led to a significant reduction of drug released and to the formation of degradation products specially for diclofenac and levofloxacin. Gamma irradiation led to darkening of the loaded Si-Hys and to the complete degradation of levofloxacin. Steam heat led to smoother surfaces and to a decrease of the amount of drug released, however, with no formation of degradation products. This difference in the total drug released could be the related to drug/polymer interactions promoted by the sterilization conditions in presence of the drug. Our findings offer important insights that, in turn, could be a useful contribution to the safe development of actual products.

Keywords: drug delivery, silicone hydrogels, sterilization, gamma irradiation, steam heat, ozone gas

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Authors: Rishi Sharma, S. N. Maiti

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The non-isothermal crystallization kinetics of PP/SEBS-g-MA blends up to 0-50% concentration of copolymer was studied by differential scanning calorimetry at four different cooling rates. Crystallization parameters were analyzed by Avrami and Jeziorny models. Primary and secondary crystallization processes were described by Avrami equation. Avrami model showed that all types of shapes grow from small dimensions during primary crystallization. However, three-dimensional crystal growth was observed during the secondary crystallization process. The crystallization peak and onset temperature decrease, however

Keywords: crystallization kinetics, non-isothermal, polypropylene, SEBS-g-MA

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Authors: Mauricio A. Sarabia-Vallejos, Carmen M. Gonzalez-Henriquez, Adolfo Del Campo-Garcia, Aitzibier L. Cortajarena, Juan Rodriguez-Hernandez

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In this study, it was explored the formation and the morphological differences between wrinkled hydrogel patterns obtained via generation of surface instabilities. The slight variations in the polymerization conditions produce important changes in the material composition and pattern structuration. The compounds were synthesized using three main components, i.e. an amphiphilic monomer, hydroxyethyl methacrylate (HEMA), a hydrophobic monomer, trifluoroethyl methacrylate (TFMA), and a hydrophilic crosslinking agent, poly(ethylene glycol) diacrylate (PEGDA). The first part of this study was related to the formation of wrinkled surfaces using only HEMA and PEGDA and varying the amount of water added in the reaction. The second part of this study involves the gradual insertion of TFMA into the hydrophilic reaction mixture. Interestingly, the manipulation of the chemical composition of this hydrogel affects both surface morphology and physicochemical characteristics of the patterns, inducing transitions from one particular type of structure (wrinkles or ripples) to different ones (creases, folds, and crumples). Contact angle measurements show that the insertion of TFMA produces a slight decrease in surface wettability of the samples, remaining however highly hydrophilic (contact angle below 45°). More interestingly, by using confocal Raman spectroscopy, important information about the wrinkle formation mechanism is obtained. The procedure involving two consecutive thermal and photopolymerization steps lead to a “pseudo” two-layer system. Thus, upon photopolymerization, the surface is crosslinked to a higher extent than the bulk and water evaporation drives the formation of wrinkled surfaces. Finally, cellular, and bacterial proliferation studies were performed to the samples, showing that the amount of TFMA included in each sample slightly affects the proliferation of both (bacteria and cells), but in the case of bacteria, the morphology of the sample also plays an important role, importantly reducing the bacterial proliferation.

Keywords: antibiofouling properties, hydrophobic/hydrophilic balance, morphologic characterization, wrinkled hydrogel patterns

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Authors: M. Khlifa, A. Youssef. M. Almakki

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The addition of silica nanoparticles to poly(methyl methacrylate) (PMMA) can influence its mechanical and aging properties. Dispersed PMMA in colloidal and aggregated silica revealed considerable increase in modulus above the glass transition temperature when aggregated silica nanoparticles were used, whereas colloidally dispersed silica nanoparticles showed only a marginal improvement. In addition, Dispersed PMMA in both aggregated and colloidally silica nanoparticles accelerated physical ageing.

Keywords: nanoparticles, physical aging, PMMA, chemical and molecular engineering

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Authors: Aqsa Kanwal, Min Zhang, Faisal Sharaf, Li Chengtao

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The globe is facing increasing challenges of plastic pollution due to single-use of plastic-based packaging material. The plastic material is continuously being dumped into the natural environment, which causes serious harm to the entire ecosystem. Polymer degradation in nature is very difficult, so the use of biodegradable polymers instead of conventional polymers can mitigate this issue. Due to the good mechanical properties and biodegradability, aliphatic-aromatic polymers are being widely commercialized. Due to the advancement in molecular biology, many studies have reported specific microbes that can effectively degrade PBAT. Aliphatic polyesters undergo hydrolytic cleavage of ester groups, so they can be easily degraded by microorganisms. In this study, we investigated the enzymatic degradation of poly (butylene adipate terephthalate) (PBAT) copolymer using lipase B from Candida Antarctica (CALB). Results of the study displayed approximately 5.16 % loss in PBAT mass after 2 days which significantly increased to approximately 15.7 % at the end of the experiment (12 days) as compared to blank. The pH of the degradation solution also displayed significant reduction and reached the minimum value of 6.85 at the end of the experiment. The structure and morphology of PBAT after degradation were characterized by FTIR, XRD, SEM, and TGA. FTIR analysis showed that after degradation many peaks become weaker and the peak at 2950 cm-1 almost disappeared after 12 days. The XRD results indicated that as the degradation time increases the intensity of diffraction peaks slightly increases as compared to the blank PBAT. TGA analysis also confirmed the successful degradation of PBAT with time. SEM micrographs further confirmed that degradation has occurred. Hence, biodegradable polymers can widely be used. The effect of PBAT biodegradation on plant growth was also studied and it was found that PBAT has no toxic effect on the growth of plants. Hence PBAT can be employed in a wide range of applications.

Keywords: aliphatic-aromatic co-polyesters, polybutylene adipate terephthalate, lipase (CALB), biodegradation, plant growth

Procedia PDF Downloads 55

Authors: Bruno Baptista, Andreia S. R. Oliveira, Patricia V. Mendonca, Jorge F. J. Coelho, Fani Sousa

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Drug delivery systems are designed to allow adequate protection and controlled delivery of drugs to specific locations. These systems aim to reduce side effects and control the biodistribution profile of drugs, thus improving therapeutic efficacy. This study involved the synthesis of polymeric nanoparticles, based on amphiphilic diblock copolymers, comprising a biocompatible, poly (oligo (ethylene oxide) methyl ether methacrylate (POEOMA) as hydrophilic segment and a pH-sensitive block, the poly (2-diisopropylamino)ethyl methacrylate) (PDPA). The objective of this work was the development of polymeric pH-responsive nanoparticles to encapsulate and carry small RNAs as a model to further develop non-coding RNAs delivery systems with therapeutic value. The responsiveness of PDPA to pH allows the electrostatic interaction of these copolymers with nucleic acids at acidic pH, as a result of the protonation of the tertiary amine groups of this polymer at pH values below its pKa (around 6.2). Initially, the molecular weight parameters and chemical structure of the block copolymers were determined by size exclusion chromatography (SEC) and nuclear magnetic resonance (1H-NMR) spectroscopy, respectively. Then, the complexation with small RNAs was verified, generating polyplexes with sizes ranging from 300 to 600 nm and with encapsulation efficiencies around 80%, depending on the molecular weight of the polymers, their composition, and concentration used. The effect of pH on the morphology of nanoparticles was evaluated by scanning electron microscopy (SEM) being verified that at higher pH values, particles tend to lose their spherical shape. Since this work aims to develop systems for the delivery of non-coding RNAs, studies on RNA protection (contact with RNase, FBS, and Trypsin) and cell viability were also carried out. It was found that they induce some protection against constituents of the cellular environment and have no cellular toxicity. In summary, this research work contributes to the development of pH-sensitive polymers, capable of protecting and encapsulating RNA, in a relatively simple and efficient manner, to further be applied on drug delivery to specific sites where pH may have a critical role, as it can occur in several cancer environments.

Keywords: drug delivery systems, pH-responsive polymers, POEOMA-b-PDPA, small RNAs

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Authors: Yi Li, Rui Lu, Lianjun Wang

Abstract:

With the rapid development of chemical industry, the consumption of volatile organic compounds (VOCs) has increased extensively. In the process of VOCs production and application, plenty of them have been transferred to environment. As a result, it has led to pollution problems not only in soil and ground water but also to human beings. Thus, it is important to develop a sensitive and cost-effective analytical method for trace VOCs detection in environment. Surface-enhanced Raman Spectroscopy (SERS), as one of the most sensitive optical analytical technique with rapid response, pinpoint accuracy and noninvasive detection, has been widely used for ultratrace analysis. Based on the plasmon resonance on the nanoscale metallic surface, SERS technology can even detect single molecule due to abundant nanogaps (i.e. 'hot spots') on the nanosubstrate. In this work, a self-supported flexible silver nitrate (AgNO3)/ethylene-propylene copolymer (EPM) hybrid nanofibers was fabricated by electrospinning. After an in-situ chemical reduction using ice-cold sodium borohydride as reduction agent, numerous silver nanoparticles were formed on the nanofiber surface. By adjusting the reduction time and AgNO3 content, the morphology and dimension of silver nanoparticles could be controlled. According to the principles of solid-phase extraction, the hydrophobic substance is more likely to partition into the hydrophobic EPM membrane in an aqueous environment while water and other polar components are excluded from the analytes. By the enrichment of EPM fibers, the number of hydrophobic molecules located on the 'hot spots' generated from criss-crossed nanofibers is greatly increased, which further enhances SERS signal intensity. The as-prepared Ag/EPM hybrid nanofibers were first employed to detect common SERS probe molecule (p-aminothiophenol) with the detection limit down to 10-12 M, which demonstrated an excellent SERS performance. To further study the application of the fabricated substrate for monitoring hydrophobic substance in water, several typical VOCs, such as benzene, toluene and p-xylene, were selected as model compounds. The results showed that the characteristic peaks of these target analytes in the mixed aqueous solution could be distinguished even at a concentration of 10-6 M after multi-peaks gaussian fitting process, including C-H bending (850 cm-1), C-C ring stretching (1581 cm-1, 1600 cm-1) of benzene, C-H bending (844 cm-1 ,1151 cm-1), C-C ring stretching (1001 cm-1), CH3 bending vibration (1377 cm-1) of toluene, C-H bending (829 cm-1), C-C stretching (1614 cm-1) of p-xylene. The SERS substrate has remarkable advantages which combine the enrichment capacity from EPM and the Raman enhancement of Ag nanoparticles. Meanwhile, the huge specific surface area resulted from electrospinning is benificial to increase the number of adsoption sites and promotes 'hot spots' formation. In summary, this work provides powerful potential in rapid, on-site and accurate detection of trace VOCs using a portable Raman.

Keywords: electrospinning, ethylene-propylene copolymer, silver nanoparticles, SERS, VOCs

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Authors: Abdel-Mohdy, A. Abou-Okeil, S. El-Sabagh, S. M. El-Sawy

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Chitosan polyacrylic acid composite membranes were prepared by a bulk polymerization method in the presence of N, N'-methylene bisacrylamide (crosslinker) and ammonium persulphate as initiator. Membranes prepared from this copolymer in presence and absence of Ag nanoparticles were characterized by measuring mechanical and physical properties, water up-take and antibacterial properties. The results obtained indicated that the prepared membranes have antibacterial properties which increases with adding Ag nanoparticles.

Keywords: Ag nanoparticles , antimicrobial, Membrane, composites, mechanical properties, physical properties

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Authors: Petr Slobodian, Pavel Riha, Jiri Matyas, Robert Olejnik, Nuri Karakurt

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Thermoelectric devices generate an electrical current when there is a temperature gradient between the hot and cold junctions of two dissimilar conductive materials typically n-type and p-type semiconductors. Consequently, also the polymeric semiconductors composed of polymeric matrix filled by different forms of carbon nanotubes with proper structural hierarchy can have thermoelectric properties which temperature difference transfer into electricity. In spite of lower thermoelectric efficiency of polymeric thermoelectrics in terms of the figure of merit, the properties as stretchability, flexibility, lightweight, low thermal conductivity, easy processing, and low manufacturing cost are advantages in many technological and ecological applications. Polyethylene-octene copolymer based highly elastic composites filled with multi-walled carbon nanotubes (MWCTs) were prepared by sonication of nanotube dispersion in a copolymer solution followed by their precipitation pouring into non-solvent. The electronic properties of MWCNTs were moderated by different treatment techniques such as chemical oxidation, decoration by Ag clusters or addition of low molecular dopants. In this concept, for example, the amounts of oxygenated functional groups attached on MWCNT surface by HNO₃ oxidation increase p-type charge carriers. p-type of charge carriers can be further increased by doping with molecules of triphenylphosphine. For partial altering p-type MWCNTs into less p-type ones, Ag nanoparticles were deposited on MWCNT surface and then doped with 7,7,8,8-tetracyanoquino-dimethane. Both types of MWCNTs with the highest difference in generated thermoelectric power were combined to manufacture polymeric based thermoelectric module generating thermoelectric voltage when the temperature difference is applied between hot and cold ends of the module. Moreover, it was found that the generated voltage by the thermoelectric module at constant temperature gradient was significantly affected when exposed to vapors of different volatile organic compounds representing then a self-powered thermoelectric sensor for chemical vapor detection.

Keywords: carbon nanotubes, polymer composites, thermoelectric materials, self-powered gas sensor

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Authors: N. P. D. Tran, H. Q. D. Nguyen, M. C. Yang

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In this study, contact lenses were prepared through the polymerization of tris-(trimethyl-silyl-propyl-methacrylate) (TRIS), N,N-dimethylacrylamide (DMA), N-vinylpyrrolidone (NVP), and cross-linked with ethylene glycol dimethylacrylate (EGDMA). The equilibrium water content (EWC), oxygen permeability (Dk), light transmittance, and in vitro cytotoxicity of TRIS-DMA-NVP with various ratios were measured. The results showed that the EWC increased while the Dk decreased with the increase of NVP content. For the sample with 25 wt% NVP, the EWC attained 53% whereas the Dk decreased to 46 barrers. All these lenses exhibited light transmittance over than 95%. In addition, all these lenses exhibited no inhibition to the growth of L292 fibroblasts. Thus, this study showed that TRIS-DMA-NVP can be applicable for making contact lens.

Keywords: DMA, TRIS, NVP, silicone hydrogel, contact lens

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Authors: Asmaa M. Fahim

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

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

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Authors: Junkal Gutierrez, Hernane S. Barud, Sidney J. L. Ribeiro, Agnieszka Tercjak

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Nowadays the interest on green nanocomposites and on the development of more environmental friendly products has been increased. Bacterial cellulose has been recently investigated as an attractive environmentally friendly material for the preparation of low-cost nanocomposites. The formation of cellulose by laboratory bacterial cultures is an interesting and attractive biomimetic access to obtain pure cellulose with excellent properties. Additionally, properties as molar mass, molar mass distribution, and the supramolecular structure could be control using different bacterial strain, culture mediums and conditions, including the incorporation of different additives. This kind of cellulose is a natural nanomaterial, and therefore, it has a high surface-to-volume ratio which is highly advantageous in composites production. Such property combined with good biocompatibility, high tensile strength, and high crystallinity makes bacterial cellulose a potential material for applications in different fields. The aim of this investigation work was the fabrication of novel hybrid inorganic-organic composites based on bacterial cellulose, cultivated in our laboratory, as a template. This kind of biohybrid nanocomposites gathers together excellent properties of bacterial cellulose with the ones displayed by typical inorganic nanoparticles like optical, magnetic and electrical properties, luminescence, ionic conductivity and selectivity, as well as chemical or biochemical activity. In addition, the functionalization of cellulose with inorganic materials opens new pathways for the fabrication of novel multifunctional hybrid materials with promising properties for a wide range of applications namely electronic paper, flexible displays, solar cells, sensors, among others. In this work, different pathways for fabrication of multifunctional biohybrid nanopapers with tunable properties based on BC modified with amphiphilic poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) (EPE) block copolymer, sol-gel synthesized nanoparticles (titanium, vanadium and a mixture of both oxides) and functionalized iron oxide nanoparticles will be presented. In situ (biosynthesized) and ex situ (at post-production level) approaches were successfully used to modify BC membranes. Bacterial cellulose based biocomposites modified with different EPE block copolymer contents were developed by in situ technique. Thus, BC growth conditions were manipulated to fabricate EPE/BC nanocomposite during the biosynthesis. Additionally, hybrid inorganic/organic nanocomposites based on BC membranes and inorganic nanoparticles were designed via ex-situ method, by immersion of never-dried BC membranes into different nanoparticle solutions. On the one hand, sol-gel synthesized nanoparticles (titanium, vanadium and a mixture of both oxides) and on the other hand superparamagnetic iron oxide nanoparticles (SPION), Fe2O3-PEO solution. The morphology of designed novel bionanocomposites hybrid materials was investigated by atomic force microscopy (AFM) and scanning electron microscopy (SEM). In order to characterized obtained materials from the point of view of future applications different techniques were employed. On the one hand, optical properties were analyzed by UV-vis spectroscopy and spectrofluorimetry and on the other hand electrical properties were studied at nano and macroscale using electric force microscopy (EFM), tunneling atomic force microscopy (TUNA) and Keithley semiconductor analyzer, respectively. Magnetic properties were measured by means of magnetic force microscopy (MFM). Additionally, mechanical properties were also analyzed.

Keywords: bacterial cellulose, block copolymer, advanced characterization techniques, nanoparticles

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Authors: Devi Eka Septiyani Arifin, Jrjeng Ruan

Abstract:

As an approach to manipulate the performance of polymer thin film, epitaxy crystallization within polymer blends of poly(vinylidene fluoride) (PVDF) and its copolymer poly(vinylidene fluoride-trifluoroethylene) P(VDF-TrFE) was studied in this research, which involves the competition between phase separation and crystal growth of constitutive semicrystalline polymers. The unique piezoelectric feature of poly(vinylidene fluoride) crystalline phase is derived from the packing of molecular chains in all-trans conformation, which spatially arranges all the substituted fluorene atoms on one side of the molecular chain and hydrogen atoms on the other side. Therefore, the net dipole moment is induced across the lateral packing of molecular chains. Nevertheless, due to the mutual repulsion among fluorene atoms, this all-trans molecular conformation is not stable, and ready to change above curie temperature, where thermal energy is sufficient to cause segmental rotation. This research attempts to explore whether the epitaxial interactions between piezoelectric crystals and crystal lattice of hexamethylbenzene (HMB) crystalline platelet is able to stabilize this metastable all-trans molecular conformation or not. As an aromatic crystalline compound, the melt of HMB was surprisingly found able to dissolve the poly(vinylidene fluoride), resulting in homogeneous eutectic solution. Thus, after quenching this binary eutectic mixture to room temperature, subsequent heating or annealing processes were designed to explore the involve phase separation and crystallization behavior. The phase transition behaviors were observed in-situ by X-ray diffraction and differential scanning calorimetry (DSC). The molecular packing was observed via transmission electron microscope (TEM) and the principles of electron diffraction were brought to study the internal crystal structure epitaxially developed within thin films. Obtained results clearly indicated the occurrence of heteroepitaxy of PVDF/PVDF-TrFE on HMB crystalline platelet. Both the concentration of poly(vinylidene fluoride) and the mixing ratios of these two constitutive polymers have been adopted as the influential factors for studying the competition between the epitaxial crystallization of PVDF and P(VDF-TrFE) on HMB crystalline. Furthermore, the involved epitaxial relationship is to be deciphered and studied as a potential factor capable of guiding the wide spread of piezoelectric crystalline form.

Keywords: epitaxy, crystallization, crystalline platelet, thin film and mixing ratio

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Authors: Kumaran Letchmanan, Shou-Cang Shen, Wai Kiong Ng

Abstract:

Postoperative implant-associated infections in soft tissues and bones remain a serious complication in orthopaedic surgery, which leads to impaired healing, re-implantation, prolong hospital stay and increase cost. Drug-loaded implants with sustained release of antibiotics at the local site are current research interest to reduce the risk of post-operative infections and osteomyelitis, thus, minimize the need for follow-up care and increase patient comfort. However, the improved drug release of the drug-loaded bone cements is usually accompanied by a loss in mechanical strength, which is critical for weight-bearing bone cement. Recently, more attempts have been undertaken to develop techniques to enhance the antibiotic elution as well as preserve the mechanical properties of the bone cements. The present study investigates the potential influence of addition of mesoporous silica nanoparticles (MSN) on the in vitro drug release kinetics of gentamicin (GTMC), along with the mechanical properties of bone cements. Simplex P was formulated with MSN and loaded with GTMC by direct impregnation. Meanwhile, Simplex P with water soluble poragen (xylitol) and high loading of GTMC as well as commercial bone cement CMW Smartset GHV were used as controls. MSN-formulated bone cements are able to increase the drug release of GTMC by 3-fold with a cumulative release of more than 46% as compared with other control groups. Furthermore, a sustained release could be achieved for two months. The loaded nano-sized MSN with uniform pore channels significantly build up an effective nano-network path in the bone cement facilitates the diffusion and extended release of GTMC. Compared with formulations using xylitol and high GTMC loading, incorporation of MSN shows no detrimental effect on biomechanical properties of the bone cements as no significant changes in the mechanical properties as compared with original bone cement. After drug release for two months, the bending modulus of MSN-formulated bone cements is 4.49 ± 0.75 GPa and the compression strength is 92.7 ± 2.1 MPa (similar to the compression strength of Simplex-P: 93.0 ± 1.2 MPa). The unaffected mechanical properties of MSN-formulated bone cements was due to the unchanged microstructures of bone cement, whereby more than 98% of MSN remains in the matrix and supports the bone cement structures. In contrast, the large portions of extra voids can be observed for the formulations using xylitol and high drug loading after the drug release study, thus caused compressive strength below the ASTM F541 and ISO 5833 minimum of 70 MPa. These results demonstrate the potential applicability of MSN-functionalized poly(methyl methacrylate)-based bone cement as a highly efficient, sustained and local drug delivery system with good mechanical properties.

Keywords: antibiotics, biomechanical properties, bone cement, sustained release

Procedia PDF Downloads 236

Authors: R. Trad Khodja, A. Guessmi, R. Ghoul, A. Mahtout, S. A. Benbouali, M. A. Boulahlib

Abstract:

Cranioplasty is a surgical act that aims to restore cranial bone losses in order to protect the brain from external aggressions and to improve the patient's aesthetic appearance. This objective can be achieved by taking advantage of the current technological development in computer science and biomechanics. The objective of this paper is to present an approach for the realization of high-precision biocompatible cranial implants using new 3D printing technologies at the lowest cost. The proposed method is to reproduce the missing part of the skull by referring to its healthy contralateral part. Once the model is validated by the neurosurgeons, a mold is 3D printed for the production of a biocompatible implant in Poly-Methyl-Methacrylate (PMMA) acrylic cement. Using this procedure, ten patients underwent this procedure with excellent aesthetic results.

Keywords: cranioplasty, cranial defect, PMMA, 3d printing, custom made implants

Procedia PDF Downloads 21

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

Abstract:

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

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

Procedia PDF Downloads 145

Authors: Li Li, Li-Ru Xia, He-Ye Wang, Xiao-Dong Bi

Abstract:

In this paper, we presented a highly sensitive immune-affinity monolithic array for detection of α-fetoprotein (AFP) and carcinoembryonic antigen (CEA). Firstly, the epoxy functionalized monolith arrays were fabricated using UV initiated copolymerization method. Scanning electron microscopy (SEM) image showed that the poly(BABEA-co-GMA) monolith exhibited a well-controlled skeletal and well-distributed porous structure. Then, AFP and CEA immune-affinity monolithic arrays were prepared by immobilization of AFP and CEA antibodies on epoxy functionalized monolith arrays. With a non-competitive immune response format, the presented AFP and CEA immune-affinity arrays were demonstrated as an inexpensive, flexible, homogeneous and stable array for detection of AFP and CEA.

Keywords: chemiluminescent detection, immune-affinity, monolithic copolymer array, UV-initiated copolymerization

Procedia PDF Downloads 308

Authors: Shimaa M. Elsaeed, Reem K. Farag, Ibrahim M. Nassar

Abstract:

Hydrogel conductive polymer nanocomposite fabricated via in-situ polymerization of polyaniline (PANI) inside thermosensitive hydrogels based on hydroxy ethyl meth acrylate (HEMA) copolymer with 2-acrylamido-2-methyl propane sulfonic acid (AMPS). SEM micrographs show the nanometric size of the conductive material (polyaniline, PANI) dispersed in the hydrogel matrix. The swelling parameters of hydrogel are measured. The incorporation of PANI improves the mechanical properties and swelling up to 30,000% without breaking. X-ray diffraction shows that typical polyaniline crystallization is formed in composite, which is advantageous to increase the electrical conductivity of the composite hydrogel. Open-circuit voltage (I-V) curve fill factor of the highest photo-conversion efficiency and enhanced to use in solar cell.

Keywords: hydrogel, solar cell, conductive polymer, nanocomposite

Procedia PDF Downloads 371

Authors: Hiroyuki Aoki

Abstract:

The glass transition phenomenon has been extensively studied for a long time. The glass transition of polymer materials is assigned to the transition of the dynamics of the chain backbone segment. However, the detailed mechanism of the transition behavior of the segmental motion is still unclear. In the current work, the single molecule detection technique was employed to reveal the trajectory of the molecular motion of the single polymer chain. The center segment of poly(butyl methacrylate) chain was labeled by a perylenediimide dye molecule and observed by a highly sensitive fluorescence microscope in a defocus condition. The translational and rotational diffusion of the center segment in a single polymer chain was analyzed near the glass transition temperature. The direct observation of the individual polymer chains revealed the intermittent behavior of the segmental motion, indicating the spatial inhomogeneity.

Keywords: glass transition, molecular motion, polymer materials, single molecule

Procedia PDF Downloads 296

Authors: Nigus Maregu Demewoz, Shu-Kai Yeh

Abstract:

Low-density nanocellular foam is a fascinating new-generation advanced material due to its mechanical strength and thermal insulation properties. In nanocellular foam, reducing the density increases the insulation ability. However, producing a nanocellular foam of densities less than 0.3 with a cell size of less than 100 nm is very challenging. In this study, poly (methyl methacrylate) (PMMA) was blended with Polyether block amide (PEBAX) to study the effects of PEBAX on the nanocellular foam structure of the PMMA matrix. We added 2 wt% of PEBAX in the PMMA matrix, and the PEBAX nanostructured domain size of 45 nm was well dispersed in the PMMA matrix. The foaming result produced a new generation special bouquet-like nanocellular foam of cell size less than 50 nm with a relative density of 0.24. Also, we were able to produce a nanocellular foam of a relative density of about 0.17. In addition to thermal insulation applications, bouquet-like nanocellular foam may be expected for filtration applications.

Keywords: nanocellular foam, low-density, cell size, relative density, PMMA/PEBAX

Procedia PDF Downloads 51

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

Abstract:

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

Procedia PDF Downloads 427

Authors: A. Karimzad Ghavidel, M. Zadshakouyan

Abstract:

Laser cutting is a very common production method for cutting 2D polymeric parts. Developing of polymer composites with nano-fibers makes important their other properties like laser workability. The aim of this research is investigation of the influence different laser cutting conditions on the dimensional accuracy of parts and holes from poly methyl methacrylate (PMMA)/carbon nanotubes (CNTs) material. Experiments were carried out by considering of CNTs (in four level 0,0.5, 1 and 1.5% wt.%), laser power (60, 80, and 100 watt) and cutting speed 20, 30, and 40 mm/s as input variable factors. The results reveal that CNTs adding improves the laser workability of PMMA and the increasing of power has a significant effect on the part and hole size. The findings also show cutting speed is effective parameter on the size accuracy. Eventually, the statistical analysis of results was done, and calculated mathematical equations by the regression are presented for determining relation between input and output factor.

Keywords: dimensional accuracy, PMMA, CNTs, laser cutting

Procedia PDF Downloads 281

Authors: Nigus Maregu Demewoz, Shu-Kai Yeh

Abstract:

Low-density nanocellular foam is a fascinating new-generation advanced material due to its mechanical strength and thermal insulation properties. In nanocellular foam, reducing the density increases the insulation ability. However, producing a nanocellular foam of densities less than 0.3 with a cell size of less than 100 nm is very challenging. In this study, poly (methyl methacrylate) (PMMA) was blended with Polyether block amide (PEBAX) to study the effects of PEBAX on the nanocellular foam structure of the PMMA matrix. We added 2 wt% of PEBAX in the PMMA matrix, and the PEBAX nanostructured domain size of 45 nm was well dispersed in the PMMA matrix. The foaming result produced a new generation special bouquet-like nanocellular foam of cell size less than 50 nm with a relative density of 0.24. Also, we were able to produce a nanocellular foam of a relative density of about 0.17. In addition to thermal insulation applications, bouquet-like nanocellular foam may be expected for filtration applications.

Keywords: nanocellular foam, low-density, cell size, relative density, PMMA/PEBAX blend

Procedia PDF Downloads 54

Authors: Jadranka Blazhevska Gilev

Abstract:

IR laser-induced ablation of poly(butylacrylate-methylmethacrylate/hydroxyl ethyl methacrylate)/reduced graphene oxide (p(BA/MMA/HEMA)/rGO) was examined with 0.5, 0.75 and 1 wt% reduced graphene oxide content in relation to polymer. The irradiation was performed with TEA (transversely excited atmosphere) CO₂ laser using incident fluence of 15-20 J/cm², repetition frequency of 1 Hz, in an evacuated (10-3 Pa) Pyrex spherical vessel. Thin deposited nanocomposites films with large specific area were obtained using different substrates. The properties of the films deposited on these substrates were evaluated by TGA, FTIR, (Thermogravimetric analysis, Fourier Transformation Infrared) Raman spectroscopy and SEM microscopy. Homogeneous distribution of graphene sheets was observed from the SEM images, making polymer/rGO deposit an ideal candidate for SERS application. SERS measurements were performed using Rhodamine 6G as probe molecule on the substrate Ag/p(BA/MMA/HEMA)/rGO.

Keywords: laser ablation, reduced graphene oxide, polymer/rGO nanocomposites, thin deposited film

Procedia PDF Downloads 169