Search results for: nanolayers

Authors: Dawid Stawski, Silviya Halacheva, Dorota Zielińska

Abstract:

The surface properties of many materials can be readily and predictably modified by the controlled deposition of thin layers containing appropriate functional groups and this research area is now a subject of widespread interest. The layer-by-layer (lbl) method involves depositing oppositely charged layers of polyelectrolytes onto the substrate material which are stabilized due to strong electrostatic forces between adjacent layers. This type of modification affords products that combine the properties of the original material with the superficial parameters of the new external layers. Through an appropriate selection of the deposited layers, the surface properties can be precisely controlled and readily adjusted in order to meet the requirements of the intended application. In the presented paper a variety of anionic (poly(acrylic acid)) and cationic (linear poly(ethylene imine), polymers were successfully deposited onto the polypropylene nonwoven using the lbl technique. The chemical structure of the surface before and after modification was confirmed by reflectance FTIR spectroscopy, volumetric analysis and selective dyeing tests. As a direct result of this work, new materials with greatly improved properties have been produced. For example, following a modification process significant changes in the electrostatic activity of a range of novel nanocomposite materials were observed. The deposition of polyelectrolyte nanolayers was found to strongly accelerate the loss of electrostatically generated charges and to increase considerably the thermal resistance properties of the modified fabric (the difference in T50% is over 20°C). From our results, a clear relationship between the type of polyelectrolyte layer deposited onto the flat fabric surface and the properties of the modified fabric was identified.

Keywords: layer-by-layer technique, polypropylene nonwoven, surface modification, surface properties

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

Abstract:

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

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

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Authors: Dipali Nagaonkar, Mahendra Rai

Abstract:

Nanotechnology has experienced significant developments in engineered nanomaterials in the core-shell arrangement. Nanomaterials having nanolayers of silver and gold are of primary interest due to their wide applications in catalytical and biomedical fields. Further, mycosynthesis of nanoparticles has been proved as a sustainable synthetic approach of nanobiotechnology. In this context, we have synthesized silver and silver (core)-gold (shell) bimetallic nanoparticles using a fungal extract of Fusarium graminearum by sequential reduction. The core-shell deposition of nanoparticles was confirmed by the red shift in the surface plasmon resonance from 434 nm to 530 nm with the aid of the UV-Visible spectrophotometer. The mean particle size of Ag and Ag-Au nanoparticles was confirmed by nanoparticle tracking analysis as 37 nm and 50 nm respectively. Quite polydispersed and spherical nanoparticles are evident by TEM analysis. These mycosynthesized bimetallic nanoparticles were tested against some pathogenic bacteria and Candida sp. The antimicrobial analysis confirmed enhanced anticandidal and antibacterial potential of bimetallic nanoparticles over their monometallic counterparts.

Keywords: bimetallic nanoparticles, core-shell arrangement, mycosynthesis, sequential reduction

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Authors: T. Abohalkuma, J. Telegdi

Abstract:

Preparation, characterization, and application of self-assembled monolayers (SAM) formed by fluorophosphonic and undecenyl phosphonic acids on carbon steel surfaces as anticorrosive nanocoatings were demonstrated. The anticorrosive efficacy of these SAM layers was followed by atomic force microscopy, as the change in the surface morphology caused by layer deposition and corrosion processes was monitored. The corrosion process was determined by electrochemical potentiodynamic polarization, whereas the surface wettability of the carbon steel samples was tested with the use of static and dynamic contact angle measurements. Results showed that both chemicals produced good protection against corrosion as they performed as anodic inhibitors, especially with increasing the time of layer formation, which results in a more compact molecular film. According to the atomic force microscope (AFM) images, the fluoro-phosphonic acid self-assembled molecular layer can control the general as well as the pitting corrosion, but the SAM layers of the undecenyl-phosphonic acid cannot inhibit the pitting corrosion. The AFM and the contact angle measurements confirmed the results achieved by electrochemical measurements.

Keywords: nanolayers, corrosion, phosphonic acids, coatings

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

Abstract:

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

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

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

Abstract:

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

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

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Authors: S. V. Boroznin, I. V. Zaporotskova, N. P. Polikarpova

Abstract:

Studing of nanotubes sorption properties is very important for researching. These processes for carbon and boron nanotubes described in the high number of papers. But the sorption properties of boron containing nanotubes, susch as BC3-nanotubes haven’t been studied sufficiently yet. In this paper we present the results of theoretical research into the mechanism of atomic surface adsorption on the two types of boron-carbon nanotubes (BCNTs) within the framework of an ionic-built covalent-cyclic cluster model and an appropriately modified MNDO quantum chemical scheme and DFT method using B3LYP functional with 6-31G basis. These methods are well-known and the results, obtained using them, were in good agreement with the experiment. Also we studied three position of atom location above the nanotube surface. These facts suggest us to use them for our research and quantum-chemical calculations. We studied the mechanism of sorption of Cl, O and F atoms on the external surface of single-walled BC3 arm-chair nanotubes. We defined the optimal geometry of the sorption complexes and obtained the values of the sorption energies. Analysis of the band structure suggests that the band gap is insensitive to adsorption process. The electron density is located near atoms of the surface of the tube. Also we compared our results with others, which have been obtained earlier for pure carbon and boron nanotubes. The most stable adsorption complex has been between boron-carbon nanotube and oxygen atom. So, it suggests us to make a research of oxygen molecule adsorption on the BC3 nanotube surface. We modeled five variants of molecule orientation above the nanotube surface. The most stable sorption complex has been defined between the oxygen molecule and nanotube when the oxygen molecule is located above the nanotube surface perpendicular to the axis of the tube.

Keywords: Boron-carbon nanotubes, nanostructures, nanolayers, quantum-chemical calculations, nanoengineering

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Authors: Narek Margaryan, Zhozef Panosyan

Abstract:

Due to their unique properties, carbon nanofilms have become the object of general attention and intensive research. In this case it plays a very important role to study surface properties of these films. It is also important to study processes of forming of this films, which is accompanied by a process of self-organization at the nano and micro levels. For more detailed investigation, we examined diamond-like carbon (DLC) layers deposited by chemical vapor deposition (CVD) method on Ge substrate and hydro-generated grapheme layers obtained on surface of colloidal solution using grouping method. In this report surface transformation of these CVD nanolayers is studied by atomic force microscopy (AFM) upon deposition time. Also, it can be successfully used to study surface properties of self-assembled grapheme layers. In turn, it is possible to sketch out their boundary line, which enables one to draw an idea of peculiarities of formation of these layers. Images obtained by AFM are investigated as a mathematical set of numbers and fractal and roughness analysis were done. Fractal dimension, Regne’s fractal coefficient, histogram, Fast Fourier transformation, etc. were obtained. The dependence of fractal parameters on the deposition duration for CVD films and on temperature of solution tribolayers was revealed. As an important surface parameter for our carbon films, surface energy was calculated as function of Regne’s fractal coefficient. Surface potential was also measured with Kelvin probe method using semi-contacting AFM. The dependence of surface potential on the deposition duration for CVD films and on temperature of solution for hydro-generated graphene was found as well. Results obtained by fractal analysis method was related with purly esperimental results for number of samples.

Keywords: nanostructured films, self-assembled grapheme, diamond-like carbon, surface potential, Kelvin probe method, fractal analysis

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Authors: I. Kerti, G. Sezen, S. Daglilar

Abstract:

This present work is focused on studying to improve low wetting behaviour between liquid metal and ceramic particles. Ceramic particles like SiC and B4C have attracted great attention because of their usability as reinforcement for composite materials. However, poor wettability of particles is one of the major drawbacks of metal matrix composite production. Various methods have been studied to enhance the wetting properties between ceramic materials and metal substrates during ceramic reinforced metal matrix composites. Among these methods, autocatalytic nickel deposition is a unique process for the enhancement of the surface properties of ceramic particles. In fact, it is difficult to obtain continuous and uniform metallic coating on ceramic powders. In this study deposition of nickel boron layer on ceramic particles via autocatalytic plating in borohydride baths were investigated. Firstly, powders with different particle sizes were sensitized and activated respectively in order to ensure catalytic properties. Following the pre-treatment operations, particles were transferred into the coating bath containing nickel sulphate or nickel chloride as the Ni2+ source. The results show that a better bonding and uniform coating layer were obtained for Ni-B coatings with the Ni2+ source of NiCl2.6H2O as compared to NiSO4.6H2O. With the progress of the time, both particle surfaces are completely covered by a continuous and thin nickel boron layer. The surface morphology of the coatings that were analysed using scanning electron microscopy (SEM) show that SiC and B4C particles both distributed and different thickness of Ni-B nanolayers have been successfully coated onto the particles. The particles were mounted into a polimeric resin and polished in order to observe the thickness and the continuity of the coating layer. The composition of the coating layers were also evaluated by EDS analyses. The SEM morphologies and the EDS results of the coatings at different reaction times were adopted for detailed discussion of the Ni-B electroless plating mechanism.

Keywords: boron carbide, electroless coating, nickel boron deposition, silicon carbide

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

Abstract:

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

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

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Authors: G. M. Vlasceanu, H. Iovu, E. Vasile, M. Ionita

Abstract:

Herein, the synthesis and characterization of chitosan-gelatin highly porous scaffold reinforced with graphene oxide, and hydroxyapatite (HAp), crosslinked with genipin was targeted. In tissue engineering, chitosan and gelatin are two of the most robust biopolymers with wide applicability due to intrinsic biocompatibility, biodegradability, low antigenicity properties, affordability, and ease of processing. HAp, per its exceptional activity in tuning cell-matrix interactions, is acknowledged for its capability of sustaining cellular proliferation by promoting bone-like native micro-media for cell adjustment. Genipin is regarded as a top class cross-linker, while graphene oxide (GO) is viewed as one of the most performant and versatile fillers. The composites with natural bone HAp/biopolymer ratio were obtained by cascading sonochemical treatments, followed by uncomplicated casting methods and by freeze-drying. Their structure was characterized by Fourier Transform Infrared Spectroscopy and X-ray Diffraction, while overall morphology was investigated by Scanning Electron Microscopy (SEM) and micro-Computer Tomography (µ-CT). Ensuing that, in vitro enzyme degradation was performed to detect the most promising compositions for the development of in vivo assays. Suitable GO dispersion was ascertained within the biopolymer mix as nanolayers specific signals lack in both FTIR and XRD spectra, and the specific spectral features of the polymers persisted with GO load enhancement. Overall, correlations between the GO induced material structuration, crystallinity variations, and chemical interaction of the compounds can be correlated with the physical features and bioactivity of each composite formulation. Moreover, the HAp distribution within follows an auspicious density gradient tuned for hybrid osseous/cartilage matter architectures, which were mirrored in the mice model tests. Hence, the synthesis route of a natural polymer blend/hydroxyapatite-graphene oxide composite material is anticipated to emerge as influential formulation in bone tissue engineering. Acknowledgement: This work was supported by the project 'Work-based learning systems using entrepreneurship grants for doctoral and post-doctoral students' (Sisteme de invatare bazate pe munca prin burse antreprenor pentru doctoranzi si postdoctoranzi) - SIMBA, SMIS code 124705 and by a grant of the National Authority for Scientific Research and Innovation, Operational Program Competitiveness Axis 1 - Section E, Program co-financed from European Regional Development Fund 'Investments for your future' under the project number 154/25.11.2016, P_37_221/2015. The nano-CT experiments were possible due to European Regional Development Fund through Competitiveness Operational Program 2014-2020, Priority axis 1, ID P_36_611, MySMIS code 107066, INOVABIOMED.

Keywords: biopolymer blend, ectopic osteoinduction, graphene oxide composite, hydroxyapatite

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