Search results for: X-ray diffraction
10 Reinforcement of Calcium Phosphate Cement with E-Glass Fibre
Authors: Sudip Dasgupta, Debosmita Pani, Kanchan Maji
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Calcium Phosphate Cement (CPC) due to its high bioactivity and optimum bioresorbability shows excellent bone regeneration capability. Despite it has limited applications as bone implant due to its macro-porous microstructure causing its poor mechanical strength. The reinforcement of apatitic CPCs with biocompatible fibre glass phase is an attractive area of research to improve upon its mechanical strength. Here, we study the setting behaviour of Si-doped and un-doped α tri calcium phosphate (α - TCP) based CPC and its reinforcement with addition of E-glass fibre. Alpha Tri calcium phosphate powders were prepared by solid state sintering of CaCO3 , CaHPO4 and Tetra Ethyl Ortho Silicate (TEOS) was used as silicon source to synthesize Si doped α-TCP powders. Both initial and final setting time of the developed cement was delayed because of Si addition. Crystalline phases of HA (JCPDS 9- 432), α-TCP (JCPDS 29-359) and β-TCP (JCPDS 9-169) were detected in the X-ray diffraction (XRD) pattern after immersion of CPC in simulated body fluid (SBF) for 0 hours to 10 days. As Si incorporation in the crystal lattice stabilized the TCP phase, Si doped CPC showed little slower rate of conversion into HA phase as compared to un-doped CPC. The SEM image of the microstructure of hardened CPC showed lower grain size of HA in un-doped CPC because of premature setting and faster hydrolysis of un-doped CPC in SBF as compared that in Si-doped CPC. Premature setting caused generation of micro and macro porosity in un-doped CPC structure which resulted in its lower mechanical strength as compared to that in Si-doped CPC. It was found that addition of 10 wt% of E-glass fibre into Si-doped α-TCP increased the average DTS of CPC from 8 MPa to 15 MPa as the fibres could resists the propagation of crack by deflecting the crack tip. Our study shows that biocompatible E-glass fibre in optimum proportion in CPC matrix can enhance the mechanical strength of CPC without affecting its biocompatibility.
Keywords: Calcium phosphate cement, biocompatibility, e-glass fibre, diametral tensile strength.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 22139 An Analysis of the Performances of Various Buoys as the Floats of Wave Energy Converters
Authors: İlkay Özer Erselcan, Abdi Kükner, Gökhan Ceylan
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The power generated by eight point absorber type wave energy converters each having a different buoy are calculated in order to investigate the performances of buoys in this study. The calculations are carried out by modeling three different sea states observed in two different locations in the Black Sea. The floats analyzed in this study have two basic geometries and four different draft/radius (d/r) ratios. The buoys possess the shapes of a semi-ellipsoid and a semi-elliptic paraboloid. Additionally, the draft/radius ratios range from 0.25 to 1 by an increment of 0.25. The radiation forces acting on the buoys due to the oscillatory motions of these bodies are evaluated by employing a 3D panel method along with a distribution of 3D pulsating sources in frequency domain. On the other hand, the wave forces acting on the buoys which are taken as the sum of Froude-Krylov forces and diffraction forces are calculated by using linear wave theory. Furthermore, the wave energy converters are assumed to be taut-moored to the seabed so that the secondary body which houses a power take-off system oscillates with much smaller amplitudes compared to the buoy. As a result, it is assumed that there is not any significant contribution to the power generation from the motions of the housing body and the only contribution to power generation comes from the buoy. The power take-off systems of the wave energy converters are high pressure oil hydraulic systems which are identical in terms of their characteristic parameters. The results show that the power generated by wave energy converters which have semi-ellipsoid floats is higher than that of those which have semi elliptic paraboloid floats in both locations and in all sea states. It is also determined that the power generated by the wave energy converters follow an unsteady pattern such that they do not decrease or increase with changing draft/radius ratios of the floats. Although the highest power level is obtained with a semi-ellipsoid float which has a draft/radius ratio equal to 1, other floats of which the draft/radius ratio is 0.25 delivered higher power that the floats with a draft/radius ratio equal to 1 in some cases.Keywords: Black Sea, Buoys, Hydraulic Power Take-Off System, Wave Energy Converters.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 17248 Sustainable Hydrogel Nanocomposites Based on Grafted Chitosan and Clay for Effective Adsorption of Cationic Dye
Authors: H. Ferfera-Harrar, T. Benhalima, D. Lerari
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Contamination of water, due to the discharge of untreated industrial wastewaters into the ecosystem, has become a serious problem for many countries. In this study, bioadsorbents based on chitosan-g-poly(acrylamide) and montmorillonite (MMt) clay (CTS-g-PAAm/MMt) hydrogel nanocomposites were prepared via free‐radical grafting copolymerization and crosslinking of acrylamide monomer (AAm) onto natural polysaccharide chitosan (CTS) as backbone, in presence of various contents of MMt clay as nanofiller. Then, they were hydrolyzed to obtain highly functionalized pH‐sensitive nanomaterials with uppermost swelling properties. Their structure characterization was conducted by X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) analyses. The adsorption performances of the developed nanohybrids were examined for removal of methylene blue (MB) cationic dye from aqueous solutions. The factors affecting the removal of MB, such as clay content, pH medium, adsorbent dose, initial dye concentration and temperature were explored. The adsorption process was found to be highly pH dependent. From adsorption kinetic results, the prepared adsorbents showed remarkable adsorption capacity and fast adsorption rate, mainly more than 88% of MB removal efficiency was reached after 50 min in 200 mg L-1 of dye solution. In addition, the incorporating of various content of clay has enhanced adsorption capacity of CTS-g-PAAm matrix from 1685 to a highest value of 1749 mg g-1 for the optimized nanocomposite containing 2 wt.% of MMt. The experimental kinetic data were well described by the pseudo-second-order model, while the equilibrium data were represented perfectly by Langmuir isotherm model. The maximum Langmuir equilibrium adsorption capacity (qm) was found to increase from 2173 mg g−1 until 2221 mg g−1 by adding 2 wt.% of clay nanofiller. Thermodynamic parameters revealed the spontaneous and endothermic nature of the process. In addition, the reusability study revealed that these bioadsorbents could be well regenerated with desorption efficiency overhead 87% and without any obvious decrease of removal efficiency as compared to starting ones even after four consecutive adsorption/desorption cycles, which exceeded 64%. These results suggest that the optimized nanocomposites are promising as low cost bioadsorbents.
Keywords: Chitosan, clay, dye adsorption, hydrogels nanocomposites.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 10117 Nonlinear Transformation of Laser Generated Ultrasonic Pulses in Geomaterials
Authors: Elena B. Cherepetskaya, Alexander A. Karabutov, Natalia B. Podymova, Ivan Sas
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Nonlinear evolution of broadband ultrasonic pulses passed through the rock specimens is studied using the apparatus “GEOSCAN-02M”. Ultrasonic pulses are excited by the pulses of Qswitched Nd:YAG laser with the time duration of 10 ns and with the energy of 260 mJ. This energy can be reduced to 20 mJ by some light filters. The laser beam radius did not exceed 5 mm. As a result of the absorption of the laser pulse in the special material – the optoacoustic generator–the pulses of longitudinal ultrasonic waves are excited with the time duration of 100 ns and with the maximum pressure amplitude of 10 MPa. The immersion technique is used to measure the parameters of these ultrasonic pulses passed through a specimen, the immersion liquid is distilled water. The reference pulse passed through the cell with water has the compression and the rarefaction phases. The amplitude of the rarefaction phase is five times lower than that of the compression phase. The spectral range of the reference pulse reaches 10 MHz. The cubic-shaped specimens of the Karelian gabbro are studied with the rib length 3 cm. The ultimate strength of the specimens by the uniaxial compression is (300±10) MPa. As the reference pulse passes through the area of the specimen without cracks the compression phase decreases and the rarefaction one increases due to diffraction and scattering of ultrasound, so the ratio of these phases becomes 2.3:1. After preloading some horizontal cracks appear in the specimens. Their location is found by one-sided scanning of the specimen using the backward mode detection of the ultrasonic pulses reflected from the structure defects. Using the computer processing of these signals the images are obtained of the cross-sections of the specimens with cracks. By the increase of the reference pulse amplitude from 0.1 MPa to 5 MPa the nonlinear transformation of the ultrasonic pulse passed through the specimen with horizontal cracks results in the decrease by 2.5 times of the amplitude of the rarefaction phase and in the increase of its duration by 2.1 times. By the increase of the reference pulse amplitude from 5 MPa to 10 MPa the time splitting of the phases is observed for the bipolar pulse passed through the specimen. The compression and rarefaction phases propagate with different velocities. These features of the powerful broadband ultrasonic pulses passed through the rock specimens can be described by the hysteresis model of Preisach- Mayergoyz and can be used for the location of cracks in the optically opaque materials.Keywords: Cracks, geological materials, nonlinear evolution of ultrasonic pulses, rock.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 18956 Effects of the Coagulation Bath and Reduction Process on SO2 Adsorption Capacity of Graphene Oxide Fiber
Authors: Özge Alptoğa, Nuray Uçar, Nilgün Karatepe Yavuz, Ayşen Önen
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Sulfur dioxide (SO2) is a very toxic air pollutant gas and it causes the greenhouse effect, photochemical smog, and acid rain, which threaten human health severely. Thus, the capture of SO2 gas is very important for the environment. Graphene which is two-dimensional material has excellent mechanical, chemical, thermal properties, and many application areas such as energy storage devices, gas adsorption, sensing devices, and optical electronics. Further, graphene oxide (GO) is examined as a good adsorbent because of its important features such as functional groups (epoxy, carboxyl and hydroxyl) on the surface and layered structure. The SO2 adsorption properties of the fibers are usually investigated on carbon fibers. In this study, potential adsorption capacity of GO fibers was researched. GO dispersion was first obtained with Hummers’ method from graphite, and then GO fibers were obtained via wet spinning process. These fibers were converted into a disc shape, dried, and then subjected to SO2 gas adsorption test. The SO2 gas adsorption capacity of GO fiber discs was investigated in the fields of utilization of different coagulation baths and reduction by hydrazine hydrate. As coagulation baths, single and triple baths were used. In single bath, only ethanol and CaCl2 (calcium chloride) salt were added. In triple bath, each bath has a different concentration of water/ethanol and CaCl2 salt, and the disc obtained from triple bath has been called as reference disk. The fibers which were produced with single bath were flexible and rough, and the analyses show that they had higher SO2 adsorption capacity than triple bath fibers (reference disk). However, the reduction process did not increase the adsorption capacity, because the SEM images showed that the layers and uniform structure in the fiber form were damaged, and reduction decreased the functional groups which SO2 will be attached. Scanning Electron Microscopy (SEM), Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD) analyzes were performed on the fibers and discs, and the effects on the results were interpreted. In the future applications of the study, it is aimed that subjects such as pH and additives will be examined.
Keywords: Coagulation bath, graphene oxide fiber, reduction, SO2 gas adsorption.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 11805 Mechanical, Thermal and Biodegradable Properties of Bioplast-Spruce Green Wood Polymer Composites
Authors: A. Atli, K. Candelier, J. Alteyrac
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Environmental and sustainability concerns push the industries to manufacture alternative materials having less environmental impact. The Wood Plastic Composites (WPCs) produced by blending the biopolymers and natural fillers permit not only to tailor the desired properties of materials but also are the solution to meet the environmental and sustainability requirements. This work presents the elaboration and characterization of the fully green WPCs prepared by blending a biopolymer, BIOPLAST® GS 2189 and spruce sawdust used as filler with different amounts. Since both components are bio-based, the resulting material is entirely environmentally friendly. The mechanical, thermal, structural properties of these WPCs were characterized by different analytical methods like tensile, flexural and impact tests, Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC) and X-ray Diffraction (XRD). Their water absorption properties and resistance to the termite and fungal attacks were determined in relation with different wood filler content. The tensile and flexural moduli of WPCs increased with increasing amount of wood fillers into the biopolymer, but WPCs became more brittle compared to the neat polymer. Incorporation of spruce sawdust modified the thermal properties of polymer: The degradation, cold crystallization, and melting temperatures shifted to higher temperatures when spruce sawdust was added into polymer. The termite, fungal and water absorption resistance of WPCs decreased with increasing wood amount in WPCs, but remained in durability class 1 (durable) concerning fungal resistance and quoted 1 (attempted attack) in visual rating regarding to the termites resistance except that the WPC with the highest wood content (30 wt%) rated 2 (slight attack) indicating a long term durability. All the results showed the possibility to elaborate the easy injectable composite materials with adjustable properties by incorporation of BIOPLAST® GS 2189 and spruce sawdust. Therefore, lightweight WPCs allow both to recycle wood industry byproducts and to produce a full ecologic material.
Keywords: Biodegradability, durability, mechanical properties, melt flow index, spectrophotometry, structural properties, thermal properties, wood-plastic composites.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 10504 Green Synthesis of Nanosilver-Loaded Hydrogel Nanocomposites for Antibacterial Application
Authors: D. Berdous, H. Ferfera-Harrar
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Superabsorbent polymers (SAPs) or hydrogels with three-dimensional hydrophilic network structure are high-performance water absorbent and retention materials. The in situ synthesis of metal nanoparticles within polymeric network as antibacterial agents for bio-applications is an approach that takes advantage of the existing free-space into networks, which not only acts as a template for nucleation of nanoparticles, but also provides long term stability and reduces their toxicity by delaying their oxidation and release. In this work, SAP/nanosilver nanocomposites were successfully developed by a unique green process at room temperature, which involves in situ formation of silver nanoparticles (AgNPs) within hydrogels as a template. The aim of this study is to investigate whether these AgNPs-loaded hydrogels are potential candidates for antimicrobial applications. Firstly, the superabsorbents were prepared through radical copolymerization via grafting and crosslinking of acrylamide (AAm) onto chitosan backbone (Cs) using potassium persulfate as initiator and N,N’-methylenebisacrylamide as the crosslinker. Then, they were hydrolyzed to achieve superabsorbents with ampholytic properties and uppermost swelling capacity. Lastly, the AgNPs were biosynthesized and entrapped into hydrogels through a simple, eco-friendly and cost-effective method using aqueous silver nitrate as a silver precursor and curcuma longa tuber-powder extracts as both reducing and stabilizing agent. The formed superabsorbents nanocomposites (Cs-g-PAAm)/AgNPs were characterized by X-ray Diffraction (XRD), UV-visible Spectroscopy, Attenuated Total reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR), Inductively Coupled Plasma (ICP), and Thermogravimetric Analysis (TGA). Microscopic surface structure analyzed by Transmission Electron Microscopy (TEM) has showed spherical shapes of AgNPs with size in the range of 3-15 nm. The extent of nanosilver loading was decreased by increasing Cs content into network. The silver-loaded hydrogel was thermally more stable than the unloaded dry hydrogel counterpart. The swelling equilibrium degree (Q) and centrifuge retention capacity (CRC) in deionized water were affected by both contents of Cs and the entrapped AgNPs. The nanosilver-embedded hydrogels exhibited antibacterial activity against Escherichia coli and Staphylococcus aureus bacteria. These comprehensive results suggest that the elaborated AgNPs-loaded nanomaterials could be used to produce valuable wound dressing.
Keywords: Antibacterial activity, nanocomposites, silver nanoparticles, superabsorbent hydrogel.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 17043 Utilizing Fly Ash Cenosphere and Aerogel for Lightweight Thermal Insulating Cement-Based Composites
Authors: Asad Hanif, Pavithra Parthasarathy, Zongjin Li
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Thermal insulating composites help to reduce the total power consumption in a building by creating a barrier between external and internal environment. Such composites can be used in the roofing tiles or wall panels for exterior surfaces. This study purposes to develop lightweight cement-based composites for thermal insulating applications. Waste materials like silica fume (an industrial by-product) and fly ash cenosphere (FAC) (hollow micro-spherical shells obtained as a waste residue from coal fired power plants) were used as partial replacement of cement and lightweight filler, respectively. Moreover, aerogel, a nano-porous material made of silica, was also used in different dosages for improved thermal insulating behavior, while poly vinyl alcohol (PVA) fibers were added for enhanced toughness. The raw materials including binders and fillers were characterized by X-Ray Diffraction (XRD), X-Ray Fluorescence spectroscopy (XRF), and Brunauer–Emmett–Teller (BET) analysis techniques in which various physical and chemical properties of the raw materials were evaluated like specific surface area, chemical composition (oxide form), and pore size distribution (if any). Ultra-lightweight cementitious composites were developed by varying the amounts of FAC and aerogel with 28-day unit weight ranging from 1551.28 kg/m3 to 1027.85 kg/m3. Excellent mechanical and thermal insulating properties of the resulting composites were obtained ranging from 53.62 MPa to 8.66 MPa compressive strength, 9.77 MPa to 3.98 MPa flexural strength, and 0.3025 W/m-K to 0.2009 W/m-K as thermal conductivity coefficient (QTM-500). The composites were also tested for peak temperature difference between outer and inner surfaces when subjected to heating (in a specially designed experimental set-up) by a 275W infrared lamp. The temperature difference up to 16.78 oC was achieved, which indicated outstanding properties of the developed composites to act as a thermal barrier for building envelopes. Microstructural studies were carried out by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) for characterizing the inner structure of the composite specimen. Also, the hydration products were quantified using the surface area mapping and line scale technique in EDS. The microstructural analyses indicated excellent bonding of FAC and aerogel in the cementitious system. Also, selective reactivity of FAC was ascertained from the SEM imagery where the partially consumed FAC shells were observed. All in all, the lightweight fillers, FAC, and aerogel helped to produce the lightweight composites due to their physical characteristics, while exceptional mechanical properties, owing to FAC partial reactivity, were achieved.
Keywords: Sustainable development, fly ash cenosphere, aerogel, lightweight, cement, composite.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 22092 Nanostructured Pt/MnO2 Catalysts and Their Performance for Oxygen Reduction Reaction in Air Cathode Microbial Fuel Cell
Authors: Maksudur Rahman Khan, Kar Min Chan, Huei Ruey Ong, Chin Kui Cheng, Wasikur Rahman
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Microbial fuel cells (MFCs) represent a promising technology for simultaneous bioelectricity generation and wastewater treatment. Catalysts are significant portions of the cost of microbial fuel cell cathodes. Many materials have been tested as aqueous cathodes, but air-cathodes are needed to avoid energy demands for water aeration. The sluggish oxygen reduction reaction (ORR) rate at air cathode necessitates efficient electrocatalyst such as carbon supported platinum catalyst (Pt/C) which is very costly. Manganese oxide (MnO2) was a representative metal oxide which has been studied as a promising alternative electrocatalyst for ORR and has been tested in air-cathode MFCs. However the single MnO2 has poor electric conductivity and low stability. In the present work, the MnO2 catalyst has been modified by doping Pt nanoparticle. The goal of the work was to improve the performance of the MFC with minimum Pt loading. MnO2 and Pt nanoparticles were prepared by hydrothermal and sol gel methods, respectively. Wet impregnation method was used to synthesize Pt/MnO2 catalyst. The catalysts were further used as cathode catalysts in air-cathode cubic MFCs, in which anaerobic sludge was inoculated as biocatalysts and palm oil mill effluent (POME) was used as the substrate in the anode chamber. The asprepared Pt/MnO2 was characterized comprehensively through field emission scanning electron microscope (FESEM), X-Ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) where its surface morphology, crystallinity, oxidation state and electrochemical activity were examined, respectively. XPS revealed Mn (IV) oxidation state and Pt (0) nanoparticle metal, indicating the presence of MnO2 and Pt. Morphology of Pt/MnO2 observed from FESEM shows that the doping of Pt did not cause change in needle-like shape of MnO2 which provides large contacting surface area. The electrochemical active area of the Pt/MnO2 catalysts has been increased from 276 to 617 m2/g with the increase in Pt loading from 0.2 to 0.8 wt%. The CV results in O2 saturated neutral Na2SO4 solution showed that MnO2 and Pt/MnO2 catalysts could catalyze ORR with different catalytic activities. MFC with Pt/MnO2 (0.4 wt% Pt) as air cathode catalyst generates a maximum power density of 165 mW/m3, which is higher than that of MFC with MnO2 catalyst (95 mW/m3). The open circuit voltage (OCV) of the MFC operated with MnO2 cathode gradually decreased during 14 days of operation, whereas the MFC with Pt/MnO2 cathode remained almost constant throughout the operation suggesting the higher stability of the Pt/MnO2 catalyst. Therefore, Pt/MnO2 with 0.4 wt% Pt successfully demonstrated as an efficient and low cost electrocatalyst for ORR in air cathode MFC with higher electrochemical activity, stability and hence enhanced performance.
Keywords: Microbial fuel cell, oxygen reduction reaction, Pt/MnO2, palm oil mill effluent, polarization curve.
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 35061 Investigation of New Method to Achieve Well Dispersed Multiwall Carbon Nanotubes Reinforced Al Matrix Composites
Authors: A.H.Javadi, Sh.Mirdamadi, M.A.Faghisani, S.Shakhesi
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Nanostructured materials have attracted many researchers due to their outstanding mechanical and physical properties. For example, carbon nanotubes (CNTs) or carbon nanofibres (CNFs) are considered to be attractive reinforcement materials for light weight and high strength metal matrix composites. These composites are being projected for use in structural applications for their high specific strength as well as functional materials for their exciting thermal and electrical characteristics. The critical issues of CNT-reinforced MMCs include processing techniques, nanotube dispersion, interface, strengthening mechanisms and mechanical properties. One of the major obstacles to the effective use of carbon nanotubes as reinforcements in metal matrix composites is their agglomeration and poor distribution/dispersion within the metallic matrix. In order to tap into the advantages of the properties of CNTs (or CNFs) in composites, the high dispersion of CNTs (or CNFs) and strong interfacial bonding are the key issues which are still challenging. Processing techniques used for synthesis of the composites have been studied with an objective to achieve homogeneous distribution of carbon nanotubes in the matrix. Modified mechanical alloying (ball milling) techniques have emerged as promising routes for the fabrication of carbon nanotube (CNT) reinforced metal matrix composites. In order to obtain a homogeneous product, good control of the milling process, in particular control of the ball movement, is essential. The control of the ball motion during the milling leads to a reduction in grinding energy and a more homogeneous product. Also, the critical inner diameter of the milling container at a particular rotational speed can be calculated. In the present work, we use conventional and modified mechanical alloying to generate a homogenous distribution of 2 wt. % CNT within Al powders. 99% purity Aluminium powder (Acros, 200mesh) was used along with two different types of multiwall carbon nanotube (MWCNTs) having different aspect ratios to produce Al-CNT composites. The composite powders were processed into bulk material by compaction, and sintering using a cylindrical compaction and tube furnace. Field Emission Scanning electron microscopy (FESEM), X-Ray diffraction (XRD), Raman spectroscopy and Vickers macro hardness tester were used to evaluate CNT dispersion, powder morphology, CNT damage, phase analysis, mechanical properties and crystal size determination. Despite the success of ball milling in dispersing CNTs in Al powder, it is often accompanied with considerable strain hardening of the Al powder, which may have implications on the final properties of the composite. The results show that particle size and morphology vary with milling time. Also, by using the mixing process and sonication before mechanical alloying and modified ball mill, dispersion of the CNTs in Al matrix improves.Keywords: multiwall carbon nanotube, Aluminum matrixcomposite, dispersion, mechanical alloying, sintering
Procedia APA BibTeX Chicago EndNote Harvard JSON MLA RIS XML ISO 690 PDF Downloads 2325