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Nanoscale EngineeringNanostructured materials: processing and propertiesHelen REVERONLECTURE 22LECTURE 2•The conclusions LECTURE 1•Extra-topics attracting your attention•Type of materials•Processing nanostructured 3D materials•The « nanoscale » is very SMALL, invisible…•A nanometer (nm) equals (IS) one billionth of a meter (10-9m)•All around you is nano… from materials to energy, the environment to medicine, electronics to agriculture…•Nano should make anything more efficient, more resistant,cheaper and less polluting•The scope of this course : 3D nanostructured materials!-Filling the 3 dimensions-Nanograins/ Micrograins + Nanoparticles-Interfaces control properties-Grain boundaries : dislocationsNanostructured materials :The former usually refer to condensed bulk materials that are made of grains withgrain sizes in the nanometer size rangeLECTURE 1 :Grain growth-2D Ostwald repining-Model grain growth withouth second phase-Model for grain growth with second phaseGrain growth refers to the increase in size of grains (crystallites )in a material at high temperature The boundary between one grain and its neighbour is a defect in the crystal structure and so it is associated with a certain amount of energy. As a result there is a thermodynamic driving force for the total area of boundary to be reduced. If the grain size increases, thenthe total area of boundary will be reduced.56 LECTURE 1 Question1: CdSe dots (Christian)Quantum dot of CdSe synthesis? And structure?Preparation of Cadmium Selenide Quantum Dot NanoparticlesFilmStructure:Many fundamental questions regarding their structural and opto-electronic properties remain unanswered. In particular, although transmission electron microscopy (TEM) indicates that CdSe nanoparticles adopt the wurtzite structure, resolving their surface geometry and assessing the influence of organic ligands on surface reconstructions is difficult. In contrast to Type IV and III-V semiconductors the size dependence of the optical gap of CdSe nanoparticles is largely independent of the surface termination. The origin of this insensitivity is not well understood. In addition, recent optical measurements indicate the presence of a sub-band gap state, with an unknown nature and dependence on the nanoparticle structure.CdSe Structureab-initio electronic structure calculations of CdSe nanoparticles with diameters up to 1.5~nm. Calculated relaxed atomic geometries with the corresponding ideal wurtzite structures . A substantial structural relaxation is observed on the surface of each cluster, although the wurtzite core is maintained. CdSe nanoparticles with ideal wurtzite structures are quasi-metallic and surface relaxations, not passivation by organic ligands, are responsible for opening up the gap in the clusters./Research/qsg-090205/cadmiumWires_dots.html Cd atomic radius is 0.16 nm Se atomic radius is 0.11 nm7The generic constituents of a thermal barrier system for a superalloy component are illustrated in Fig. 1, along with a summary of requisite attributes for performance and durability. The baseline thermal barrier or “top coat” is a 125–250 μm layer of porous ZrO2 partially stabilized with 7±1 wt.% Y2O3 (7YSZ), applied by either air-plasma spray (APS) or electron-beam physical vapor deposition (EB-PVD). Environmental protection relies primarily on a thin (<10 μm), dense Al2O3 layer (TGO), grown during service by thermal oxidation of the underlying metalNickel superalloy,nickel aluminideCurrent Opinion in Solid State andMaterials ScienceVolume 8, Issue 1, January 2004, Pages77-91Science 12 April 2002:Vol. 296. no. 5566, pp. 280 –284Thermal Barrier Coatings for Gas-TurbineEngine ApplicationsNitin P. Padture,1* Maurice Gell,1 Eric H.Jordan2Hundreds of different types of coatings are used to protect a variety of structural engineering materials from corrosion, wear, and erosion, and to provide lubrication and thermal insulation. Of all these, thermal barrier coatings (TBCs) have the most complex structure and must operate in the most demanding high-temperature environment of aircraft and industrial gas-turbine engines. TBCs, which comprise metal and ceramic multilayers, insulate turbine and combustor engine components from the hot gas stream, and improve the durability and energy efficiency of these engines.Science 12 April 2002:Vol. 296. no. 5566, pp. 280 -284Thermal Barrier Coatings for Gas-Turbine Engine Applications Nitin P. Padture,1* Maurice Gell,1 Eric H. Jordan211 Master Schedule and OutlineWeek/Date Section TopicWeek 1/Sept. 12Intro T104Why is nano-scale specialDefinition of nanostructured materialsHow are nanostructured materials different?Week 2/Sept. 19Processing T104Types of materials. Processing of nanostructured polymers.Week 3/Sept. 26Processing T110Processing of nanostructured metals and ceramicsNanopowders: dispersion and rheologyAtomisationWeek 4/ Oct. 03Processing T110Nanopowders: characteristics, dispersion and rheologyWeek 5/Oct. 10Processing T110Nanopowders : dispersionWeek 6/Oct. 17Sintering T110Wet and dry forming methods. AtomisationPrinciples of sinteringOct. 24-Nov. 1Holydays + public holydayWeek 7/Nov. 7Sintering T110Solid state sintering: fundamentals.Week 8/Nov. 14Sintering T110Liquid phase sintering and two-step methodsWeek 9/Nov. 21Sintering T110Hot pressing, microwave sintering, spark plasma sinteringWeek 10/Nov. 28Properties T115Applications: nanocomposites, nano-bioceramics…Week11/Dec. 5Properties T104Student final presentationsWeek 12/Dec. 12Properties T104Student final presentationsDec. 19 and 26Christmas holydays•Polymers: covalent bond involving electron sharing between adjacent atoms (insulators)•Metals: metallic bond involving a « mobile gas of electrons »free electrons for electrical conduction •Ceramics: non metallic/polymeric and inorganiccovalent/ionic bond•Composites: combinations of individuals materialsex: fiberglass: composite of glass fibers embeddedin a polymer matrix (high strength of the fiber +the flexibility of the polymer matrix).+ amorphous(glasses)The mechanical and physical properties of materials are a direct consequenceof their interatomic forces (bonding)Breaking down of the bulk material into nano sizedstructures or particlesBottom-up approach Building up of a material from the bottom: atom-by-atom, molecule-by-molecule, orcluster-by-clusterTop-down approachBreaking down of the bulk material into nano sized structures or particlesNanoparticles + Forming+ SinteringFormingSintering(T,P)Metals,ceramicsBrittleFracturewhensubjected tostressThe most common procedure for 3D nanostructured materials processing:Nanoparticles OrganizingNanoparticlesHigh density/compactness(ideally 74%)(Forming)Creatingsolid-solidinterfaces High density (100%) (grains<100 nm)18 Processing of nanostructured PolymersDEFINITION•Polymers are defined as very large macromolecules consisting of repeating units of monomers•The monomers can be linked together to generate alinear polymer•Three types of polymers:-Linear-Branched-Cross linkedEx: polystyrene (molecular weight range: 1700-2 890 000)Polymerization of a simple polymer such as PE (Polyethylene) uses a single monomer (ethylene) and joins these together to form Polyethylene:The polymer therefore consists of repeated units of:Polyethylene is an example of a ‘homopolymer’ where all the mers are the same. If the repeat unit in the PE structure is called ‘A’ then the structure of a homopolymer is:In some cases two different types of mers (‘A’ and ‘B’) are joined together to form a copolymer:HMWPE: Molecular weight (Mw) of 143 000 g /molPolymers can be also produced from solutionsserv.chula.ac.th/~sanongn1/processing.pdfExtrusion MethodPolymer extrusion is a high volume manufacturing process in which raw material is melted and formed into a continuous profile. Extrusion produces items such as pipe/tubing, weather stripping, fence, deck railing, window frames and wire insulation.-Raw thermoplastic polymers: polyethylene, polypropylene, acetal, acrylic, nylon(polyamides), polystyrene -Rotating screw –heated barrel (200-275°C): beds melt and are pushed trhough the barrel -Molten polymer enters the Die: gives the final product profile from a cylindrical profile to the final shape -Cooling/Cutting stepsExtrusion MethodExtrusion MethodThin film (flat or tubular) is the most common product. Other extruded products include pipe and tubing, monofilaments and textile fibers, flat sheet (anything over 0.25 mm), wire and cable covering, and a great variety of profiles such as window frames, gaskets and channels, and house siding. The products can be cut to length or rolled up as neededInjection moldingInjection moldingLarge variety of products with different shapes and sizes. Products with complex geometry that many other processes cannot create.-Extruder, home-made -PVC pipe extrusion line -Injection moldingPolymer/clay particles NanocompositesPolymer/clay particles NanocompositesIn this new class of material, nanosized inorganic filler(at least one dimension) are dispersed in polymer matrix offering tremendous properties improvementTypically smectite-type clays are used as fillers. Montmorillonite and hectorite layered structure are dispersed in polymer matrix.According with the bonding scenariuos between polymer chain and silicate layer, new material shows excellent mechanical properties compared to polymer: superior mechanical characteristics (higher tensile strength: 40% increase), heat resistance and chemical resistance.These results are achieved with only 0.1-10 %vol. addition clay nanosized.By embedding nanoclay structure in polymer matrix we obtain a new class of materials. Unlike to other nanotechnologies, this material found applications inmediately and is commercially developed./cable/safety/index.html/weimages/Publications/PU_nanocomposites_FR.pdfAt same temperatures>350°C the mass losses are significantly lower for the nanocomposite Indicating an improved stabilization (thermal stability)The heat release rate and the peak heat release are related to the « driven force » of the fire: Reduction for the peak of heat release was 44% for a TPU nanocomposite!Increase of the fire performance index: the time available to scape in a full-scale fire(flame retardancy improved in NC)Organic/clay particles NanocompositesFilm casting process onto a glass plate: 2D material! Casting process into a porous mold! 3D material!34 Next…Processing of nanostructured Metals…。