01 introd
DESCRIPTION
TRANSCRIPT
Scienza e Tecnologia dei Materiali 2011 - M.Ferraris
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The aim of this course:
• The aim of this course is to provide Mechanical and Automotive Engineering students basic knowledge on different classes of materials
• Relationship between structure of materials and their properties (Materials Science)
• Structure of materials = chemical-physical structure, (chemical bonds, composition, …)
• To design/choose materials (Materials Engineering)• Choice of materials, production process,
structure-properties, performances, cost, life cycle
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MATERIALS OF INTEREST IN ENGINEERING
• Metals and alloys
• polymers
• composites
• glasses
• ceramics
(fuels, lubricants, paints, …....)
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http://helios.augustana.edu/physics/301/periodic-table-fix.jpg
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OVERVIEW ON METALS AND ALLOYS
• ELEMENTS (Fe, Ti, Al, Mg, Cu,…)• Heath and electricity• Prepared by melting• Can be machined• All solids at room temperature• Can form alloys• Corrosion and oxidation issues• Density ranging between 2,7 and 8 g/cm3
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OVERVIEW ON CERAMICS
• Compounds (oxydes, carbides, nitrides, ..)(Al2O3, SiC, Si3N4,…)(density ranging between 3 and 5 g/cm3)
• hard and brittle, difficult to be machined
• Insulators (heat and electricity)
• High melting point
• Prepared by sintering or other processes, never melting
• examples: bricks, concrete, tiles, porcellains, ….
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OVERVIEW ON POLYMERS• Organic macro-molecules,
natural or synthetic • Prepared by organic synthesis• Low density, less than 1g/cm3
• Easy to machine• Insulators (sound, heat and electricity)• Low thermal and mechanical properties• examples: tyres, adhesives, paints, bitumen,..
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OVERVIEW ON GLASSES
• Prepared by melting of oxides
(SiO2, Na2O, CaO, Al2O3, K2O,...)
• Hard, brittle, can be deformed only at suitable temperature, cannot be machined
• insulators (heat and electricity)• Density of about 2,5 g/cm3
• examples: window and car glasses, optical fibers
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OVERVIEW ON COMPOSITES• TWO PHASES:
MATRIX and SECOND PHASE• Classified according to the matrix:• Metal matrix composites• Polymer matrix composites• Ceramic matrix composites• Glass and glass-ceramic matrix composites• examples: wood, reinforced concrete, bones,
bamboo,….
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OVERVIEW ON COMPOSITES
• Can be classified according to the second phase morphology:
• Fiber reinforced composites (long fibers, short fibers)
• Particle reinforced composites
• The second phase can be: metal, polymer, ceramic, glass
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STRUCTURE OF MATERIALS
• CRYSTALLINE ORDERED– metals, ceramics
• AMORPHOUS DISORDERED
• glass, polymers
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EXCEPTIONS….
• Glass-ceramics, polymers, composites::
• Amorphous in some zones, crystalline in others
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CORRELATION STRUCTURE-PROPERTIES….
• …the aim of Materials Science
• CRYSTALLINE STRUCTURE– Melting Temperature
• AMORPHOUS STRUCTURE– They don’t have melting temperature,
but progressive softening
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CRYSTALLINE STRUCTURE: MELTING TEMPERATURE
• Melting temperature = Solid to liquid (Tm)
• directly proportional to the material bond strength
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MELTING TEMPERATURE
Tm (°C)
Tm (°C)
Tm (°C)
W 3410 Mg 651 Al2O3 2045
Ti 1675 Pb 270 SiO2 1730
Fe 1536 Sn 232 MgO 2800
Ni 1453 Al 660 CaCO3 1339
Cu 1083
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CRYSTALLINE STRUCTURE
• Chemical bond and crystalline structure: atoms, ions or molecules in crystalline structures are in ordered positions in crystalline cells
• atoms, ions or molecules are at the equilibrium distance between attraction and repulsion forces : bond length or bond distance
ibchem.com
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CRYSTALLINE STRUCTURE
• “CRYSTALLINE materials: ordered positioning of atoms (ex: metals), or ions (ex: ceramics) or molecules (ex: polymers)”
• CRYSTALLINE
CELL
• a,b,c
0,1-0,26 nm
Video
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CRYSTALLINE CELLS
a,b,c cell parameters cell angles
• identify the structure of crystalline materials by cell parameters
• a,b,c about 0,1-0,26 nm at room T and without external applied forces
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CRYSTALLINE CELLS
• a,b,c changes with T and applied forces
• At zero K they are at the equilibrium distance
• When T increases, vibration around the equilibrium distance cause thermal expansion, then melting.
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SEVERAL CRYSTALLINE CELLS
a = b = c = = = 90° CUBICa = b c = = = 90° TETRAGONALa b c = = = 90°
ORTOROMBIC
a = b = c = = 90° ROMBOEDRICa = b c = = 90° , = 120° HESAGONALa b c = = 90° MONOCLINE
a b c 90° TRICLINE
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Crystalline cells
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Es: Cu, Al, Ag, Au
Es: Fe, W, CrEs: Mg, Ti, Zn
Hexagonal compact
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• Lattice plane: 3 atoms (or ions or molecules) in a cell, define one lattice plane
• COORDINATION NUMBER:
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http://amscampus.cib.unibo.it/archive/00001824/01/5-Silicio_web.doc
http://www.diee.unica.it/~vanzi/Origami.PDF
http://www.lnf.infn.it/esperimenti/rap/docs/silicio.pdf
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Gold (Au) nanocluster, embedded in amorphous silica matrix(SiO2)
Au
silica, SiO2, amorphous
J. Morgiel, Cracovia
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http://ceramics.org/video/individual-carbon-atoms-in-motion/
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X-ray diffraction (XRD)
XRD of a crystalline material (Au)
XRD of amorphous silica and silica crystalline (SiO2)
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Electromagnetic radiation spectrum
E=h
energy = frequencywavelength
Energy, frequency
wavelength
High Energy, high frequency, short wavelength
Low Energy, low frequency, long wavelength
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X ray diffraction
n = 2 d sin (Bragg law)
n= number, 1, 2, 3…
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X-ray diffraction (XRD): to detect an amorphous or crystalline material
XRD of a crystalline material (Au)
XRD of amorphous silica and silica crystalline (SiO2)
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Examples of XRD
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CRYSTALLINE STRUCTURE: POLYMORPHISM
• A crystalline solid melts when heated
• Polymorphism: change of crystalline structure during heating (solid state reaction)
• examples: Ti, Fe, SiO2
• Polymorfism and variation of materials properties : (V, , k, E, d,….)
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POLYMORFISM
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CRYSTALLINE STRUCTURE: DEFECTS
• Crystalline structure is not completely ordered….LATTICE DEFECTS:
• MONODIMENSIONAL DEFECTS
• BIDIMENSIONAL DEFECTS
• TRIDIMENSIONAL DEFECTS
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MONODIMENSIONAL DEFECT: INTERSTITIAL
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MONODIMENSIONAL DEFECTS:SUBSTITUTIONAL
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MONODIMENSIONAL DEFECTS:SUBSTITUTIONAL
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MONODIMENSIONAL DEFECTS(or POINT DEFECTS)
• Vacancies (lack of one atom or ion or molecule in the lattice)
• interstials• substitutionals
vacancy
substitutionalinterstitial
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ARE POINT DEFECTS «DEFECTS»…?
• ALLOYS and in general solid solutions are possible because of interstitials and substitutionals defects
• presence of substitutional impurities are necessary for in semiconductor science
….
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Solid solutions: substitutional alloys• Metal alloys are solid solutions :
– up to 15% atoms as substitutional defects different from those of the main lattice
– Es: Cu/Ni– RNi = 1.25Å, RCu = 1.28Å– both CFC– Same electronegativity– valence Ni +2, Cu +1, +2
– Atoms with similar radius, crystalline cell, electronegativity and valence
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Solid solutions: interstitial alloys
– Atoms as interstitial defects different from those of the main lattice
– Only small atoms can enter a metallic cell as interstitial defects (max 10%)
– Ex.: carbon is an interstitial defects in the iron lattice in steels, up to about 2%
– RFe = 1.24Å, RC = 0.71Å
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BIDIMENSIONAL DEFECTS: DISLOCATONS
• Edge and screw dislocations: responsible of plastic deformation of materials
• (video)
• Commercial metal or alloy (ex. Cu) about 108 dislocations per cm3
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Dislocations in nature….!• Dislocation: one lattice plane more….
Solfuro di rame (CuS)
cactus!
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Edge dislocations
http://www.uet.edu.pk/dmems/EdgeDislocation.gif
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350Å
Nitruro di gallio(GaN)
Screw dislocations
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Dislocation motion
Vedi moto dislocazioni.ppt
1
2
3
4
5
6
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DISLOCATION AND PLASTIC DEFORMATION
• Dislocation motion means fracture of a bond and formation of another one in a different nearby lattice position
• dislocations are present in ALL crystalline materials (metals, ceramics,…)
• In ceramics, it is NOT possible to form a new bond in a different nearby lattice position due to the ionic or covalent nature of bonds. No plastic deformation (at room T)
• In metals, it IS possible to form a new bond in a different nearby lattice position due to the metal nature of bonds. Plastic deformation.
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Interaction between dislocations and point defects
Mechanical hardening, cold working
Video
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Dislocations interact with themselves: mechanical hardening of alloys
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INTERACTION DISLOCATION AND POINT DEFECTS
• DISLOCATIONS INTERACT with themselves (cold working, hardening).
• Dislocations interact with point defects: dislocation motion is slower (VIDEO) in alloys than in pure metals
• Better mechanical properties of alloys vs pure metals• Without dislocations, the plastic deformation of metals cannot
be explained • Dislocations can be seen with Scanning or Transmission
electron Microscopy (SEM, TEM).
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Dislocation motion
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Interaction dislocation substitutional defect and influence on mechanical properties of alloys vs pure metals
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Interaction dislocation/substitutional defect and influence on mechanical properties of alloys vs pure metals
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Preferential sliding planes for dislocations
Low density plane High density plane
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TRIDIMENTIONAL DEFECTS• surface is a defect : reactivity of atoms or
ions or molecules at the surface. Lower coordination number, higher reactivity
• GRAIN BOUNDARIES (gb)
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• GRAIN BOUNDARIES:
distorted bonds at the boundary between two grains in a polycrystalline material
TRIDIMENTIONAL DEFECTS
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SOLIDIFICATION OF A LIQUID AND ITS STRUCTURE
1425 °C
or SiO2
a 1730 °C
SLOW SPEEDSOLIDIFICATIONMONOCRYSTALLINE STRUCTURE
MEDIUM SPEED SOLIDIFICATIONPOLYCRYSTALLINE STRUCTURE
HIGH SPEED SOLIDIFICATIONAMORPHOUS STRUCTURE
LIQUIDGRAIN and GB
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Nucleation and growth, formation of GB in polycrystalline materials
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CRYSTALLINE STRUCTURE
• MONOCRYSTALS: crystalline cells all oriented in the same (ex. Silicon for microelectronics)
• POLYCRYSTALS: crystalline cells oriented in the same way ONLY inside grains: solidification too quick to allow same orientation in entire lattice (ex .metals, alloys, ceramics)
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Monocrystal (a) …. polycrystal(b)
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Monocrystals• Difficult to obtain compared to
polycrystalline materials
• Silicon for electronics– Extra slow molten silicon solidification
(1-10 m per second)– About 1.5m length silicon cylinders
300 mm diameter, sliced as wafers– About 10 defects/ cm 2
http://www.csc.fi/elmer/examples/czmeltflow/growth.gifhttp://www.ami.bolton.ac.uk/courseware/mdesign/ch2/SingleCrystalSiliconIngot.jpg
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http://www.ingegneriadelsole.it/celle_silicio_cristallino.htm
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Polycristalline materials• Natural solidification from a liquid metal gives a
polycrystalline metal• Several grains, same cell orientation inside the
grain, grains separated by grain boundaries(gb)
http://mimp.mems.cmu.edu/~ordofmag/alumina.jpghttp://www.mse.nthu.edu.tw/jimages/Beuty/Steel1.jpg
Grains in Al2O3
Grains in steel
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GRAIN BOUNDARIES
• Irregular bonds, impurities, dislocations, atoms with lower coordination number,…
• High reactivity • Observable by optical
microscopy and chemical etching
• (file micr_acciai_ghise; video crystalline cells, video mech
properties)
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Optical and electron Microscopy
• Optical microscopy (2000x)• Scanning Electron Microscopy (SEM)
(104x)• Transmission Electron Microscopy
(TEM) (106x)
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20 µm
TiTi2(Co,Ni)
Ti(Co,Ni)
TiCo
SEM and compositional analysis (EDS)
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Atomic Force Microscopy (AFM) (109x)
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SOLIDIFICATION OF A LIQUID AND ITS STRUCTURE
1425 °C
or SiO2
a 1730 °C
SLOW SPEEDSOLIDIFICATIONMONOCRYSTALLINE STRUCTURE
MEDIUM SPEED SOLIDIFICATIONPOLYCRYSTALLINE STRUCTURE
HIGH SPEED SOLIDIFICATIONAMORPHOUS STRUCTURE
LIQUIDGRAIN and GB
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AMORPHOUS MATERIALS
• Disordered structure, no melting point
• glasses, polymers
• Short range order (few nm) (ex: Si4+ and O--ions are situated in tetrahedra in silicate glasses
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• Local, short range order; bond angle and length are variable
• No order after few nanometers
• “Undercooled liquids”• Quick solidification of a liquid• “No time to obtain a
crystalline structure” !
http://www.research.ibm.com/amorphous/figure1.gif
Amorphous silica
AMORPHOUS MATERIALS
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Amorphous materials: silica glasses
Si4+
O--
tetrahedron amorphous structure of silica: tetrahedra chains
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Crystalline and amorphous silica (SiO2)
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AMORPHOUS MATERIALS• Amorphous materials are not
thermodynamically stable: • They become crystalline if suitable
heated• All liquids can be solidified quickly
enough to obtain amorphous solids• All liquids can be solidified slowly enough
to obtain poly- or mono-crystalline solids
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• Ex: silica glass: bond angles, force and length differ in different tetraedra
• No melting temperature
• Viscosity vs temperature
• The opposite than with crystalline materials !
AMORPHOUS MATERIALS
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VISCOSITY
• Viscosity is a measure of a fluid's resistance to flow.
• It describes the internal friction of a moving fluid (i.e. tetrahedra chains in a silica glass).
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VISCOSITY
• Viscosity Unit : Poise
10 Poise = 1 Pa∙s = 1 (N/m2)∙s
• Example of viscosity: H2O (room T) = 1 x 10-3 Pa s
SiO2(silica) (1720°) = 1 x 106 Pa s
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VISCOSITY : AMORPHOUS and CRYSTALLINE materials
Viscosity decreases continuosly for amorphous materials.
This is not the case for crystalline materials
Al2O3
Glasses, polymers
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VISCOSITY
annealing
softening
Working point
Melting point
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Viscosity curve of a glass
Viscosity for glass and glass-ceramics
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glassGlass-ceramic