Metals I. Anne Mertens

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"MECA0139-1: Techniques "MECA0462-2 additives : et Materials 3D printing", Selection", ULg, 19/09/2017 25/10/2016 Metals I Anne Mertens

Introduction Outline Metallic materials Materials Selection: case studies in metallic materials Metal structures Equilibrium constitution and phase diagrams Case studies in phase diagrams

Introduction Metallic materials

Introduction - Metals (1) Large variety of metallic materials!

Introduction : Metals (2) Cohesion due to metallic bond Electrostatic attractive force between an electron cloud of delocalized electrons and positively charged metal ions Non directional Metallic materials: Generally good conductor of electricity and heat Relatively ductile good formability

Introduction Materials Selection : Case studies in metallic materials

Materials selection for model steam engine (1) Fully working model components requirements materials [http://www.hobbydownloads.com/steamgeneral.html] Ex: Boiler components must withstand high T [http://www.hobbydownloads.com/boilers.html]

Materials selection for model steam engine (2) Use of ferrous alloys Wheels, frame low loads (σ y ~220 MPa) easy to cut, bend... cheap [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Materials selection for model steam engine (3) Use of ferrous alloys Drive shafts, gear-wheel teeths higher stresses (σ y ~400 MPa) [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Materials selection for model steam engine (3) Use of ferrous alloys [http://ww3.tiki.ne.jp/~hwata/ew-lubricator.htm] Mechanical lubricator High friction and wear Quenched and tempered high carbon steels (σ y ~1000MPa) [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Materials selection for model steam engine (4) Use of ferrous alloys Fire grates, in direct contact with burning coal High T Oxidation Creep [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Materials selection for model steam engine (5) Use of ferrous alloys Fire grates High T Oxidation Creep [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Materials selection for model steam engine (6) Use of ferrous alloys [http://core.materials.ac.uk/s EARCH/detail.php?id=1415] [http://opensourcee cology.org/wiki/file: Design-7-A.png] Cylinder block Low stresses Easy to cast Graphite acts as lubricant [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Materials selection for model steam engine (7) Use of other alloys Boiler and firetubes Load from pressurized steam Corrosion Full size: mild steel [http://www.hobbydownloads.com/boilers.html]

Materials selection for model steam engine (8) Copper alloys Boiler and firetubes High thermal conductivity Corrosion resistance in clean water High cost (prohibitive in full size) [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Materials selection for beverage can (1) Strong requirements No seam, no leak Use as little metal as possible Light High formability Recyclable Not toxic Corrosion resistance (even in coke that is highly acid) Cheap

Materials selection for beverage can (2) Aluminium alloys [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Materials selection for artificial hip joints (1) Requirements: Large loads High resistance to bending Resistance to high-cycle fatigue Resistance to corrosion in body fluids Bio-compatibility Light (density prosthesis = density bone) [https://www.news- medical.net/accolade-c-femoral- Component-from-Stryker]

Materials selection for artificial hip joints (2) Titanium alloys [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Partial summary (1) Materials selection criteria Physical properties (density, conductivity...) Mechanical properties (yield stress, fatigue...) Corrosion resistance Bio-compatibility Processability, formability Cost...

Data for metals [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Data for metals [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Data for metals [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Data for metals Properties of metallic materials may be structure independent... (= f(composition)) e.g.: Young's modulus...... vs structure dependent (=f(composition, (micro)structure processing)) e.g.: yield strength, tensile strength... One must be really careful when dealing with structure-dependent properties! influenced by cold deformation, heat treatments...

Metal structures How do we describe the structure of a metal?

Crystal vs glass Long-range order Short-range order [http://www.majordifferences.com/2013/02/differencebetween-crystalline-and.html#.wb42e9e69py] Packing of atoms inside the materials

Common crystalline structures of pure metals [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Polymorphism Some metals may change crystalline structure depending on external conditions (p, T) e.g.: Fe and Ti Polymorphism may be controlled by alloying e.g.: addition of Ni in steel FCC at Room T [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Solutions vs compounds (1) Metals are rarely used in pure state Addition elements Alloys Alloying elements may be dissolved in the crystalline lattice of the main element Up to the solubility limit Interstitial solution e.g.: C in Fe Substitutional solution [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Solutions vs compounds (2) Solutions may be random, but clustering or ordering are also possible Random Clustered Ordered [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Solutions vs compounds (3) [alloying element] > solubility limit Excess precipitates forming a new intermetallic compound (with its own crystalline structure) Cu addition in Aluminium: Formation of CuAl 2 FCC structure of Al [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2] [http://deuns.chez.com/sciences /cristallo/cristallo2.html]

Solutions vs compounds (4) [alloying element] > solubility limit Excess precipitates forming a new intermetallic compound Solubility limit of C in BCC Fe at R.T.: 10-5 mass % Excess C forms cementite (Fe 3 C) [A. Mertens, ULg]

Phases (1) Phase = region of a material that has uniform physical and chemical properties

Phases (2) Liquid water = one phase Ice = one phase Liquid water + ice = two phases Cu fully dissolved in Al = one solid solution = one phase [Cu] > solubility limit in Al = Al (solid solution) + CuAl 2 (precipitates) = two phases

Grain and phase boundaries (1) A pure metal or a solid solution are single-phase systems...... but they are usually made of many crystals (with the same crystalline structure and chemical composition) Individual small crystal = grain Grains size and shape may affect material properties! [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Grain and phase boundaries (2) Two-phases metallic materials are also made from many grains of each of the phases Interphase boundaries: types Nature of interphase boundaries may affect material properties!

Grain and phase boundaries (3) Precipitates may take shape/morphology [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Partial summary (2) Some properties (e.g.: yield strength) are influenced by the structure of the material. Crystalline (or amorphous) structure Phases (solid solution, intermetallic compounds...) Size and shape of grains Interphase boundaries Structure is determined by Chemical composition Processing method (deformation, heat treatments...)

Introduction Metal structures Outline How can we understand/control the structure of a metallic material? Influence of chemical composition? Today Equilibrium constitution and phase diagrams Case studies in phase diagrams Influence of processing method? Next week

Introduction Metal structures Outline Crystal vs glass Solutions and compounds Phases Grain and phase boundaries Equilibrium constitution and phase diagrams Case studies in phase diagrams

Equilibrium constitution and phase diagrams How do we describe the influence of the chemical composition and external conditions (T,p) on the structure of a metallic materials?

Equilibrium (1) Intuitively: A system is in equilibrium when it exhibits no further tendency to change with time

Equilibrium (2) Intuitively: A system is in equilibrium when it exhibits no further tendency to change with time Thermodynamics: A system is in equilibrium when its energy is minimized

Equilibrium (2) Intuitively: A system is in equilibrium when it exhibits no further tendency to change with time Thermodynamics: A system is in equilibrium when its energy is minimized Equilibrium = G minimum with G: enthalpy

Phase diagrams x B : fraction of element B 1-x B : fraction of element A Atmospheric pressure Equilibrium = G minimum Equilibrium state of a binary system (A,B) at T 3 2 phases are present (liquid, solid) Compositions of each phase Fractions of each phase 100% A x 1 x 2 100% B [L. Zhigilei, Phase diagrams and Kinetics, University of Virginia] x 1 x 2

Reading phase diagrams: The Lever Rule Binary system with 2 phases (α, β) C α C 0 C β Relative fractions of each phase W α = (C β -C 0 )/(C β -C α ) W β = (C 0 -C α )/(C β -C α ) [L. Zhigilei, Phase diagrams and Kinetics, University of Virginia]

Example: Al-Cu alloys (1) T melting is minimum Eutectic

Example: Al-Cu alloys (2) Eutectic One single crystalline structure (α Al): FCC Intermetallic precipitates

Example: Al-Cu alloys (3) Eutectic Miscibility gap - Solubility of Cu in Al decreases with T One single crystalline structure (α Al): FCC Intermetallic precipitates x Cu

Example: Pb-Sn alloys (1) Common alloys for solder One phase: Liquid solution of Pb and Sn Eutectic Two phases (i.e. solid solutions) co-exist Solid solution of Sn in Pb [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Example: Pb-Sn alloys (2) Consider an alloy with 50% Pb and 50% Sn Number of phases at R.T.: 2 (Sn) and (Pb) [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Example: Pb-Sn alloys (3) Consider an alloy with 50% Pb and 50% Sn Composition of (Pb) at R.T.: 2 wt% Sn. [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Example: Pb-Sn alloys (4) Consider an alloy with 50% Pb and 50% Sn Fraction of (Pb) at R.T.: (50-0,3)/(98-0,3)=50,9 % (50-0,3) [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2] (98-0,3)

Example: Pb-Sn alloys (5) Consider an alloy with 50% Pb and 50% Sn Shape and size of (Sn) and (Pb)? Not from phase diagrams Depend on processing method Deformation, heat treatments (isothermal hold, cooling rate...) How can we use phase diagrams for materials selection? Case studies in phase diagrams

Outline Introduction Metal structures Equilibrium constitution and phase diagrams Case studies in phase diagrams Materials for soft solders Pure silicon for microchips : zone refining

Case studies in phase diagrams Selecting a material for soft solders

Solder materials (1) Based on the Sn-Pb system For electronics: low melting T + easy flow Eutectic [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Solder materials (2) Based on the Sn-Pb system For plumbing: Pipes used to be made of Pb Solders were built up in thick deposits around joints "Pasty" solder Roman baths, Bath (GB) [A. Mertens]

Solder materials (3) Based on the Sn-Pb system For plumbing: "pasty" solder = solid + liquid mixture Sn with 65 wt% Pb Melting range: 183-244 C At 210 C: L + (Pb) slurry No risk of melting the Pb pipes [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Solder materials (4) Boiler in model steam engines High service T Ag-based soft solder (T melting ~600 C) High Pb-content soft solder ~ T melting pure Pb i.e. 327 C [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Solder materials (5) Pb Ag [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Case studies in phase diagrams Zone refining for the production of pure silicon for microchips

Zone refining (1) Starting from Si with a small content of impurity C 0 Local equilibrium at the liquid/solid interface [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2] Impurity is "pushed" into the liquid

Zone refining (2) Starting from Si with a small content of impurity C 0 Concentration of impurity in liquid Concentration of impurity in the next solid layer [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Zone refining (3) Starting from Si with a small content of impurity C 0 Impurity is removed from the left-hand side of the bar and dumped at the righ-hand end. Process may be repeated to increase the refined volume. [M.F. Ashby and D.R.H. Jones, Engineering Materials, vol. 2]

Summary Materials selection criteria Properties (physical, mechanical...) Cost Some properties are structure-sensitive Chemical composition Processing method (deformation, heat treatments...) Understand/describe the structure of a material Equilibrium (phase diagram) - today Out-of-equilibrium - next week