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A: Invest casting Liquid-to-solid transformation An example of phase transformationSlide3: Czochralski crystal pulling technique for single crystal SiSlide4: Quenching of steel components a solid->solid phase transformationSlide5: Liquid solidification evaporation sublimation Solid gas melting condensation Solid state phase transformation Solid 2 1Slide6: Thermodynamic driving force for a phase transformation Decrease in Gibbs free energy Liquid-> solid gs - gl = g = -veSlide7: g gL gS gS < gL gL < gS Liquid is stable Tm T Gibbs free energy as a function of temperature, Problem 2.3 gL gS g Solid is stable Tfreesing Fig. 9.1Slide8: How does solidification begins? Usually at the walls of the container Why? To be discussed later. Heterogeneous nucleation.Slide9: Spherical ball of solid of radius R in the middle of the liquid at a temperature below Tm Homogeneous nucleation gL = free energy of liquid per unit volume gS = free energy of solid per unit volume g = gS - gLSlide10: Change in free energy of the system due to formation of the solid ball of radius r : +ve: barrier to nucleation r r*Slide11: r r* Solid balls of radius r < r* cannot grow as it will lead to increase in the free energy of the system !!! Solid balls of radii r > r* will grow r* is known as the CRITICAL RADIUS OF HOMOGENEOUS NUCLEATIONSlide12: r r* Eqn. 9.5 Eqn. 9.4Slide13: T Eqn. 9.7Slide14: f r Eqn. 9.8 Eqn. 9.7 Fig. 9.3 r1* f1* f2* r2* T1 T2 <Slide15: Critical particle Fig. 9.4 Formation of critical nucleus by statistical flucctuation Atoms surrounding the critical particle Diffuse jump of a surrounding atom to the critical particle makes it a nucleationSlide16: The Nucleation Rate Nt=total number of clusters of atoms per unit volume N* = number of clusters of critical size per unit volume By Maxwell-Boltzmann statisticsSlide17: s*= no. of liquid phase atoms facing the critical sized particle Hd = activation energy for diffusive jump from liquid to the solid phase = atomic vibration frequency The rate of successful addition of an atom to a critical sized paticle Eqn. 9.10 Eqn. 9.9Slide18: Rate of nucleation, I , (m3 s-1) With decreasing T 1. Driving force increases 2. Atomic mobility decreases = No. of nucleation events per m3 per sec = number of critical clusters per unit volume (N*) x rate of successful addition of an atom to the critical cluster (’) Eqn. 9.11 Slide19: Growth Increase in the size of a product particle after it has nucleated Slide20: Overall Transformation Kinetics U I dX/dt T I : Nucleation rate U : Growth rate Overall transformation rate (fraction transformed per second) X=fraction of product phaseSlide21: Fraction transformed as a function of time ts tf X t Slow due to very few nuclei Slow due to final impingement Slide22: TTT Diagram for liquid-to-solid transformation T Stable liquid Under Cooled liquid crystal Crystallization begins L+ Crystallization ends log t Tm C- curves Slide23: TTT Diagram for liquid-to-solid transformation Coarse grained crystals Fine grained crystals glass Slide24: T log t ts metals ts SiO2 Hd ∝ log (viscosity) Metals: high hm, low viscosity SiO2: low hm, high viscosity Silica glass Metallic glass Eqn. 9.11 Eqn. 9.8Slide25: Cooling rate 106 ºC s-1 F r o m P r i n c i p l e s o f E l e c t r o n i c M a t e r i a l s a n d D e v i c e s , S e c o n d E d i t i o n , S . O . K a s a p ( © M c G r a w - H i l l , 2 0 0 2 ) h t t p : / / M a t e r i a l s . U s a s k . C a Melt Spinning for metallic glass ribbonsSlide26: L+ T log t Tm T Tm Tg Log (viscosity) 12 18 crystal Stable liquid Undercooled liquid glass 30 Fig. 9.17Slide27: Tm Specific volume Stable liquid Undercooled liquid Fast cool Slow cool Tgs Tgf crystal Fig. 9.18 TSlide28: log t L+ T Stable liquid Undercooled liquid Tm devitrification time T Glass ceramics nucleation growth glass Glass ceramic Liquid glass crystal Very fine crystalsSlide29: Corning’s new digital hot plates with PyroceramTM tops. Corningware PyroceramTM heat resistant cookware ROBAX® was heated until red-hot. Then cold water was poured on the glass ceramic from above - with NO breakage.Slide30: Czochralski crystal pulling technique for single crystal Si SSPL: Solid State Physics Laboratory, N. Delhi J. Czochralski, (1885-1953) Polish MetallurgistSlide31: You may collect slide handouts for chapters 6, 7 and 8 from Scoops Xerox Shop no more grades, no more pencils, no more sharing/using stencils, no more reading, no more books, no more teachers dirty looks, so when we hear that final bell, we drop our books and run like hell !! Slide32: A Steel Hardness Rockwell C 15 0.8 Wt% C Micro-structure Coarse pearlite fine pearlite bainite Tempered martensite martensite 0.8 0.8 0.8 0.8 30 45 55 65 Heat treatment Annealing normalizing austempering tempering quenching B C D E TABLE 9.2Slide33: HEAT TREATMENT Heating a material to a high temperature, holding it at that temperature for certain length of time followed by cooling at a specified rate is called heat treatmentSlide34: A N AT T Q heating holding time T Annealing Furnace cooling RC 15 Normalizing Air cooling RC 30 Quenching Water cooling RC 65 Tempering Heating after quench RC 55 Austempering Quench to an inter- RC 45 mediate temp and hold Slide35: Ammount of Fe3C in Pearlite Red Tie Line below eutectoid tempSlide36: Phase diagrams do not have any information about time or rates of transformations. We need TTT diagram for austenite-> pearlite transformationSlide37: Stable austenite unstable austenite TTT diagram for eutectoid steel start finishSlide38: Annealing: coarse pearlite Normalizing: fine pearlite TTT diagram for eutectoid steelSlide39: CallisterSlide40: Stable austenite unstable austenite start finish TTT diagram for eutectoid steel A+M M Ms Mf Ms : Martensite start temperature Mf : Martensite finish temperature ’: martensite (M) QUENCHING Hardness RC 65 Extremely rapid, no C-curvesSlide41: BCT Amount of martensite formed does not depend upon time, only on temperature. Atoms move only a fraction of atomic distance during the transformation: 1. Diffusionless (no long-range diffusion) 2. Shear (one-to-one correspondence between and ’ atoms) 3. No composition change Martensitic transformationSlide42: Problem 3.1 BCT unit cell of (austenite) BCT unit cell of ’ (martensite) 0% C (BCC) 1.2 % C Martensitic transformation (contd.) Fig. 9.12Slide43: Hardness of martensite as a function of C content Wt % Carbon → 20 40 60 0.2 0.4 0.6 Hardness, RC Hardness of martensite depends mainly on C content and not on other alloying additions Fig. 9.13 Martensitic transformation (contd.)Slide44: A N AT T Q heating T Slide45: Heating of quenched steel below the eutectoid temperature, holding for a specified time followed by ar cooling. TEMPERING T<TE ?Slide46: Tempering (contd.) +Fe3C PEARLITE A distribution of fine particles of Fe3C in matrix known as TEMPERED MARTENSITE. Hardness more than fine pearlite, ductility more than martensite. Hardness and ductility controlled by tempering temperature and time. Higher T or t -> higher ductility, lower strength Slide47: Tempering Continued CallisterSlide48: Austempering Bainite Short needles of Fe3C embedded in plates of ferriteSlide49: Problems in Quenching Quench Cracks High rate of cooling: surface cooler than interior Surface forms martensite before the interior Austenite martensite Volume expansion When interior transforms, the hard outer martensitic shell constrains this expansion leading to residual stressesSlide50: But how to shift the C-curve to higher times? Solution to Quench cracks Shift the C-curve to the right (higher times) More time at the nose Slower quenching (oil quench) can give martensiteSlide51: By alloying All alloying elements in steel (Cr, Mn, Mo, Ni, Ti, W, V) etc shift the C-curves to the right. Exception: Co Substitutional diffusion of alloying elements is slower than the interstitial diffusion of C Slide52: Plain C steel Alloy steel Alloying shifts the C-curves to the right. Separate C-curves for pearlite and bainite Fig. 9.10Slide53: Hardenability Ability or ease of hardening a steel by formation of martensite using as slow quenching as possible Alloying elements in steels shift the C-curve to the right Alloy steels have higher hardenability than plain C steels.Slide54: Hardnenability Hardness Ability or ease of hardening a steel Resistance to plastic deformation as measured by indentation Only applicable to steels Applicable to all materials Alloying additions increase the hardenability of steels but not the hardness. C increases both hardenability and hardness of steels.Slide55: High Speed steel Alloy steels used for cutting tools operated at high speeds Cutting at high speeds lead to excessive heating of cutting tools This is equivalent to unintended tempering of the tools leading to loss of hardness and cutting edge Alloying by W gives fine distribution of hard WC particles which counters this reduction in hardness: such steels are known as high speed steels.Slide56: Airbus A380 to be launched on October 2007Slide57: A shop inside Airbus A380Slide58: Alfred Wilm’s Laboratory 1906-1909 Steels harden by quenching Why not harden Al alloys also by quenching?Slide59: time Wilm’s Plan for hardening Al-4%Cu alloy Sorry! No increase in hardness. 550ºC T Heat Quench Hold Check hardness Eureka ! Hardness has Increased !! One of the greatest technological achievements of 20th centurySlide60: Hardness increases as a function of time: AGE HARDENING Property = f (microstructure) Wilm checked the microstructure of his age-hardened alloys. Result: NO CHANGE in the microstructure !!Slide61: As- quenched hardness Hardness time Peak hardness Overaging Hardness initially increases: age hardening Attains a peak value Decreases subsequently: OveragingSlide62: + : solid solution of Cu in FCC Al : intermetallic compound CuAl2 4 Tsolvus supersaturated saturated + FCC FCC Tetragonal 4 wt%Cu 0.5 wt%Cu 54 wt%Cu Precipitation of in Slide63: Stable unstable Tsolvus As-quenched start finsh + Aging TTT diagram of precipitation of in A fine distribution of precipitates in matrix causes hardening Completion of precipitation corresponds to peak hardnessSlide64: Driving force for coarsening / interfacial energySlide65: 0.1 1 10 100 hardness Aging time (days) 180ºC 100ºC 20ºC Aging temperature Peak hardness is less at higher aging temperature Peak hardness is obtained in shorter time at higher aging temperature Fig. 9.15Slide66: U I T Stable unstable As-quenched start finsh + Aging Tsolvus 100 ºC 180 ºCSlide67: Recovery, Recrystallization and grain growth Following slides are courtsey Prof. S.K Gupta (SKG) Or Prof. Anandh Subramaniam (AS)Slide68: Cold work ↑ dislocation density ↑ point defect density Plastic deformation in the temperature range above(0.3 – 0.5) Tm → COLD WORK Point defects and dislocations have strain energy associated with them (1 -10) % of the energy expended in plastic deformation is stored in the form of strain energy ASSlide69: Cold work ↑ Hardness ↑ Strength ↑ Electrical resistance ↓ Ductility ASSlide70: Cold work Anneal Recrystallization Recovery Grain growth ASRecovery, Recrystallization and Grain Growth: Recovery, Recrystallization and Grain Growth During recovery 1. Point Defects come to Equilibrium 2. Dislocations of opposite sign lying on a slip plane annihilate each other (This does not lead to substantial decrease in the dislocation density) SKGSlide72: POLYGONIZATION Bent crystal Low angle grain boundaries Polygonization ASRecrystallization: Recrystallization Strained grains Strain-free grains Driving force for the Process = Stored strain energy of dislocations SKGSlide74: Recrystallization Temperature: Temperature at which the 50% of the cold-worked material recrystallizes in one hour Usually around 0.4 Tm (m.p in K) SKGSlide75: Factors that affect the recrystallization temperature: 1. Degree of cold work 2. Initial Grain Size 3. Temperature of cold working 4. Purity or composition of metal Solute Drag Effect Pinning Action of Second Phase Particle SKGSolute Drag Effect: Solute Drag Effect SKGGrain Boundary Pinning: Grain Boundary Pinning SKGGrain Growth: Grain Growth Increase in average grain size following recrystallization Driving Force reduction in grain boundary energy Impurities retard the process SKGSlide79: Grain growth Globally ► Driven by reduction in grain boundary energy Locally ► Driven by bond maximization (coordination number maximization) ASSlide80: Direction of grain boundary migration Boundary moves towards its centre of curvature JUMP ASSlide81: Hot Work and Cold Work Hot Work Plastic deformation above TRecrystallization Cold Work Plastic deformation below TRecrystallization Cold Work Hot Work Recrystallization temperature (~ 0.4 Tm) ASSlide82: Cold work Recovery Recrystallization Grain growth Tensile strength Ductility Electical conductivity Internal stress Fig. 9.19 %CW Annealing Temperature AS You do not have the permission to view this presentation. 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