Course D - Microstructure Flashcards
how should you prepare a sample for reflected light microscopy
1) mount, grind, polish the sample to achieve a flat, level surface
2) etch the surface to highlight important features - usually done using chemicals
what does etching do
- etching is treating a sample with a chemical to highlight features, the etching process occurs quicker at grain boundaries and other impurities so they will reflect light differently
what sort of samples are required for transmitted light microscopy
- Transmitted light microscopy relies on detecting the light that has passed through a sample
- very thin samples required
- good for showing grain sizes
what causes contrast in transmitted light microscopy
- differences in absorption
- differences in birefringence
what properties must a material sample have for SEM
- should be prepared through polishing and etching
- cannot be conductive
what is atomic force microscopy (AFM)
- a very sharp tip is mounted on a cantilever and moved across the surface of a material
- this measures the height of the sample
- atomic level resolution can be achieved
what do pressure-temperature phase diagrams show
- for a given composition they show which phase is most THERMODYNAMICALLY stable at some temperature and pressure
why is the most thermodynamically stable phase not necessarily the phase present at a given temp/pres.
- kinetics can prevent a phase from forming
what do temperature-composition phase diagrams show
- they show which phase is most stable at some temperature and composition for a constant, given pressure
what do we mean when we talk about a system
“The subject of a thermodynamic analysis”
what are the 4 types of equilibrium (or not equilibrium) that a phase can be in at any given point
1) stable equilibrium - in a potential energy minimum, the overall minimum for the system
2) unstable equilibrium - at a potential energy maximum, unstable to any perturbations
3) not in equil - not at a max/min, there’s a driving force
4) metastable equil. - stable to small perturbations but not lowest energy state, local potential energy min. but not overall min.
what are the first and second laws of thermodynamics
1st law of thermodynamics: Total energy of universe is conserved
2nd law of thermodynamics: Entropy of the universe cannot decrease
what is the internal energy, U of a system, give the differential form of the equation for U
internal energy of a system, U = potential energy + kinetic energy
dU = δq + δw
q = heat
w = work done
define heat, give a differential equation for it
“The energy that ‘flows’ across a system boundary in response to a temperature gradient”
δq = CdT
C = heat capacity
define work done, give a differential equation for it
“the energy that flows across a system boundary in response to a force moving through a distance”
δw = -p dV
p = pres.
V = vol.
using the differential definitions for heat and work done, redefine the differential equation for internal energy
we know
dU = δq + δw
so
dU = CdT - pdV
give the overall equation for enthalpy, H
H = U +PV
give a differential form of the equation for enthalpy
dH = dU + PdV + VdP
and dU = CdT - pdV
so
dH = CdT + VdP
i.e. enthalpy is the heat transferred at a constant pressure
define entropy, how does it link to the 2nd law of thermodynamics
entropy, S, is a measure of disorder
from 2nd law of TD we get
dS(univ) > 0
what is entropy at equilibrium
dS = δqrev / T
define Gibbs free energy and give both differential and non-differential eq.’s
Gibbs free energy, G, is the energy available to do useful work
- G allows us to find the equil. state of a system, using only properties of the system, not the surroundings
G = H -TS
dG = dH - TdS - SdT
we know dH = δq + VdP
so
dG = δq + VdP - TdS - SdT
at const. temp. and pres.
dG = δq -TdS
what can we say about G at equil for a single phase
dG = 0
Gibbs free energy, G, tends to a minimum at equil.
for spontaneous processes dG<0
for a single phase of constant composition, what can we say about the variation of G with temp
- it will ALWAYS decrease
G = H-TS
its a straight line
y-int = H
grad at any point (draw tangent) = -S
what can we say about which phase is most stable at a temperature for a system of two phases of const. identical comp (e.g. liquid, solid of same phase)
link to G-T graph
- we have two curves on a G-T graph
- whichever is the lowest G phase at any point is the more stable phase
- the point at which the two lines cross is the equil. temp
phase 1: G1 = H1 - TS1
phase 2: G2 = H2 - TS2
difference in G:
ΔG = ΔH - T ΔS
we are interested in the sign of ΔG
how does G change with composition for a mechanical mixture of two phases A and B
- it simply changes as a weighted average of the two phases
- i.e. at 100% A, mark Ga on the y-axis, at 100% B, mark Gb on the y-axis, draw a straight line between them
what are the three things we must consider when determining the free energy curve for a single phase of A and B (or the change in free energy of mixing)
1) an enthalpy change associated with the fact that A-B interactions are different to A-A or B-B interactions, ΔHmix
2) an enthalpy change due to the random mixing of A and B atoms, ΔSmix
3) combining these to form a change in free energy when mixing
derive the expression for ΔHmix when forming a solution of A and B from a solid solution for 1 mole of atoms
ΔHmix = Hs - Hmm
let:
XA = fraction of A atom
XB = 1-XA = fraction of B atoms
EAA = interaction energy between A-A as nearest neighbours
EBB = “”
EAB = “”
coordination number of A,B = Z
Hmm = (NAZ / 2) (XA EAA + XB EBB)
Hs = (NAZ / 2) ( XA^2 EAA + XB^2 EBB + 2 XA XB EAB)
combining and rearranging using XA + XB = 1 gives
ΔHmix = Hs - Hmm = (NA*Z /2) XA XB (2EAB - EAA - EBB) = XA XB ψ
ψ = (NA*Z /2) (2EAB - EAA - EBB)
what 3 cases does the expression for ΔHmix imply (regarding the sign of ψ)
1) ψ = 0 , EAA = EBB = EAB, totally randomly mixed solid solution
2) ψ < 0, EAB < EAA, EBB, totally ordered alternating A-B structure, ΔHmix < 0
3) ψ > 0, EAA,EBB < EAB, totally separated, unmixed, ΔHmix > 0
derive the expression for ΔSmix when forming a solution of A and B from a solid solution for one mole
we start with
S = kln(ω)
where ω is the number of distinguishable ways of arranging atoms on the available sites
Ωmm = 1
(A atoms on A sites, B atoms on B)
Ωs = NA! / ((XANA)! ((1-XA)NA)!)
ΔSmix = kln(Ωs) - kln(Ωmm) = kln(Ωs)
once the Stirling approximation has been used this gives
ΔSmix = -R(XA ln(XA) + XB ln(XB))
derive the expression for ΔGmix when forming a solution of A and B from a mechanical mixture
ΔGmix = ΔHmix - TΔSmix
= XA XB ψ + RT(XA ln(XA) + XB ln(XB))
consider the same 3 cases regarding the sign of ψ, explain what this means for when forming a solution is favourable
1,2) ψ = 0 or ψ < 0, ΔHmix <= 0, ΔSmix, >0, ΔGmix<0 at ALL TEMPS – always favourable to form solid solution
3) ψ > 0, ΔHmix, ΔSmix >0, ΔGmix sometimes<0 depending on temp, shape of curve depends on temp
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in case 3) (ψ > 0, ΔHmix, ΔSmix >0, ΔGmix sometimes<0 depending on temp, shape of curve depends on temp), how do we know when it’s better in 2 phases or a solid solution
- at high T, the curve will have 1 minimum, it is always favourable to form a solid solution in this case
- at lower T, the curve will have two minimums, between the two minimums it is NOT favourable to form a solid solution, elsewhere it is
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what process can we apply to a two phase mixture with lines plotted on a G against comp diagram, to work out whether it is more favourable to have one of the two phases or a mixture
- draw a common tangent between the two curves of interest
- mark the compositions of the two phases where the common tangent meets their curve
- if the composition is between these two then it will split into two different phases of the compositions marked, the proportions are just a weighted average
- if it is outside of this region, then it will remain as the relevant phase
NOTE: the compositions that the common tangent touches are NOT necessarily the minimum of the curve
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Define a phase
A phase can be defined as a portion of a system whose structure, properties and
composition are homogeneous and which is physically distinct from other parts of the
system.
how do G curves relate to a phase diagram
- G-composition plots can be obtained for a range of temperatures
- for each plot the points where there is the boundary between two phases and one phase can be determined then plotted on a temperature- composition plot as points
- this can be repeated and phase boundaries determined
- or the same can be done in reverse to determine the G-Composition plot
using a Temp-comp. phase diagram, if you’re in a two phase region, how can the proportions of each phase be determine
- use the lever rule
- basically take weighted averages of each phase to give the correct overall composition
what can we say about the free energy curves of the phases in a ‘complete solubility in liquid and solid phases’ phase diagram
give some features of the phase diagram
- this is the case where 3) ψ <= 0 for both liquid and solid phases
- hence the curves for both phases only have 1 minimum
- the phase diagram has a solid phase section at bottom, a liquid phase section at top and a tilted disc shape section of (L+S) spanning the whole composition range midway
what is the key feature of a Eutectic system
what does the phase diagram look like
- the defining feature of a Eutectic system is that at some (Eutectic) composition, solidification occurs at a single temp. and we have L —> α + β
- the phase diagram has thin(ish) p-shaped sections at either extreme of composition, a large liquid section at top, a large α + β section at bottom and then two sections which meet at the Eutectic point of L+α and L+β
describe the process of Eutectic solidification
- as the alpha phase forms in the liquid, B-atoms are rejected out of the α
- a B-rich section of liquid then surrounds the α phase
- this causes β to form, generally adjacent to the α
- α + β forms
describe how the Eutectic microstructure forms
- α, β form simultaneously, forming a microstructure of alternating lamallae (plates) of α, β
As α, β form:
- B-atoms are pushed out the front of the α phase, and vice versa as they advance
- the atoms must redistribute in the liquid to allow solid phases to grow correctly
- the extent to which they can redistribute determines the length-scale (thickness) of the plates
give an example of a Eutectic system and a common use of eutectic alloys
Pb-Sn is a eutectic system
Eutectic systems (but not necessarily Pb-Sn) are often used as solders because if not at eutectic comp, they will go mushy before solidifying fully so can still be manipulated on solidifying
how do eutectic systems (once solidified) tend to appear under a microscope
stripy due to the lamallae