Diffusion and Solid Electrolytes

At melting temperature ,TM, 10

-3
< NV/NA< 10
-4
.
At 0.5TM, drops to <10
-6
Diffusion: the mass transfer by atomic migration; solids, liquids, gases. Atoms
move from regions of high concentration to regions of low concentration. Steeper
concentration gradient (dc/dx m
-4
) faster rate of diffusion.
Flicks 1
st
law of diffusion: Applies to steady state w. constant concentration
gradient.

J-flux of atoms moving across unit area, D-diffusion

coefficient, -ve due to flow from high->low conc.
Vacancy Diffusion: Subst. atoms diffuse by changing places w. a
vacancydependent on no. vacancies available. Direction of movement of atoms
opposes movement of vacancies.
Interstitial Diffusion: Interst. atoms diffuse by squeezing between larger solute
atoms moving between interstitial sites. Much faster than vacancy diffusion:
more interstitial than vacancy sites.
Diffusing atoms must overcome an energy barrier. Atoms around diffusing atoms
forced apart.
Energy supplied by heat increased thermal vibration of atoms diffusion
temperature sensitive.
Arhennius equation: temp. dependence of diffusion coefficient, D.

exp

D0 temperature independent constant, QD is the

activation energy for diffusion.
Flicks 2
nd
law of diffusion: Applies to non steady-state. Diffusion process
attempting to eliminate concentration gradient.

eif

Cs constant surface concentration, Co concentration at

large distances, Cx concentration at some distance x, erf(x/2(Dt)^(-1/2)
Gaussian error function

Cx a fixed value, Co = 0. When Cx 1/2Cs, constant = 1,

Solid ceramic conduction: occurs via the migration of ions (and counter
migration of vacancies) subst/vac. diffusion process. If cations of lower valence
are introduced into a ceramic, anion vacancies must be produced to maintain
electrical neutrality. [e.g. replacing Zr
4+
in ZrO2 w. divalent cation or two trivalent
cations to balance the formation of one O
2-
anion vacancy. Doping ZrO2 with CaO
or Y2O3 stabilise the cubic phase. Ceramics are ionically conductive; form basis of
solid electrolytes. Conductivity increases with temperature.
Polymers
Combine lightness and resistance to environmental degradation with toughness
and low cost.
Hydrocarbon: Carbon and hydrogen are covalently bonded. Strong inter-
molecular bond vs. weak Van der Waals. Low MP and BP; increases w. molecular
weight.
Polymers: Larger than hydrocarbon molecules; macromolecules. Based on
covalent bonding. Long flexible chains, backbone of carbon atoms. Chain
molecules made up of mer units repeated along the chain. Single mer unit:
monomer. Many mers: polymer.
Types of polymer: Size given by molecular weight. Degree of polymerisation:
expressing avg no. mer units in molecular chain. Homopolymer: one type of
repeating unit (monomer). Copolymer: two or more different mer units, can be
random, alternating, block or graft. Shape depends on arrangement of bonds. C-
C bonds @ 109.5 separation: rotation around bonds results in twisted molecule.
Structure of polymer can be linear (long, flexible single chains w. VdW forces
between chains. Polyethylene, polystyrene, nylon, fluorocarbons); branched (side
branches reduce packing efficiency, lowers density); crosslinked (adjacent linear
chains joined w. covalent bonds achieved by synthesis or high temp rxn:
vulcanisation in Rubbers); network (three active covalent bond form three-
dimensional networks).
Amorphous polymers: molecules arranged randomly in space.
Crystalline polymers: molecules assume a regular pattern in 3D. Complex unit
cells. Linear chained polymers more likely to be crystalline (rather than irregular
or branched chains). Mre dense than amorphous polymers; more efficient
packing in 3D. Increased strength and heat resistant. Degree of crystallinity
varies from completely amorphous to nearly entirely crystalline, can be
controlled via polymer chemistry.
Mechanical p: dissimilar to metals, lower elastic modulus, high ductility, more
temperature sensitive and strain rate. Exhibit 3 different stress-strain behaviours:
brittle (similar to metals; elastic deform, yielding, plastic deform, fracture);
plastic (similar to metals, elastic deform, eventual fracture); elastomers.
Elastomers: rubber-like elastic behaviour w. large recoverable strains at low
stresses; results from uncoiling, untwisting and straightening of molecular chains.
Criteria: must be amorphous w. molecular chains naturally coiled and kinked in
the unstressed state, easy chain bond rotation so coiled chains can readily
straighten out @ low stresses, onset of plastic deformation must be delayed
(achieved by crosslinks).
Semicrystalline: plastic deform. in stages: 1. Amorphous molecular chains align in
direction of tensile stress; 2. Crystalline regions tilt so chain folds align with
tensile axis; 3. Crystalline blocks break into segments; 4. Linked blocks and tie
chains align with tensile axis highly orientated structure.
Consequence: early stage neck formation; stronger than material in undeformed
portions due to more highly orientated structure. Elongation proceeds by
propagation of the neck along the length of the specimen.
Glass Transition: At high T, molecular chains rotate. At low T < Tg (glass transition
temp.) motion of molecular chains ceases. Polymer becomes rigid & brittle. More
rigid/crosslinking in chains, higher Tg. Rigid polymers used below Tg and
elastomers used above Tg.
Molecular Weight: limited effect on elastic modulus, but increasing increases
tensile strength.
Degree of Crystallinity: In crystalline region, extensive secondary bonding
between adjacent chain segments, increasing elastic modulus and tensile
strength.
Pre-deformation: drawing produces an orientated structure stronger than the
original polymer. If performed at elevated temperatures, cooling required for
significant improvements to be retained.
Heat treating: (or annealing) modify crystallite size and perfection, changes
modulus, tensile strength and ductility. Thermosetting polymers become
permanently hard on heating and do not soften on subsequent heating. Harder,
stronger and more brittle than thermoplastics.
Amorphous polymer behave like glass at low temp, rubber at intermediate temp
(>Tg) and a vicious liquid at higher temp. Vicious materials deform with stress
proportional to strain rate:

n viscosity of material.
Creep in polymers:

Ec(t) - creep modulus, 0 initial stress, t strain

after time t. Creep modulus time sensitive, decreases with increasing
temperature.
Stress Relaxation in polymers:

. Bigger stress drop (smaller t) lower

relaxation modulus; decreases with increasing temperature. Relaxation modulus:

: glassy region,

: leathery region,

: rubbery region,

: near Tm
Degradation of Polymers and Corrosion of Metals
Corrosion: destructive, electrochemical rxn. Electrochemical corrosion (metals)
occurs in moist environments. Oxidation occurs at the anode, reduction at the
cathode. No net electrical charge accumulation.
E.g. rusting of iron: 2Fe2Fe
3+
+6e
-
[ + ]O2+3H2O+6e
-
6(OH)
-
[ =
]2Fe+O2+3H2O2Fe(OH)3
Essential to have an electrolyte to transport ions participating in corrosion.
Reactivity of Metals:
2 dissimilar metals in
contact, more anodic
will be oxidised;
sacrificial anode prevent
(less anodic) component
from corroding. E.g.
Zn/Mg prevents Fe
corrosion.
Corrosion rate: depends
on electrolyte
conductivity;
polarisation (departure
of corrosion potentials
from equilibrium values) or passivity. Passivity: corrosion product precipitate
deposited as a surface film and protects underlying metal. Precipitate film must
adhere to metal, not be porous, capable of self healing, not a conductor. (E.g. Al
and stainless steel highly anodic, -ve EMF)
Forms of corrosion: Uniform attack (equal intensiy, may leave scale), galvanic
(dissamiliar metals In contact w. electrolyte), crevice (difference in conc. of ions
between 2xsame component), pitting (localised attack, generates own crevices),
intergranular (occurs along grain boundaries. Forms precipitates @ grain
boundary), selective leaching (preferential removal of one constituent in an
allow), erosion (corrosion + erosion), stress (applied tensile stress + corrosive
atmosphere = cracking + failure)
Corrosion prevention: Passivation, coatings (must adhere well and prevent
contact between metal + atmosphere, inert, damage leads to local corrosion),
sacrificial coatings (attacked in preference to underlying metal, e.g. galvanised
steel Zn coating),cathodic protection (changing potential of component to be
cathodic via external voltage or using sacrificial anode).
Degradation of polymers: physical and chemical processes. Chemical attack
ruptures covalent bonds. Dissolution is the physical removal of polymer chains,
reduced by high molecular weight, more crosslinking and lower service
temperatures. Swelling occurs when polymers are exposed to liquids. Liquid
solute diffuses into and is absorbed. Solute molecules force polymer chains apart.
Reduced by lower service temperatures, increased molecular weight, crosslinking
and/or crystallinity. Radiation (UV, electrons, x-rays, - & - radiation) penetrates
a polymer and interacts with constituent atoms. Can remove atoms like C and
break a C-C bond. Bond breaking leads to scission or rearrangement. Stabilisers
(Carbon black or TiO2) additions protect. - radiation IS used commercially to
produce crosslinking to improve resistance to softening and flow at high T.
Thermal degradation (scission of molecular chains at high T).
Light
Faradays law: changing magnetic field induces an electric field. Amperes law:
changing electric field induces a magnetic field. Electromagnetic waves: both
field types continuously induce the other, results in electromagnetic disturbance
propagating through space as a wave. Electric and magnetic fields of an EM wave
are perp. in vacuum. Both also perp. to direction of propagation. EM=transverse
wave

E-electric field, B-magnetic

field.
Energy described by intensity:

. (Incident on surface perp to

direction of propagation.)

=permeability constant=

Momentum

; Radiation pressure=momentum/unit time x unit

area:

Periodic oscillation of an electric field in both space and time:

Eo=Amplitude: max |electric field|, k=wave number, =anglular
frequency, =phase factor.
Period (T): time for one oscillation of field (time for 2 phase). Frequency (F): 1/T,
number of cycles/second. Angular frequency (): 2f. Wavelength (): distance
for one spatial oscillation. Wavenumber (k): 2/. Wave velocity (c): speed of
light propogation: f. [=2f=2c/=kc]
If

, phase of wave is the argument of co/sine

function: =kx-t+.
=2/k; T=2/=1/f; ccm=c/n; m=cm/f=c/nf=/n.
Fermat principle : The path taken by light is such that the time of travel is
minimum.
Law of reflection: i (incident angle)=r(reflected angle)
Snells law of refraction n1sin1=n2sin2
Normal incidence: 1= 2=0
Reflected intensity:

Optics
Intensity = amplitude
2

cos

4 x intensity: constructive
interference.

Average intensity:

cos

Ep peak electric field

Maximum intensity: occurs when

(with m = integer) OR

; Gives
fringe positions, gives intensity variation in between.
Constructive interference: when =0,
2, 4,( =1) max S. Double
amplitude, 4x intensity.
Destructive interference: when = , 3
, - min S. Waves out of phase, S=0.
Double slit interface: Bright fringes (in
phase) dsin =m; Dark bands (out of
phase) dsin =(m+1/2)

Diffraction: Rays emerge from each point in the slit; interfere destructively,
causing minimum when asin=l (l=1,2,3..)
Diffraction and resolution: large angle of separation between light
sourcesresolved image. Converging light sources central maximum overlap.
Completely coinciding central maximum meet Rayleigh Criterion:

Thin films: Light passing partially reflected on both front and back surfaces;
interference between different beams. 5% intensity reflected. Reflected light:
maximum=2ndcos2=(m+1/2); minimum=2ndcos2=m. Transmitted light:
maximum=2ndcos2=m; minimum=2ndcos2=(m+1/2).
Antireflection coatings: layer dielectric material. Reflected S 0 destructive
interference for reflected light; Normal incidence: both reflected beams reflect
off denser medium and get phase shift. 1<n1<n2; condition for destructive
interference:

Layer thickness:

Fibre Optics
Pros: larger range of modulation frequencies possible,
single fibre can carry 10x10
3
calls, lighter, more rugged
than copper, less vulnerable to tapping, less susceptible to
noise. Cons: expensive to install, requires electronic
amplification.
Total internal reflection:

. Confines light in optical fibres. Crit. angle

determines how easy it is to get light into a fibre.

.
Numerical aperture: (Measure of range of angles that can enter the fibre)

sin

Large aperture very

convenient. NeedNeed light to be nearly straight on to get into fibre.

. Angle of incidence at cladding must be large enough to

get TIR. M=
Optics of propagation:

sin

Skip distance: (distance between two
successive reflections)

Resolving power:

Optical Materials
Glass: non crystalline solids, chemically similar to crystalline ceramics.
Predominant category: silicates (e.g. soda-lime-silica). Major ingredient: SiO2
(sand). Window glass = 70SiO2.10CaO.15Na2) (wt%). Other additives: Al2O3 &
B2O3. Si+4OSiO4 tetrahedral unit; amorphous. Softening point reduced by adding
Na ions (reduces x-links and Tg). @T>Tg, viscous. T<Tg, brittle-no mechanism for
plastic deformation (amorphous). Ideal elastic & isotropic. Failure: thermal shock,
impact. Due to tensile stress at surface. Surface flaw->fracture. Tempered glass:
strengthened by quenching (surface in compression, interior in tension). Glazes:
noble metals (gold, silver, copper) coated 5-10nm layers. Optically transparent, IR
reflectors. Opaque due to photon absorption by electron excitation into empty
electron states. Thus metals thinner than 100nm transparent to visible light. LCD:
Glass critical constituent, must have high surface finish, thickness 0.5mm,
thermal stability at high T, alkali free, chemical stable. Alkali earth
aluminoborosilicate glasses used. Optical fibres: low cost ($0.10/m), thin
(125m). Pure silica substrate, less light lost. Selectively doped with GeO2, P2O5 or
F change refractive index. Hollow silica rod coated internally then drawn or
ceramic externally coated and withdrawn prior t drawing longer fibres.
Materials Selection
Critical attributes: Cost, function (what product has to do), shape(inc.
appearance), manufacturing method or processes (simple $, complex $$$$).
Materials selected to ensure product function is achieved. More subtle aspects:
availability, ease of processing, reliability in service, current fashion,
environmental impact. Iterative process. Material class can be restricted by
concept and definition of components function (need for conductivity, high
temperature exposure, etc). Can mix material classes to achieve optimum
characteristics. Quantitative data: available in literature or electronic databases.
Can compare properties to select candidate materials. Materials selection charts.