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Chapter 2

Overview on Basic
Materials’ Properties

Reference: William F. Smith, Javad Hashemi, 2006,


“Foundations of Materials Science and Engineering”,
4th ed., McGraw-Hill

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Only for Teaching 1
Materials’ Categories

• Metallic Materials
---Inorganic and have crystalline structure.
---Good thermal and electric conductors.
• Polymeric (Plastic) Materials
¾ Organic giant molecules and mostly noncrystalline.
¾ Some are mixtures of crystalline and noncrystalline regions.
¾ Poor conductors of electricity and hence used as insulators.
¾ Strength and ductility vary greatly.
¾ Low densities and decomposition temperatures.

¾ Examples :- Poly vinyl Chloride (PVC), Polyester.


¾ Applications :- Appliances, DVDs, Fabrics etc.

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Materials’ Categories

• Ceramic Materials
„ Metallic and nonmetallic elements are chemically
bonded together.
„ Inorganic but can be either crystalline, noncrystalline
or mixture of both.
„ High hardness, strength and wear resistance.
„ Very good insulator. Hence used for furnace lining for
heat treating and melting metals.
„ Also used in space shuttle to insulate it during exit and
reentry into atmosphere.
„ Other applications : Abrasives, construction materials,
utensils etc.

„ Example:- Porcelain, Glass, Silicon nitride.

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Materials’ Categories

• Composite Materials
‹ Mixture of two or more materials.
‹ Consists of a filler material and a binding material.
‹ Materials only bond, will not dissolve in each other.
‹ Mainly two types :-
---Fibrous: Fibers in a matrix
---Particulate: Particles in a matrix
---Matrix can be metals, ceramic or polymer
‹ Examples :-
‹ Fiber Glass ( Reinforcing material in a polyester or
epoxy matrix)
‹ Concrete ( Gravels or steel rods reinforced in cement
and sand)
‹ Applications:- Aircraft wings and engine, construction.

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Materials’ Categories

Electronic Materials

Not Major by volume but very important.


Silicon is a common electronic material.
Its electrical characteristics are changed by adding impurities.

Examples:- Silicon chips, transistors


Applications :- Computers, Integrated Circuits, Satellites etc.

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Space Lattice & Unit Cells

• Atoms, arranged in repetitive 3-Dimensional pattern, in long range


order (LRO) give rise to crystal structure.
• Properties of solids depends upon crystal structure and bonding
force.
• An imaginary network of lines, with atoms at intersection of lines,
representing the arrangement of atoms is called space lattice.

Space Lattice
• Unit cell is that block of
atoms which repeats itself
to form space lattice.
• Materials arranged in
short range order are
called amorphous materials
Unit Cell
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Crystal Systems and Bravais Lattice

• Only seven different types of unit cells are


necessary to create all point lattices.
• According to Bravais (1811-1863) fourteen
standard unit cells can describe all possible lattice
networks.
• The four basic types of unit cells are
¾ Simple
¾ Body Centered
¾ Face Centered
¾ Base Centered

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Unit Cells
• Cubic Unit Cell
• a=b=c
• α = β = γ = 90°

Simple Body Centered Face centered

• Tetragonal
• a =b ≠ c
• α = β = γ = 90°

Simple Body Centered


能源材料 Ref: W.G. Moffatt, G.W. Pearsall, & J. Wulff,
8
“The Structure and Properties of Materials,” vol. I: “Structure,” Wiley, 1964, p.47.)
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Unit Cells
• Orthorhombic
• a≠ b≠ c
• α = β = γ = 90°
Simple Base Centered

Face Centered Body Centered


• Rhombohedral
• a =b = c
• α = β = γ ≠ 90°

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9
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Unit Cells

• Hexagonal
¾ a = b =a ≠ c
¾ α = β = 900, γ = 1200 Simple

• Monoclinic
¾ a≠ b≠ c
Base
¾ α = γ = 900, β ≠ 900
Centered
Simple

• Triclinic
¾ a≠ b≠ c
¾ α ≠ β ≠ γ ≠ 900
Simple
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Direction Indices

• Determine direction indices of the given vector.


Origin coordinates are (3/4 , 0 , 1/4).
Emergence coordinates are (1/4, 1/2, 1/2).

Subtracting origin coordinates


from emergence coordinates,
(3/4 , 0 , 1/4) - (1/4, 1/2, 1/2)
= (-1/2, 1/2, 1/4)

Multiply by 4 to convert all


fractions to integers
4 x (-1/2, 1/2, 1/4) = (-2, 2, 1)
Therefore, the direction indices are [ 2 2 1 ]

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Miller Indices
• Miller Indices are used to refer to specific lattice
planes of atoms.
• They are reciprocals of the fractional intercepts (with
fractions cleared) that the plane makes with the
crystallographic x,y and z axes of three nonparallel
edges of the cubic unit cell.

Miller Indices =(111)

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Polymorphism or Allotropy

• Metals exist in more than one crystalline form. This is


called polymorphism (同質多形體) or allotropy (同素異形體).
• Temperature and pressure leads to change in crystalline
forms.
• Example:- Iron exists in both BCC and FCC form
depending on the temperature.
Liquid
Iron

-2730C 9120C 13940C 15390C

α Iron γ Iron δ Iron


BCC FCC BCC
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X-Ray Diffraction

• Crystal planes of target metal act as


mirrors reflecting X-ray beam.

• If rays leaving a set of planes


are out of phase (as in case of
arbitrary angle of incidence)
no reinforced beam is
produced.

• If rays leaving are in phase,


reinforced beams are
produced.

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XRD

• For rays reflected from different planes to be in phase, the extra


distance traveled by a ray should be a integral multiple of wave
length λ .

nλ = MP + PN (n = 1,2…)
n is order of diffraction

If dhkl is interplanar distance,

Then MP = PN = dhkl.Sinθ

Therefore, λ = 2 dhkl.Sinθ

Ref: A.G. Guy and J.J. Hren, “Elements of Physical Metallurgy,” 3d ed., Addison-Wesley, 1974, p.201.)

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Example of XRD

λ = 2 dhkl.Sinθ

能源材料 H-Y Chang et al, Nanotechnology 14 (2003) 603–608 16


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Substitutional Solid Solution

• Solute atoms substitute for parent solvent atom in a


crystal lattice.
• The structure remains unchanged.
• Lattice might get slightly distorted due to change in
diameter of the atoms.
• Solute percentage in solvent
can vary from fraction of a
percentage to 100%

Solvent atoms

Solute atoms
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Substitutional Solid Solution

• The solubility of solids is greater if


¾ The diameter of atoms not differ by more than 15%
¾ Crystal structures are similar.
¾ No much difference in electronegativity (else compounds
will be formed).
¾ Have some valence.

• Examples:- Atomic Electro- Solid


System radius negativity Solubility
Difference difference
Cu-Zn 3.9% 0.1 38.3%
Cu-Pb 36.7% 0.2 0.17%
Cu-Ni 2.3% 0 100%
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Interstitial Solid Solution
• Solute atoms fit in between the voids (interstices) of
solvent atoms.
• Solvent atoms in this case should be much larger than
solute atoms.
• Example:- between 912 and 13940C, interstitial solid
solution of carbon in γ iron (FCC) is formed.
• A maximum of 2.8%
of carbon can dissolve
interstitially in iron.

Iron atoms r=0.129nm

能源材料 Carbon atoms r=0.075nm 19


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Crystalline Imperfections

• No crystal is perfect.
• Imperfections affect mechanical properties,
chemical properties and electrical properties.
• Imperfections can be classified as
¾ Zero dimension point defects.
¾ One dimension / line defects (dislocations).
¾ Two dimension defects (planar defects).
¾ Three dimension defects (cracks).

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Point Defects – Vacancy
• Vacancy is formed due to a missing atom.
• Vacancy is formed (one in 10000 atoms)
during crystallization or mobility of atoms.
• Energy of formation is 1 eV.
• Mobility of vacancy results in cluster of
vacancies.
• Also caused due to
plastic deformation,
rapid cooling or particle
bombardment.

Figure: Vacancies moving to form vacancy cluster


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Point Defects - Interstitially

• Atom in a crystal, sometimes, occupies interstitial site.


• This does not occur naturally.
• Can be induced by irradiation.
• This defects caused structural distortion.

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Point Defects in Ionic Crystals

• Complex as electric neutrality has to be maintained.


• If two oppositely charged particles are missing, cation-
anion divacancy is created. This is Schottky imperfection.
• Frenkel imperfection is created when cation moves to
interstitial site.
• Impurity atoms are
also considered as
point defects.

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Dislocations

*Line Defects (Dislocations)—


*Edge Dislocation---
*Screw Dislocation---
*Mixed Dislocation---

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Grain Boundaries (GB)
• Grain boundaries separate grains.
• Formed due to simultaneously growing crystals
meeting each other.
• Width = 2-5 atomic diameters.
• Some atoms in grain boundaries have higher energy.
• Restrict plastic flow and prevent dislocation movement.

3D view of
grains

Grain Boundaries
In 1018 steel
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(ref:A.G. Guy, “ Essentials of materials Science,” McGraw-Hill, 1976.)
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Planar Defects

• Grain boundaries, twins, low/high angle


boundaries, twists and stacking faults

• Free surface is also a defect : Bonded to


atoms on only one side and hence has
higher state of energy ⇒ Highly reactive

• Nanomaterials have small clusters of


atoms and hence are highly reactive.

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Atomic Diffusion in Solids

• Diffusion is a process by which a matter is


transported through another matter.

• Examples:
---Movement of smoke particles in air : Very fast.
---Movement of dye in water : Relatively slow.
---Solid state reactions : Very restricted movement due
to bonding.

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Diffusion mechanism

• Atoms diffuse in solids if


¾ Vacancies or other crystal defects are present
¾ There is enough activation energy

• Atoms move into the vacancies present.

• More vacancies are created at higher temperature.

• Diffusion rate is higher at high temperatures.

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Substitutional Diffusion

• Example: If atom ‘A’


has sufficient activation
energy, it moves into the
vacancy self diffusion.

Activation Activation Activation


Energy of = Energy to + Energy to
Self diffusion form a move a
Vacancy vacancy

• As the melting point increases, activation energy also


increases
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Interstitial Diffusion mechanism

• Atoms move from one


interstitial site to another.
• The atoms that move must
be much smaller than the
matrix atom.
• Example:
Carbon interstitially
diffuses into BCC α or FCC
γ iron. Interstitial atoms
Matrix
atoms

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Steady State Diffusion

• There is no change in concentration of solute atoms at


different planes in a system, over a period of time.
• No chemical reaction occurs. Only net flow of atoms.

Solute atom flow


C1
Concentration
Of diffusing C
2
atoms

Distance x

Net flow of atoms


Diffusing Unit Per unit area per
atoms Area Unit time = J

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Fick’s First Law

• The flux or flow of atoms is given by


J = Flux or net flow of atoms.
dc
J = −D D = Diffusion coefficient.
dc
dx = Concentration Gradient.
dx

• i.e. for steady state diffusion condition, the net flow of


atoms by atomic diffusion is equal to diffusion D times
the diffusion gradient dc/dx .

• Example: Diffusivity of FCC iron at 500oC is 5 x 10-15


m2/s and at 1000oC is 3 x 10-11 m2/s

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Diffusivity

• Diffusivity depends upon


¾ Type of diffusion : Whether the diffusion is
interstitial or substitutional.
¾ Temperature: As the temperature increases
diffusivity increases.
¾ Type of crystal structure: BCC crystal has lower
APF than FCC and hence has higher diffusivity.
¾ Type of crystal imperfection: More open
structures (grain boundaries) increases diffusion.
¾ The concentration of diffusing species: Higher
concentrations of diffusing solute atoms will affect
diffusivity.

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Non-Steady State Diffusion
• Concentration of solute atoms at any point in metal
changes with time in this case.
• Fick’s second law:- Rate of compositional change is
equal to diffusivity times the rate of change of
concentration gradient. Plane 2
Plane 1
dC x d ⎛ dc x ⎞
= ⎜⎜ D ⎟⎟
dt dx ⎝ dx ⎠

Change of concentration of solute


Atoms with change in time in different planes
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Fick’s Second Law
Cs − C x ⎛ x ⎞
= erf ⎜ ⎟
C s − C0 ⎜2 D ⎟
⎝ t ⎠
• Cs = Surface concentration of Cs
element in gas diffusing Time = t2
into the surface. Cx Time= t1
• C0 = Initial uniform concentration
Time = t0
of element in solid.
C0
• Cx = Concentration of element at
distance x from surface at
time t1. x Distance x
• x = distance from surface
• D = diffusivity of solute
• t = time.
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Phase Diagrams

• Phase: A region in a material that differs in structure


and function from other regions.
• Phase diagrams:
¾ Represents phases present in metal at different conditions
(Temperature, pressure and composition).
¾ Indicates equilibrium solid solubility of one element in
another.
¾ Indicates temperature range under which solidification
occurs.
¾ Indicates temperature at which different phases start to
melt.

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Phase Diagram of Pure Substances
• Pure substance exist as solid, liquid and vapor.
• Phases are separated by phase boundaries.
• Example : Water, Pure Iron.

• Different phases coexist at triple point.


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張宏宜 Ref: W. G. Moffatt, et al., “The Structure and Properties of Materials,” vol I: “Structure,” Wiley, 1965, p.151
Phase Rule

• P+F = C+2 P = number of phases that coexist in a system


C = Number of components
F = Degrees of freedom
• For pure water, at triple point, 3 phases coexist.
• There is one component (water) in the system.
• Therefore 3 + F = 1 + 2 F = 0.
• Degrees of freedom indicate number of variables that
can be changed without changing number of phases.

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Phase Diagram from Cooling Curves
• Series of cooling curves at different metal composition
are first constructed.
• Points of change of slope of cooling curves (thermal
arrests) are noted and phase diagram is constructed.
• More the number of cooling curves, more accurate is
the phase diagram.

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The Lever Rule

• The Lever rule gives the weight % of phases in any


two phase regions.

Wt fraction of solid phase


= X s = w0 – w 1
ws – w1

Wt fraction of liquid phase


= X 1 = ws – w 0
ws – w1

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Iron Carbide Phase Diagram
• Plain carbon steel: 0.03% to 1.2% C, 0.25 to 1% Mn and
other impurities.
• α Ferrite: Very low solubility
of carbon. Max 0.02 % at 7230C
and 0.005% at 00C.
• Austenite: Interstitial solid
solution of carbon in γ
iron. Solubility of C is
2.08% at 11480C and 0.8%
at 00C.
• Cementite: Intermetallic compound.
6.67% C and 93.3% Fe.
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Binary Eutectic Alloy System
• In some binary alloy systems, components have limited
solid solubility.
Example : Pb-Sn alloy.

• Eutectic composition freezes


at lower temperature than all
other compositions.
• This lowest temperature is
called eutectic temperature.

Eutectic temperature
Liquid α solid solution + β solid solution
Cooling
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Intermediate Phases and Compounds

• Terminal phases:
Phases occur at the end
of phase diagrams.
• Intermediate phases:
Phases occur in a
composition range inside
phase diagram.
• Examples: Cu-Zn
diagram has both
terminal and
intermediate phases.
• Five invariant peritectic
points and one eutectic
point.
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Intermediate Phases in Ceramics
• In Al2O2 – SiO2 system, an intermediate phase called
Mullite is formed, which includes the compound
3Al2O3.2SiO2.

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張宏宜 Ref: A. G. Guy, “Essentials of Materials Science, “McGraw-Hill, 1976
Ternary Phase Diagrams
• Three components
• Constructed by using a equilateral triangle (等邊三角形)
as base.
• Pure components at each
end of triangle.
• Binary alloy composition
represented on edges.

Temperature can be
represented as uniform
throughout the
Whole Diagram -----
Isothermal section.
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Ternary Phase Diagram
• Example:- Iron-Chromium-Nickel phase diagrams.

•Isothermal reaction at 6500C


for this system
• Composition of any metal
at any point on the phase
diagram can be found by
drawing perpendicular
from pure metal corner to
opposite side and calculating
the % length of line at that
point

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張宏宜 Ref: “Metals Handbook,” vol. 8: American Society of Metals, 1973, p. 425.
Ceramics

• Ceramics are inorganic and nonmetallic.


• Bounded by ionic or covalent bonds.
• Good electrical and heat insulation property.
• Brittle, and lesser ductility and toughness than
metals.
• High chemical stability and high melting
temperature.
• Traditional Ceramics: Basic components (Clay and
Silica).
• Engineering Ceramics: Pure compounds (Al2O3,
SiC).

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Zinc Blende (ZnS) Crystal Structure

• Four zinc and four sulfur atoms.


• One type (Zn or S) occupies lattice points and another
occupies interstitial sites of FCC unit cell.
• S Atoms (0,0,0) ( ½ ,½ ,0) ( ½ , 0, ½ ) (0, ½ , ½ )
Zn Atoms ( ¾ ,¼ ,¼ ) ( ¼ ,¼ ,¾ )( ¼ ,¾,¼ ) ( ¾ ,¾ ,¾ )
• Tetrahedrally covalently bonded
• (87% covalent character) with
CN = 8.
• CdS, InAs, InSb and ZnSe have
similar structures.

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ref: W. D. Kingery, H. K. Bowen, D. R. Uhlmann, “ Introduction to Ceramics,”2nd ed., Wiley, 1976
Important Crystal Structures
• Perovskite (CaTiO3) : Ca2+ and O2- ions form FCC unit
cell.
¾ Ca2+ Ions occupy corners
¾ O2- Ions occupy face centers.
¾ Ti4+ ions are at octahedral
sites.
• Graphite : Polymorphic form
of compound.
• Layered structure with carbon
atoms in hexagonal arrays.
• Good lubricating properties.

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張宏宜 Ref: W. D. Kingery, H. K. Bowen, D. R. Uhlmann, “ Introduction to Ceramics,”2nd ed., Wiley, 1976.
Silicate Structures
• Silicate (SiO44-) is building block of silicates.
• 50% ionic and 50% covalent.
• Many different silicate structures
can be produced.
• Island structure: Positive ions
bond with the oxygen of SiO44-
tetrahedron.
• Chain/ring structure: Two
corners of each SiO44- tetrahedron
bonds with corners of other
tetrahedron.

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Ref: M. Eisenstadt, “Mechanical properties of Materials,” Macmillan, 1971, p.82.
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Sheet Structures of Silicates
• Sheet structure: Three corners of same planes of silicate
tetrahedron bonded to the corners of three other silicate
tetrahedra.
• Each tetrahedron has one
unbounded oxygen and hence
chains can bond with other
type of sheets.
• If the bondings are weak,
sheets slide over each other
easily.

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張宏宜 Ref: M. Eisenstadt, “Mechanical properties of Materials,” Macmillan, 1971, p.83.
Silicate Networks

• Silica: All four corners of the SiO44- tetrahedra share


oxygen atoms.
• Basic structures: Quartz, tridymite and cristobalite.
• Important compound
of many ceramic and
glasses.
• Feldspars: Infinite 3D
networks.
• Some Al3+ Ions replace
Si4+ Ions Net negative charge.
• Alkaline and alkaline fit into interstitial sites.

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Ref: W. D. Kingery, H. K. Bowen, D. R. Uhlmann, “ Introduction to Ceramics,”2nd ed., Wiley, 1976
Traditional Ceramics
• Made up of clay, silica and feldspar.
• Clay: Provide workability and hardness.
• Silica: Provide better temperature resistance and MP.
• Potash Feldspar: Makes glass when ceramic is fired.

SEM of Porcelain

Quartz
grain High-silica
glass
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張宏宜 Source: F. Norton, Elements of Ceramics, 2nd ed., Addision-Wesley,1974, p.140 .
Engineering Ceramics
• Alumina (Al2O3): Aluminum oxide is doped with
magnesium oxide, cold pressed and sintered.
¾ Uniform structure. Used for electric applications.

• Silicon Nitride (Si3N4): Compact of silicon powder is


nitrided in a flow of nitrogen gas.
¾ Moderate strength and used for parts of advanced engines.

• Silicon Carbide (SiC): Very hard refractory carbide,


sintered at 21000C.
¾ Used as reinforcement in composite materials.

• Zirconia (ZrO2): Polymorphic and is subject to cracking.


¾ Combined with 9% MgO to produce ceramic with high
fracture toughness.
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Electrical Properties

• Basic properties of dielectric:


¾ Dielectric constant:-
Q = CV
Q = Charge
V = Voltage
C = Capacitance
C = ε0A/d ε0 = permittivity of free space
= 8.854 x 10-12 F/m
• When the medium is not free space
C = Kε0A/d Where K is dielectric constant of the
material between the plates
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Dielectric Strength and Loss Factor

• Dielectric strength is measure of ability of material to hold


energy at high voltage.
¾ Defined as voltage gradient at which failure occurs.
¾ Measured in volts/mil. 1 mil=(1/1000) in=25 μm
• Dielectric loss factor: Current leads voltage by 90 degrees
when a loss free dielectric is between plates of capacitor.
• When real dielectric is used, current leads voltage by 900 – δ
where δ is dielectric loss angle.
• Dielectric loss factor = K tan δ measure of electric
energy lost.

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Ceramic Materials for Capacitors

• Ceramics are used as dielectric materials for capacitors.


• Example: Disk ceramic capacitors.
¾ BaTiO3 + additive
¾ Very high dielectric
constant
¾ Used in ceramic based
thick film hybrid
electronic circuit
¾ Higher capacitance per unit area

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Ceramic Semiconductors

• Ceramics can be used as semiconducting materials.


• Thermistor: Thermally sensitive resistor.
• NTC thermistor: Conductivity raises with temperature.
• Solid solution oxides of Mn, Ni, Fe, Co and Cu are used to
obtain necessary property ranges.
• By combining low conducting metal oxide with low
conducting oxides intermediate properties are obtained.
• Example: Conductivity of Fe3O4 is reduced gradually by
adding increasing amounts in solid solution of MgCr2O4

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Thermal Properties of Ceramics

• Low thermal conductivity and high heat


resistance.
• Many compounds are used as industrial
refractories.
• For insulating refractories, porosity is desirable.
• Dense refractories have low porosity and high
resistance to corrosion and errosion.
• Aluminum oxide and MgO are expensive and
difficult to form and hence not used as refractories.

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Insulation for Space Shuttle Orbital
• About 70% of external surface is protected from heat by
24000 ceramic tiles.
• Material: Silica fiber compound.
• Density is 4kg/ft3 and withstands temperature up to 12600C.

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Oxidation – Reduction Reactions

• A metal (e.g. – Zn) placed in HCl undergoes corrosion.

Zn + 2HCl ZnCl2 + H2
or
Zn + 2H+ Zn2+ + H2
also
Zn Zn 2+ + 2e- (oxidation half cell reaction)
2H+ + 2e- H2 (Reduction half cell reaction)
• Oxidation reaction: Metals form ions at local anode.
• Reduction reaction: Metal is reduced in local charge at
Local cathode.
• Oxidation and reduction takes place at same rate.
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Macroscopic Galvanic Cells with 1M Electrolyte
• Two dissimilar metal electrodes immersed in
solution of their own ions.
• Electrode that has more
negative oxidation potential
will be oxidized.

Zn Zn2+, Cu2+ Cu
Half cell reactions are
Zn Zn 2+ + 2e- E0 = -0.763 V
Cu Cu2+ + 2e- E0 = + 0.337 V
Or Cu2+ + 2e- Cu E0 = -0.337 V (negative sign)
Adding two reactions,
Zn + Cu2+ Zn2+ + Cu E0cell = -1.1V
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Galvanic Cells With Electrolytes not 1M

• If the concentration of electrolyte surrounding anode is


not 1 molar, driving force for corrosion is greater.
• There will be more negative emf half cell reaction
M Mn+ + ne-
• Nernst Equation:

0.0592
E=E + 0
log Cion
n
E = Net emf of half cell
E0 = Standard emf of half cell
n = Number of electrons transferred
Cion = Molar concentration of ions.
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Galvanic Cells With Acid or Alkaline Electrolytes
• Consider iron and copper electrodes in acidic electrolyte.
• Since standard electrode potential of Fe to oxidize is
–0.44 , compared to 0.337 of copper,
Fe Fe2+ + 2e-

• Since there are no copper ions to reduce


2H+ + 2e- H2
• If electrolyte contains oxidizing agent
O2 + 4H+ + 4e- 2H2O
• If electrolyte is neutral or basic,
O2 + 2H2O + 4e- 4OH-

能源材料 64
張宏宜 Ref: J. Wulff et al., “ The Structure and Properties of Materials,” vol. II, Wiley, 1964, p.164.
Grain – Grain boundary Electrochemical cells

• Grain boundaries are more anodic and hence get corroded


by electrochemical attack.
• Grain boundaries are at higher energy.
• Impurities migrate to grain boundaries.
• Solute segregation might cause grain boundaries to
become more cathodic.
Grain
Boundary Grain boundary
Grain boundary (cathode)
(anode) anode

Cartridge Brass
能源材料 65
張宏宜

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