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Chap.6 Surface Energy: (1) Background
Chap.6 Surface Energy: (1) Background
(1) Background:
Consider the atoms in the bulk and surface regions of a crystal:
Surface: atoms possess higher energy since they are less tightly bound.
Bulk: atoms possess lower energy since they are much tightly bound.
→ The sum of all the excess energies of the surface atoms is the
surface energy.
2. Experimental approaches:
a. Stretching film: 表面拉膜法
rρgh
⇒r=
2 cos θ
For one-mole crystal, there are NA atoms and at least 0.5NA bonds will
form among them. Take the coordination number into account, there
will be (0.5NA*Z) bonds in one-mole crystal.
For the (111) plane in FCC crystal, atoms at the surface possess a CN
of 9, which means that 3 bonds per atoms are broken at the surface of
(111).
As a result, the energy required to form one (111) surface in FCC can
be given as:
E (111) = (energy of one bond)*(number of bonds broken / atom)
ΔH S
= ε *3 ≡ (Z=12 for FCC) … energy required per surface atom
2N A
ΔH S ⎛ N ⎞
/surface area) = ⎜ ⎟
2N A ⎝ A ⎠
ΔH S ⎛ 4 ⎞ ΔH S
∴ γ (111) = ⎜ ⎟
2N A ⎜ 3a 2 ⎟ = 3 N a 2
⎝ 0 ⎠ A 0
2Δ H S
→ E (100) = ε * 4 = … energy required per surface atom
3N A
⎛N⎞ 2Δ H S ⎛ 2 ⎞ 4Δ H S
∴ γ (100) = E(100) ⎜ ⎟ = ⎜ 2⎟=
⎝ A ⎠100 3N A ⎜ a ⎟ 3N a 2
⎝ 0 ⎠ A 0
γ 23 γ γ
⇒ = 12 = 31 , one can determine the relative surface
sinθ1 sinθ3 sinθ 2
energy by measuring the angles among those phases.
10° < θ C < 30°, the surface is of high wettability or called “hydrophilic”.
70° < θ C < 90°, the surface is of low wettability or called “hydrophobic”.
increase γ s,v .
c2 c2
A( 001) = a 2 − ∴ Etop − surf = (a 2 − ) * γ ( 001) * 2
4 4
dEedge da da 1 ⎛⎜ γ (110) ⎞
= (2 − 2 ) * γ (100) + γ (110) = 0 ⇒ = 2− ⎟
dc dc dc 2 ⎜⎝ γ (100) ⎟⎠
dEtop − surf da c da 1 c
= ( 2a − ) * γ ( 001) = 0 ⇒ =
dc dc 2 dc 4 a
c ⎛ γ (110) ⎞
∴ = 2⎜ 2 − ⎟
a ⎜ γ ⎟
⎝ (100 ) ⎠
c
a. The size of (100) is proportional to (a − ).
2
The size of (110) is proportional to c.
b. If γ (110) is equal to or greater than ( 2 * γ (110) ) ,c will be zero
c ⎛ γ ⎞
d. At equilibrium: = 2⎜ 2 − (110) ⎟
a ⎜ γ (100) ⎟⎠
⎝
c
γ 2−
⇒ (110) = 2 −
c
= 2 = h(110)
γ (100) 2a a h(100)