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G LS = L
T TE
L T
=
0
TE
TE
G = G S + Gv
Cluster r =
2 LS
G LS
G =
3
T2
16 LS
2 E2
3 L ( T )
3
16
LS
nr *
G *
G L2S
3
= exp
= exp
N
KT
KT
(velocidad de nucleacin)
G
I hom ognea = 10 33 exp
KT
(velocidad de nucleacin)
I heterogne
siendo f ( ) =
K1
ncleos
= 10 33 exp
3
2
cm seg
TT
G f ( ) ncleos
K f ()
= 10 33 exp
= 10 33 exp 1 2
3
KT
cm seg
TT
Solidificacin. 2
Velocidades (I,V)
v = K 2 T
0,8 TE
K
I = 1033 exp 1 2
T T
I v 3t 4
) (JAP, pag. 528)
4
Solidificacin. 3
2 LS
TE
LT1
r (hom) =
2 LS
TE
LT1
25 r (hom) =
2 LS
TE
LT2
T2
1
=
25 T1
T1 660 475 = 185 C
T2 =
185
7, 4 C
25
Solidificacin. 4
2 SL
2 SL
=
TE
G LS
LT
2 SL
2 SL
TE = 18
TE
L Thet
L Thom
T ( het ) =
1
1
T (hom) =
0,20 TE
18
18
T (h
e
t
) =
0,0
1 TE
Solidificacin. 5
H f = 3658 cal
T f =1536 ,5 C
tomo g Fe
(1809 ,5 K )
Solucin numrica:
G f (T = 1809 ,5) = 0 = H f TS f
S f =
3658 cal
tomo g
cal
= 2,02
1809 ,5 K
tomo g K
cal
+ (1723 K ) ( 2,02 ) = 178 cal
tomo g
tomo g
Solidificacin. 6
H f = 3658cal
tom ogr Fe
T f = 1 5 3 ,65 C
S f = 2,02 cal
S L = 204 ergios 2
cm
( F e) = 7,4 3 g r 3
cm
tom ogr F e K
= 204
16
1 Julio 0,24 cal
ergios
cm 2
7 cal 10
=
49
10
cm 2 10 7 ergios 1 Julio
cm 2
1 A2
G ( solidifica cin ) = H S (1
Gv = 393
T
T
cal
200
) = H S
= 3658
= 393
Tf
Tf
1809
,
5
tomo
gr
1 tomo gr
cal
cal 7,43 gr Fe
cal
= 7,04
= 52
3
tomo gr 55 ,85 gr Fe
gr Fe
1 cm
cm 3 Fe
2 4910 7 cal 2
cm = 1,8810 7 cm 19
r (crtico) =
52 cal 3
cm
G (sup erficial ) = 4 r 2 SL = 4 ( 20 ) 2 (10 8 ) 2 204
G (volumtric a ) =
T
4
r 3 H
T
3
f
ergios
cm 2
0,24 cal
10 7 ergios
cal
18 cal
= ncleo = 2,46 10
ncleo
7,43 gr cm 3
= 1,80 10 18 cal
ncleo
55 ,85 gr mol
Solidificacin. 7
Subenfriamiento
E. Libre
E. Superficial
200
(cal./cm3 Fe)
53,78742403
(ergios/cm2)
204
E. Libre (Sup.)
E. Libre (Vol.)
1,53862E-19
6,15447E-19
1,38476E-18
2,46179E-18
3,84654E-18
5,53902E-18
9,84715E-18
1,53862E-17
2,21561E-17
-2,81631E-20
-2,25305E-19
-7,60404E-19
-1,80244E-18
-3,52039E-18
-6,08323E-18
-1,44195E-17
-2,81631E-17
-4,86658E-17
cal./ ncleo
1,257E-19
3,9014E-19
6,2435E-19
6,5935E-19
3,2616E-19
-5,4421E-19
-4,5724E-18
-1,2777E-17
-2,651E-17
3.0x10
(1)
-18
1.5x10
(2)
(3)
0
-18
-1.5x10
2
-24 3
G(1) = 4 49.0 10-23
r - (4/3) 30.0 10 r
-23 2
-24 3
G(2) = 4 49.0 10-23 r2 - (4/3) 40.0 10 -24
r
G(3) = 4 49.0 10 r - (4/3) 53.78 10 r3
-18
-3.0x10
20
40
60
Solidificacin. 8
Radio
Crtico(A)
200
250
300
350
400
450
500
550
600
18,2
14,56
12,13333333
10,4
9,1
8,088888889
7,28
6,618181818
6,066666667
6,825E-19
4,368E-19
3,0333E-19
2,2286E-19
1,7063E-19
1,3481E-19
1,092E-19
9,0248E-20
7,5833E-20
1x10
E N E R G A L IB R E , G , E N C A L O R A S .
(1)
T = 380 K
(2) T = 390 K
-13
-1x10
-21
-24
G(3) = 1.706 10-19-19 nr - 4.65 10-21
nr (1- Ln1.66 10 nr )
G(2) = 1.79510-19 nr - 4.68410-21 nr(1- Ln 1.66 10-24-24 nr )
G(1) = 1.8910 nr - 4.71 10 nr(1- Ln 1.6610 nr )
(3)
T = 400 K
-13
-2x10
1x10
2x10
3x10
4x10
Solidificacin. 9
I = 10 33 exp
TT
V = 350
T
T
Solidificacin. 10
1,0E-09
1,0E-06
1,0E-03
1,0E+00
1,0E+03
1,0E+06
1,0E+09
Log t
100
x=1%
Subenfriamiento (K)
200
x=99%
300
400
500
600
700
800
900
1000
1,0E-12
1356 K0
100
Subenfriamiento (K)
200
1,0E-09
1,0E-06
1,0E-03
1,0E+00
1,0E+03
1,0E+06
1,0E+09 Log t
x=1%
x=9
300
400
500
600
700
800
900
1000
Solidificacin. 11
Datos
TE = 660C = 933 K
L = 2.550 cal/mol
sl = 121 erg/cm2
= 2.7 g/cm3
PAl = 27 g/mol
a= 4
v m = 27
g 1cm 3
cm 3
=10
mol 2,7g
mol
= 6 10 22
mol
27 g cm 3
16
(121) 3 (933 ) 2
1,65 10 9
3
= 52,45 =
=
2550 4,18 10 7 2
T T 2
16
2
(
) 1,38 10 T T
10
ln
1
6 10 22
G
1,65 10 9
=
K T
T T 2
T T 2 =3,14 10 7
933 0,2 = 186,6
190C (190 K)
= 2,93 10 7
(933-200)
(933-210) 210 2 = 3,19 10 7
208
= 0.22 TE
933
c.q.d
Solidificacin. 12
r* =
2
2 121 933
10 8 A
TE =
= 10 A (10 ,2 A )
2550
L T
cm
7
(
)4,18 10 208
10
a3
4
( N ) = (10 A ) 3 ;
4
3
f( ) =
G *het
0.02TE 19 C (K)
(933-19 ) 19 2 = 3,3 10 5
(933 10 ) 10 2 = 9,23 10 4
(933 12 ) 12 2 =1,3 10 5
(933 11) 11 2 =1,1 10 4
(933 9,5) 9,5 2 = 8,33 10 4
T
10
=
= 0,01
TE
933
r * en condiciones heterogeneas:
*
rhet
=
c.q.d
10 8 A
2 121 933
= 212 A
2550
cm
7
(
) 4,18 10 10
10
a3
4
) N = ( 212 ,0) 3 2,67 10 3
4
3
Solidificacin. 13
I = NA
D2 1
G *
exp
(
)
KT
b 2 Va
16
2
2 10 cm ;
b 2 = 10 A
2
1A
I = 6 10 22
nucleos
)
cm 3 s
4,41 10 6
) = 2,8 10 83 10 33 = 2,8 10 50
928 25
v = Va n s
D l G v
a 3A
1
2550 4,18 10 7
1A
T
5
10
.
2
23
16
8
2
2
KT
4
T
b
10 cm
7,1 A
(2,86 A ) 933 6 10 1,38 10
T
v = 380
T
T = 5 C ( 5K ) v =
380 5
cm
= 2,05
928
s
Fraccin solidificada:
X=1-exp(
t0.01(1%)= 4
t0.99= 4
Clculo de la I con T = 5 y = 20
1
=1
Va
10 5
G *
G *
33
exp(
10
exp(
)
KT
KT
10 15
I = 10 33 exp (
D 2 = 10 5 cm 2 / s;
Iv 3 t 4
)
4
ln 0,99 4
= 1,16 10 12 s
50
3
2,8 10 (2)
(= 36656 aos )
ln 0,01 4
= 169718 aos
2,8 10 50 (2) 3
Solidificacin. 14
I= 10 33 exp (
4,41 10 6
) =10 33 exp ( 47 ,8) =1,8 10 12 (misterios, diabluras de
923 100
la mecnica estadstica)
V=
380 10
4.1cm / s
623
0,04
=1 10 4 s
12
3
1,8 10 ( 4,1)
t0.01=
t0.99 = 0,0006 s ( milsimas de segundo)
quasiexplosivo
log t