Upload
daniel-popescu
View
234
Download
0
Embed Size (px)
Citation preview
7/21/2019 Murad Spectroscopy
1/32
57Fe Mssbauer Spectroscopy
Enver Murad
Marktredwitz, Germany
Enver Murad
Marktredwitz, Germany
:
a Too !or t"e #emote $"aracterization o! %"yosiicates&
7/21/2019 Murad Spectroscopy
2/32
'asic principes o!
Mssbauer spectroscopy
7/21/2019 Murad Spectroscopy
3/32
E m i s s i o n ( b s o r p t i o n
# e c o i
Free emittin)and absorbin)atoms
Ener)y o! recoi
*+ray ener)y
Mass o! atom
7/21/2019 Murad Spectroscopy
4/32
E m i s s i o n ( b s o r p t i o n
o r e c o i
Emittin)and absorbin)atoms !i-ed in a attice
Mass o! partice
Mssbauer spectroscopy is t"e recoi+!ree emission
and absorption o! )amma rays
7/21/2019 Murad Spectroscopy
5/32
(ppearance o! Mssbauer spectra
.ependin) on t"e oca environments o! t"e Fe atoms and t"e
ma)netic properties, Mssbauer spectra o! iron o-ides can consist o! a
sin)et, a doubet, or a se-tet/
Symmetric c"ar)eo ma)netic !ied
(symmetric c"ar)eo ma)netic !ied
Symmetric or asymmetric c"ar)eMa)netic !ied 0interna or e-terna1
2 '"!34somers"i!t
5uadrupoe
spittin)
Ma)netic"y
per!ine!ied
7/21/2019 Murad Spectroscopy
6/32
Fe6
+ 8 + 9 : 9 8
; e o c i t y 0 m m < s 1
#
e
a
tiv
e
T
ra
n
s
m
is
s
io
n
Fe9
+ 8 + 9 : 9 8
; e o c i t y 0 m m < s 1
7/21/2019 Murad Spectroscopy
7/32
+ = : + 5 : 5 = :
; e o c i t y 0 m m < s 1
T
ra
n
s
m
is
s
io
n
+ = : + 5 : 5 = :
> = : / : : m m < s ?
= : / 8 = m m < s
7/21/2019 Murad Spectroscopy
8/32
@se o! Mssbauer spectroscopy as a
A!in)erprintin)B tec"niCue
4somer s"i!ts and
Cuadrupoe spittin)s
o! Fe+bearin) p"ases
vary systematicay
as a !unction o! Fe
o-idation, Fe spin
states, and Fe
coordination/
Dnowed)e o! t"e
Mssbauer
parameters can
t"ere!ore be used to
A!in)erprintB an
unknown p"ase/
7/21/2019 Murad Spectroscopy
9/32
yper!ine parameters o! Fe6o-ides
Minerarderin)
temperature 0D1Ma)netic "yper!ine !ieds
RT: '"!0T1 4.2 K: '"!0T1 2 0mm
7/21/2019 Murad Spectroscopy
10/32
4ron in p"yosiicates
7/21/2019 Murad Spectroscopy
11/32
=:= p"yosiicates
9:= p"yosiicates
Fe2+, Fe3+
Fe2+, Fe3+
O H , O
S i
A l
O
S i
S i
O H
A l
O
O
Fe6
Fe6
7/21/2019 Murad Spectroscopy
12/32
$assi!ication o! cay+sized p"yosiicates
0cay mineras sensu stricto1
Oayer typecta"edraoccupancy
cta"edra
c"ar)e1$entracation0s1
Group $ommon species
= : = .i2 ( Daoin Daoinite, "aoysite
= : = Tri3 M) Serpentine Oizardite, c"rysotie
9 : = .i R /9 ( %yrop"yite %yrop"yite
9 : = Tri R /9 M) Tac Tac, minnesotaite
9 : = .i < Tri /9 N /I (, M), Fe Smectite Montmorionite, nontronite
9 : = .i < Tri /I N / (, M), Fe ;ermicuite ;ermicuite
9 : = .i < Tri / (, M), Fe Mica 4ite, )auconite
9 : = 0: =1 .i < Tri (, M), Fe $"orite $inoc"ore, c"amosite
1%er !ormua unit >=019?, 2/3.iocta"edra
7/21/2019 Murad Spectroscopy
13/32
Mssbauer spectra o! seected
AsimpeB 0pure1 cay mineras
7/21/2019 Murad Spectroscopy
14/32
T"e AsimpestB cay minera:
kaoinite >(9Si95018?
Daoin < ari U 95D
O H , O
S i
A l
O
+ 5 : 5+ 7 / 5 + 9 / 5 9 / 5 7 / 5
; e o c i t y 0 m m < s 1
G H
G H / 5
G G
G G / 5
= : :
T
ra
ns
m
is
s
io
n
0V
1
7/21/2019 Murad Spectroscopy
15/32
+ = : + 5 : 5 = :; e o c i t y 0 m m < s 1
G 7
G H
G G
= : :
T
ra
n
s
m
is
s
io
n
0V
1
Daoin < ari U 8/9D
7/21/2019 Murad Spectroscopy
16/32
Mssbauer parameters o! cay mineras
Minera Temp4somer s"i!t03
7/21/2019 Murad Spectroscopy
17/32
4ite: 0D,61-y0(9+-M-10Si8+y(y1=019
4ite E$. Q5
+ I + 6 : 6 I
G 5
G I
G 7
G H
G G
= : :
G 7
G H
G G
= : :
T
ra
n
s
m
is
s
io
n
0V
1
Fe6: 92
G 7
G H
G G
= : :
G 7
G H
G G
= : :
+ I + 6 : 6 I
G 5
G I
G 7
G H
G G
= : :
G 5
G I
G 7
G H
G G
= : :
Tr
a
n
s
m
is
s
io
n
0V
1
G 7
G H
G G
= : :
G 7
G H
G G
= : :
+ I + 6 : 6 I
G 5
G I
G 7
G H
G G
= : :
G 5
G I
G 7
G H
G G
= : :
: : / 9 5 : / 5 : / 7 5 = = / 9 5 = / 5 = / 7 5 9 9 / 9 5
0 m m < s 1
:
8
H
= 9
= I
Tr
a
n
s
m
is
s
io
n
0V
1
%
0V
1
Fe6
: %021
7/21/2019 Murad Spectroscopy
18/32
Mssbauer parameters o! cay mineras
Minera Temp4somer s"i!t03
7/21/2019 Murad Spectroscopy
19/32
ontronite: M-Fe9 0Si8+-Fe-1=0196
7 :
H :
G :
= : :
T
ra
n
s
m
is
s
io
n
0V
1
+ = : + 5 : 5 = :
; e o c i t y 0 m m < s 1
#T
ontronite (%4 66a
96/8I V Fe
=/88 V FedX 9/6 V Gt
From (se-tX =/8 V Gt
77D
7 :
H :
G :
= : :
T
ra
n
s
m
is
s
io
n
0V
1
+ = : + 5 : 5 = :
; e o c i t y 0 m m < s 1
H 5
G :
G 5
= : :
+ = : + 5 : 5 = :
H 5
G :
G 5
= : :
+ = : + 5 : 5 = :
H 5
G :
G 5
= : :
7/21/2019 Murad Spectroscopy
20/32
ontronite: M-Fe9 0Si8+-Fe-1=0196
ontronite (%4 66a
+ 8 + 9 : 9 8
; e o c i t y 0 m m < s 1
G I
G H
= : :
T
ra
n
s
m
iss
io
n
0V
1
G I
G H
= : :
T
ra
n
s
m
iss
io
n
0V
1
+ 8 + 9 : 9 8
; e o c i t y 0 m m < s 1
G 9
G 8
G I
G H
= : :
+ 8 + 9 : 9 8
G 9
G 8
G I
G H
= : :
Fe9
7/21/2019 Murad Spectroscopy
21/32
Mssbauer parameters o! cay mineras
Minera Temp4somer s"i!t03
7/21/2019 Murad Spectroscopy
22/32
$ompe- natura cays:
AT"e rea wordB
7/21/2019 Murad Spectroscopy
23/32
%"ysics Today 610H1%"yosiicate wit" intercaated interayer
a
$89
ote: Fe+containin) interayer must be!rozen to s"ow Mssbauer E!!ect%"yosiicate wit" intercaated interayer:AatureZs tras"canB
Fe9
Fe6
7/21/2019 Murad Spectroscopy
24/32
G G / I
G G / H
= : : / :
T
ra
n
s
m
is
s
io
n
0V
1
+ = : + 5 : 5 = :
; e o c i t y 0 m m < s 1
G G / I
G G / H
= : : / :
+ = : + 5 : 5 = :
G G / I
G G / H
= : : / :
Daoin A[o!kaB U 8/9D
.$'+treated \/==V )oet"ite
G G / I
G G / H
= : : / :
T
ra
n
s
m
is
s
io
n
0V
1
+ = : + 5 : 5 = :
; e o c i t y 0 m m < s 1
G G / I
G G / H
= : : / :
7/21/2019 Murad Spectroscopy
25/32
'au-ite
G I
G H
= : :
+ = : + 5 : 5 = :
; e o c i t y 0 m m < s 1
G I
G H
= : :
T
ra
n
s
m
is
s
ion
0V
1
G I
G H
= : :
' ] +
G I
G H
= : :
G I
G H
= : :
G I
G H
= : :
+ = : + 5 : 5 = :
; e o c i t y 0 m m < s 1
G H
G G
= : :
T
ra
n
s
m
itta
n
c
e
0V
1
G H
G G
= : :
G H
G G
= : :
G H
G G
= : :
' ] +
6 - . $ ' 9 G 5 D
= : :
7/21/2019 Murad Spectroscopy
26/32
#ed soi
G 9
G 8
G I
G H
= : :
T
ra
n
s
m
is
s
io
n
0V
1
+ = : + 5 : 5 = :
; e o c i t y 0 m m < s 1+ = : + 5 : 5 = :+ = : + 5 : 5 = :
9 G 5 D
G I
G H
= : := 9 : D
G I
G H
= : :7 7 D
G I
G H
= : : 8 / 9 D
7/21/2019 Murad Spectroscopy
27/32
E-traterrestria Mssbauer
spectroscopy
Ounar sampesIn situMssbauer spectroscopy on Mars
Ounar AsoiB =H8
7/21/2019 Murad Spectroscopy
28/32
S/S/ a!ner, =75: AT"e data s"oud not /// be interpreted
in an isoated !orm, but /// correated wit" t"e resuts o!
ot"er tec"niCues ///B/
F e 9 i n ) a s sF e 9 i n p y r o - e n e
F e 9 i n i m e n i t eF e 9 i n o i v i n e
M e t a i c i r o n a n o p " a s e i r o n
#
e
s
o
n
a
n
t
a
b
s
o
rp
tio
n
+ 5 : 5; e o c i t y 0 m m < s 1
[ a n ) e t a / , = G G 5
Ounar AsoiB =H8
For unar sampes, t"is is possibe ^
7/21/2019 Murad Spectroscopy
29/32
7/21/2019 Murad Spectroscopy
30/32
AT"e data s"oud not /// be interpreted in an isoated !orm,
but /// correated wit" t"e resuts o! ot"er tec"niCues ///B
0S/S/ a!ner =751
A_ we assi)n t"e broad doubet present in Mssbauer
spectra o! >Mars? sois to be due to Fe9su!ates rat"er
t"an oivine _ B 0'is"op et a/ 981
Fe2su!ate&
(S(
7/21/2019 Murad Spectroscopy
31/32
Summary
St t" d k ! 57F
7/21/2019 Murad Spectroscopy
32/32
Stren)t"s and weaknesses o! 57FeMssbauer spectroscopy
` Sensitive ony to 57Fe0no matri- e!!ects1
` Sensitive to o-idation state
` (ows distinction o!ma)netic p"ases
` ;ery sensitive towardsma)netic p"ases
` on+destructive` #esoution imited by
uncertainty principe
` Sensitive ony to 57Fe0AseesB ony 57Fe1
` $oordination & to
` %arama)netic p"ase datao!ten ambi)uous
` .iama)netic eementsubstitution rea-ation
` Sow` 4! possibe, use ot"er
tec"niCues as we
Stren)t"s [eaknesses
!ten a combination o! Mssbauer spectroscopy wit"ot"er tec"niCues can "ep sove probems t"at cannotb d i M b t