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九州大学 稲垣 八穂広

バックエンド週末基礎講座 2010.10.30-31 福井大学
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2010
3

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+ "0('%/8DOE 1982 6:Borosilicate glass: BSG; 9

:High-silica glass: HSG; #":Synroc: SYN;
 9.9)#$:FUETAP concrete: FUE; :Tailored ceramics: TC; <7-:Glass marbles in lead matrix: Pb-M;
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9
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2

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

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DOE 1982

248#(Product performance)(Process factor)
%)$:> (Waste loading)" .# < >(Complexity-reliability)

13! > (Mechanical stability)

&  >(Personal safety)'* >
(Leaching)7-+=75> (Quality control & assurance)/( > (Resource requirement)10



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 (DOE 1982)$ " #!&  
$% 11 *(,

(SiO2 (SiO2%+'

Si(IV)O

Na, Li, Ca, Sr, ..(+I, +II)
B, Al, ..(+III)
Actinides(+III, +IV)
Other elements(  

)$&#%+' " ! 12   MCC-1
Temp.= 90°C
S/V = 10 m-1Time = 28days
Composition with leach rate < 0.1g/m2/d
SiO2: 51-53wt%
B2O3+Na2O: 24-28wt%
Al2O3+ Fe2O3+WP: 21-25wt%





3

(Hench 1983) SiO2   13

 ’


%U$ #7BV1EXL&WMN0DG562.
 <QIKT%43!P"2.O:  
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14

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 ’ ’

$% # ().! -*"'"'/  &+/,+      Grambow 1509=:"& )Q

MCC-1, MCC-2

MCC-3

MCC-4

MCC-5

VHT

L4

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F2

MCC-1: 40,70,90
MCC-2: 110,150,190

7

   

Y=
3M


W ^ R400mm2

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<9J

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ml / minCZ 10.2 ml / min

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16

>B? ;-( '
50

B
Li
Mo
Cs
Si
Na
Al

40

NL i

30

[g/m 2 ]Normalized elemental mass loss&,D+,E
NLi = Ci fi V/S

JSS-A glass
MCC-1
Temp. = 90°C
S/V=10m-1
deionized water

Ci :i"
fi F>B?i"+,
V : !
S : >B?$.!

Si

20

10

0

0

50

100

150

200

250

300

350

400

time [d] JSS Project Phase IV, 1987 

";'F'*#88<: 459675=0
1-( '2/);  '8A@C3%017  Grambow’s reaction path model  

  
Rate Equation

PHREEQE
Matrix dissolution(congruent)
Each element
Soluble or precipitate ?
SolublePrecipitate

SiO2(am) + 2H2O = H4SiO4
1st order dissol. rate for SiO2(am)ar = k+ ( 1 - aSi ) + rfin
sat

Solution
B, Li, …

Secondary phase
Fe, Al, …

Solution concentrationfor each element
SiO2 saturationr : glass matrix disol. ratek+: initial dissol.rate(constant)aSi: H4SiO4 activity
asat: H4SiO4 activity at saturation
rfin: final dissol.rate18 %$& ' Grambow’s reaction path model
50

B
Li
Mo
Cs
Si
Na
Al

40

NL i

30

[g/m 2 ]B, Li, Mo, Cs
Na
Si

20
10

0

JSS-A glass
MCC-1
Temp. = 90°C
S/V=10m-1
deionized water

Al
0

50

100

150

200

250

300

350

400

time [d]

 Grambow modelJSS Project Phase IV, 1987





Grambow model " #  !  %$&(D.Strachan )19

&+(! 

UO2 fuel 30GWd/t
Waste loading 20wt%

Displacements in HLW glass per decay event
-decay: 130(-particle)+ 2000(recoil nuclei)-decay: 0.07

(Lutze, 1988 ) (Lutze, 1988 ), - . $% !"#  ,&+(")+*'(   20  ’’
%*"#.,=@!5B6?9;'-   <3?5B6?C)
4($0@!
12FAG E/3?5B6? '"#7&,=@! %*"#,=@!D8+>,:

21



  ’’

0$*1-1 (#"!$*.,'+.   %)+  )+/&22

<@=#B !
P0798 glass
Temp. = 90°C
S/V=1,200m-1
deionized water&S/V
Si $2%
Si% 6-5,:

S/V  Grambow 

(Inagaki, 1994)

;"/0:196&S/V267)Grambow?>A6827 2.4+*('#6 3?>A- *
23

/21 6 
R7T7 glass
Temp. = 110°C
S/V=10 - 21,000m-1
MgCl2 brine water

S/Vt, day1/2/m

t  Grambow, 1992 4S/V&*,5(t & "%#,
+ ' ! -
4/21' )$(03.' 7524         

Rate [g/m2/d] = ro · 10 •pH · exp(-Ea/RT) · [1-(Q/K)] + rf
05;<(

pH$+

4($+

%:!

2$5;<((>05;<()

r005;<(A"/<(&-8,$B [g/m2/d]
5;pH$+Ea3+  [kJ/mol]Q 3=7ASi or Si+AlB
K5; * '9&-A5;(7BASi or Si+Al+ etc. B
rf@!)2$5;<( [g/m2/d].? 6#1$+ B

J >G<&7 31)/(SiO2(am) + 2H2O = H4SiO4 )JAFD?K, Ea, etc…L8'/J &) rf8(&J 'JE@H0%/J8+%98 J7:246;/----

KEU.!L5 ,BI=FC0"#*$/
25

152-"BMIDGNRO)V
/

*0




+*0
*0

9='&=#:==X1;=536=2X1

NRO)
NRO

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

NRO

9='&=(.
:==
;=536=2

W F $W
!"E?

1527 !- <NRO)V +HT74>%UFJK @A ==8"%,.&- %*-(< F-CL 0QSPTF,UHE?
==82$-#%'0/*-463 %(26

,.-( /$& 01

N2 gasGlass

Peristaltic
pump

Reaction cell
Oven
Input solution

 

Output solution SPFT: Single-pass flow-through PNNL  ( %(,.- 2#!
("& 0S/V 1'*+)!
27

3;5-  >   8;:6-
SON68 glassat pH=9r0 = 2.1 [g/m2/d] at 100°C
Q = 76 [kJ/mol]

-9
-10

90°C

log r0 -11[mol/cm2/s]
-12

50°C

-13

1



2

3

4

5

6 7
pH

8

9 10 11 12    SON68 glassr0pH (Advocat, 1991)= ""9<4>,%$*",+ !8;:6- 7>6 "&,/12(#=  -0/12(&".)'#28

   ’’

#>O?M- <M "TB#*+1V'(@.5 

#!6IN%H9,3'(6IN%RAG$;U
#S8<MW/P>O?MW ")Q2
&(6IN%J



#S86IN%-DF0C?M7Q2
:L=N%4K6E  29   ’

<"'6=9*8 ./-+6%5(
7*8+627
 ,27
$0 #=;)
1=4:& 3!



30

053' 9 !,3462


I



II

IIIIV

Jiricka, 2001

Stage I : 1/%*,7 8
Stage II : 1/%( +")*,7#;8
Stage III:,&+-.$7  

831

.2/ 4103(2)"Si(1)"SiSi

Na, B, etc.





 



 


Na, B, etc.

Si

Si

Na, B, etc.

(2)Si(1) (3)  

H 2O








(2) 





(3)
(1)





 





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





(4) "
(3) $# "

!


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

  










2004

.2/#' -$!+'103,"(  &)*%+532

$! ) (#"%Q = 49kJ/mol

P0798 glass
S/V=7,400m-1
0.001M NaOH

Ref. data for activation energy- Ion-exchange in Na2O-Al2O3-SiO2 glass : Q = 49 kJ/mol (McGrail, 2001)- Initial dissolution rate for SON68 glass: Q = 71 kJ/mol (Techer, 2000)'   & 

(Inagaki, 2006)
33)/+ 4% 1  %
P0798 glass
Temp. = 120°C
S/V=7,400-12,000m-1
Alkalline water









(Inagaki, 2006)

0 +.*,(- 5
$&'42#3! (analcime) 5 4%
0   
"34

KVO:"4^ 7H *+ &%4 ] EG5<
UJMZWIMP 5<2/H3>(Inagaki, 2009))6/&

-7:.3:2

;'<%!" #4(*905:18
;$$""'<"#C

,:27:+& \CH! \C D-DRYLNSX\>M]T[$HKVO5
CC;,D 8H=.G
CCKVO1;H'&D 9&GB"!Q]PFH)6\>UJMZWIMP
35
CC=@?A>B=.G!(0GMI"Q!;  P 9KPJ
2

Present work (Micro-reactor)
90
70
25-70 5 μL/min50
90  20 μL/min25

r0   

P0798 glass

1
0

PNNL work (SPFT)
90
50
25

-1
-2
2

4

6

pH

8

10

12


(r0 )(  
)(Inagaki, 2010)
LFHONEHJ #:AC %15D;

:216@/-0;%.)% 
%+*(,:AC 8>?
%$$.)7<+*(,:=431%&AB9KPJ'

36

     Reacted area

SIMS area

Intensity (arbitrary unit)   SIMS  (Inagaki, 2009)SIMS profiles for altered layer
100
10-1
Si
10-2
10-3
10-4

After test at 90°C, pH5.6 for 1000 h

Fe
B
Si

Fe

B
6 m

6 m

Layer(1) Layer(2)
0
5
10
15
Depth (m)20

Layer (1):  6 μm 
B: fully depleted, Fe: enriched  
Layer (2):  6 μm 
B: partly depleted  !

37?




 # JNC-H12!#

Rate = r0•[1-(Q/K)] + rf

( r0 >> rf )H12!#!!"#A+CB
ZSXU4J%TYR&K6(>IK:EO@ (/ 9Q'.)>> Rate = rf
Z"3\]IMO6%0K
>(I'.D?%05HEO@$

 %

60=%TYR&: GJ# 2;
W[V\%05J$]MN?
rlong\at 60=<]Q1@Rate = rf = 10-3 [g/m2/d]

PIMOSXU-8* _10
SXU!),_^\ F%0EOLGJ7]

38

"!



 (Gin, 2009)

















#$
39

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CCIM: Cold Crucible Induction Melter



"

  (&$# )

#


'!%



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
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T:/4

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T:.eKVmSaRBhG

0U+mSaRB
iE5_)#\GCNX\G7Lj[9I<o  pWJ!*g@qCNX;3=EHb+T:/4
SaTk>83Yn Z
TMJ`l=^F6-

  (&$# )+]PF6-o%,$*)'!
* #%1Qp40   

41’


4qJNgRjBYZDVSgX[ab
4KfOi9r6LpQTG!/& 5+5,'"W78Uc@D!/&*2# h^]
4!/&Ng>FqJVCnr>F&(5%sSg
4 1.5)r\6L?s
4PI$"0lEmF!/&`GtekMHdr-/3& s
4_A!/&BYX[<o;=:
42   43 5 5:B<! G JNC-H12D@G>:B<5$

Rate = r0•[1-(Q/K)] + rf

( r0 >> rf )H12D@G>D?9DE<;G<4-/7:B<$5
A+CB
ZSXU4J%TYR&K6(>IK:EO@ (/ 9Q'.)>> Rate = rf
Z"3\]IMO6%0K
>(I'.D?%05HEO@

H!A=CI
60=%TYR&: GJ# 2;
W[V\%05J$]MN?
rlong\at 60=<]Q1@Rate = rf = 10-3 [g/m2/d]

PIMOSXU-8* _10
SXU!),_^\ F%0EOLGJ7] F26+7.)F
263,*'&%5 8 01"3(($#!5445 <67 3412" :9<800/00 0/0= >!%+%.($0#-%$(&($
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