SURFACE FILM CHARACTERIZATION OF CORRODED HLW GLASS SPECIMENS

GERHARD BART, ERNST T. AERNE, ROLF GRAUER, HANSPETER LINDER, DORIS Z'BERG,
HANS U. ZWICKY
Swiss Federal Institute for Reactor Research, CH-5303 Wuerenlingen

ABSTRACT

In a joint Japanese, Swedish, Swiss HLWglass characterization pro-

gramme, interactions of real waste glass specimens with possible burial
system components are studied. The report describes the glass surface ana-
lytical work performed at the Swiss Federal Institute for Reactor Research
(EIR) during the first completed phase of the programme.

INTRODUCTION

The Swiss Federal Institute for Reactor Research (EIR) is actively

participating in the joint Japanese-Swedish-Swiss (JSS) project, funded by
CRIEPI, SKB and NAGRA in the three respective countries. The aim of this
project is to characterize a specific borosilicate high level waste glass
with its interactions to ground water, overpack, backfilling material and
granite, in order to predict its long term behaviour under repository con-
ditions. The main task of EIR in the first (completed) phase of the project
consisted of corrosion film characterization on active samples by Secondary
Ion Mass Spectrometry (SIMS), autoradiography and light microscopy. Some
glass corrosion experiments and micro gamma scanning tests were additionally
run in parallel to Swedish work, performed at Studsvik (1).
This report describes the EIR results from this first phase. The ex-
perimental equipment and procedures used in the programme are reviewed.

EXPERIMENTAL

Glass composition and description of corrosion experiments

The radioactive French JSS-A glass, with activity levels of 6 E9 Bq

((,y) and 5 E8 Bq (•) per gram was prepared by CEA at Marcoule, France,
using the laboratory scale vitrification line "vulcain". The detailed che-
mical and radiochemical specifications of this borosilicate glass are given
in reference (1) and in table I. The main activity is made up by 137-Cs,
90-Sr and 144-Ce. The principal alpha emitter is 238-Pu. Specimens of
9x9x3 mm were cut and ground to 600 grit. They were then subjected to (3-182)
day, static MCC-] type corrosion experiments at 900 C. Various leachate com-
positions (distilled water, silicate water and synthetic ground water) and
two SA/V ratios (0.1 and 3 cm-I) were used both, with and without the pre-
sence of granite (1). Subsequently, Inductively Coupled Plasma (ICP) and
AAS leachate analysis were performed to calculate normalized elemental mass
loss data.

Mat. Res. Soc. Symp. Proc. Vol. 44. ' 1985 Materials Research Society
214

Table I: JSS-A glass composition, SIMS analyzed nuclides

component weight S atomic S nuclide for component weight S atomic 1 nuclide for
SIMSanalysis SIKSanalysis
LI20 1.97 6.70 L1-07 K003 1.69 0.60 Ms-97
8203 14.40 21.09 8-11 RuO2 0.04 0.015
No20 9.79 16.11 NA-23 RhO
3 0.01 0.004
i90 0.04 0.05 49.24 Ag2O 0.03 0.013
A1203 4.67 4.87 A1-27 CdO 0.03 0.012
$102 45.15 38.34 SI-28 SnO
2 0.02 0.0069
P2 05 0.48 0.35 S-
b2 03 0.01 0.0034
Cao 4.01 3.65 Ca-40 TeO2 0.23 0.074
Cr2 03 0.50 0.34 -Cs
20 1.41 0.51 Cs-133
1n02 0.67 0.39 BaO 0.56 0.19 Bi-138
Fe203 2.89 1.85 Fe-56 La203 0.89 0.28 La-139
CuO 0.11 0.075 Ce2 03 0.92 0.29
NiO 0.73 0.50 Pr2 03 0.44 0.14
CuO 0.01 0.0065 Nd2 03 1.58 0.48
ZnO 2.52 1.58 Zn-64 ThO2 0.16 0.031
SrO 0.33 0.16 Sr-88 U02 0.52 0.10 UO-254
Y203 0.20 0.090 PU02 0.22 0.041 PuO-255
ZrO
r 1 2.63 1.09 Zr-91

Glass specimen characterization after corrosion

Remotely operated, contained and shielded instruments were available

for light microscopy, mechanical surface topography measurements, micro
gamma scanning and alpha autoradiography. The spatial resolution reached
with the latter two techniques was 200 and 100 jimrespectively. Micro gamma
scanning, detecting the fission products 125-Sb, 134-Cs, 137-Cs, 144-Ce and
154-Eu, provides information concerning the activity distribution within
the whole sample along the scanned line. The alpha autoradiographic sampling
depth lies at < = 20 sjm. The depth resolution reached with mechanical profi-
lometry for surface roughness and SIMS crater depth determination is better
than 10 nm. Elemental in depth analysis was performed with the shielded SIMS
instrument (2), as presented in figure 1. The quadrupole mass analyzer
equipped system is process controlled by an HP-9836 computer combined with an
HP-6942 multiprogrammer. It provides for sequential counting of > 20 nuclides
with varying counting times and mass filter parameters. A list of the actual-
ly SIMS analyzed nuclides is added in table I. A 5 kV electron gun assures
efficient charge compensation of the insulating samples, bombarded with 12 kV
02+ primary ions. To avoid crater edge effects, a central zone of 70x70 vImis
electronically gated for data collection only. This central zone lies in an
ion etched glass surface area-of 200x200 jim(figure 2a). Based on mechanical
depth determination of the final crater and on experimentally estimated ero-
sion rate variations between bulk glass (vl) and gel layer (v2), with v2=2vl,
corrosion depth values were determined using the SIMS boron or alkali element
profiles. Taking the Si concentration (Csi) as an internal standard, sensiti-
vity factors (fx) were determined for each element (x) out of the bulk glass
elemental count rates (rx).

CSi rx
fx (1)
Cx rSi
 215

Figure 1: Refurbished SIMS equipment for active sample analysis, biologi-

cal shield in the open position. A) Process controller,
B) Power supply, C) Primary beam formation, D) Sample recipient,
E) a-box for sample manipulation.

Figure 2: Light microscopical analysis of JSS-A sample leached for 28 days

at 90oC in distilled water, SA/V - 0.1 cm-1
a) sample overview, with SIMS crater of 200x200 Um
b) magnified SIMS crater bottom (magnification 500 x)
216

Since Si remains the main concentration in the gel layer and the Si/O ratio
presumably is not altered between bulk glass and gel layer, it is assumed
that the elemental sputtering and ionization yields do not change drastically
either, hence the sensitivity factors determined in the bulk glass can be
used in a first order approach also to calculate semi quantitative atomic
elemental concentrations in the gel layer.

1 rx(gel)
Cx(gel) - fx rSi(gel) CSi(gel) (2)

Since CSi(gel) is not known, it is set to one and the assessed relative ele-
mental concentrations (including Si) are finally normalized at each profile
point to 100 % (figure 3).

E
0 Erosion Speed Vi on
+ 10 ufceSeed V2
< 1 gel bulk

0 .. _SI-128

2[0]

*Z10

S. MA-27

E . Sr-..
....88i
10-2
! ' .2 6 8 0 12

depth-I SIMS prolfile depth [pm]

Step 1 2 3 4

Figure 3: Converted SIMS profile of JSS-A sample corroded for 91 days at

900 C in distilled water, SA/V = 0.1 cm- 1 . Depth step 1 = Zn(Mg)
maximum, depth step 2 = AI(Fe) maximum, depth step 3 = Sr(Ba)
plateau, depth step 4 = bulk composition.

> cx = 100 % (3)

x=l

Based on these calculations, atomic elemental concentration variations from

bulk glass to gel layer or within the gel layer can only be considered on a
relative basis, comparing elements among each other (e.g. The Pu/Zn atomic
concentration ratio in the inner gel layer is higher than in the bulk glass).
The relative atomic concentration values should not be automatically inter-
preted as absolute volumetric concentration changes from gel layer to bulk
glass.
 217

Results and discussion

The micro gamma scanning and autoradiography results show that the JSS-A
glass samples are homogeneous within the tested spatial resolution scale of
100 jim. Light microscopy reveals that the corroded samples are covered with a
compact corrosion layer, which at some locations is slightly damaged due to
sample handling. The surface still shows polishing scratches which otherwise
would be concealed if covered by thick deposits. All optically analyzed speci-
mens display a fine grained structure on the SIMS crater bottom (figure 2b).
This may be due to initial surface roughness of the corroded samples. (Eroded
craters on a polished, non-corroded, similar, inactive glass (ABS-118) show a
smooth flat bottom). Dealing with rough corroded sample surfaces, however re-
duces the expected elemental in depth profile resolution. All the samples
leached without granite, show at the outermost sample surface a thin (-=31m)
Zn, Mg rich layer with 15-30 atom % of Zn and about 1 % of Mg. The layer
forms very early during the corrosion event, then increases in thickness only
slightly with progressing corrosion time (figure 4).

)0 a I Ulsled waler leached 11'i.oL@!L I' PA~fL

wal WL1!tAd

"3"---
wli

depth rpm
n depth [ImI

Figure 4: Evolution of Zn rich surface film with time

When leaching is performed in Mg containing ground water (4 ppm), Mg con-

centration increases dramatically in the layer (up to 10 atom %). The Zn rich
surface layer is described also for glass PNL-7668 and is addressed in (3)as
a smectitc clay mineral precursor. In parallel to the deposition (precipita-
tion) layer formation, the gel layer becomes correspondingly depleted in Zn
and Mg with progressive corrosion time.
218

10 Li 30- 2.0o

a ~25 1.

05 .0-
u-

0 0.1

3 7 U4 28 91 182 3 7 11 28 91 182 3 7 I/ 28 91 182

1i
1-0- Sr
,.-.--
... 0......... .-
1.0- Cs
)-,- 0.2 - Pu
........
0.8- CA

02 0,05

00 0
3 7 , is
28 41 182 3 7 14 28 91 182 3 7 U. 2 9 1 12
Durationof corrosion experiment 1days)
-step 1 -- step2 -.... step3 --- step4

Figure 5: Relative atomic concentration variation at key profile

step positions in function of time

The corrosion history for Li, B, Mg, Sr, Cs and Pu is also presented in
figure 5. For this plot, the atomic concentration values were extracted at
the key depth step positions shown in figure 3, with step 1 = Zn,(Mg) maxi-
mum, step 2 = Fe,(Al) maximum, step 3 = alkaline earth plateau, step 4 = bulk
atomic concentration.
The highly soluble elements such as B, Na, Li, Mo are strongly depleted
in the gel layer. Figure 5 shows that the boron loss at depth step 2 is al-
most complete already after short corrosion periods. (At depth step 1 the bo-
ron concentrations lie in the range of 0.05-0.1 atom % and are not visible in
the linear plot.) However Na and Li may be retained in the outermost surface
precipitation, possibly forming insoluble alkali silicates (4). (See Li in
figure 5. After > = 91 days of corrosion a slight concentration increase in
depth step one is seen again.) In parallel to the loss of the highly soluble
elements, there exists a relative gel layer concentration increase for the
slightly soluble elements Fe, Al and the lanthanides, which show maximum ato-
mic concentration values immediately underneath the surface precipitation. U
and Pu also belong to this group. The SIMS profiles of these two elements
match very closely together. On the other hand, the alkali earth elements
(as well as Zr) show concentration maxima deeper inside the gel layer, with
the relative concentration increase generally diminishing in the sequence
Ba > Sr > Ca. Due to its much lower ionic radius, Mg doesn't follow the al-
kali earth elemental trends, but matches the Zn behaviour.
The corrosion therefore has to be addressed as incongruent network break
down. The incongruent corrosion behaviour is also reflected in the fact that
any granite present in a corrosion experiment, contains significant fission
product concentrations even after acidifying for leachate analysis. The for-
mation of a structured sequence of surface deposition over a slightly struc-
tured gel layer could best be explained, if the network break down proceeded
as topochemical reattion of a homogeneous glass (5). However selective corro-
sion of an inhomogeneous glass or a dissolution reprecipitation reaction can-
not be excluded at the present time.
The SIMS determined corrosion layer thickness values match closely to
leachate boron calculated depletion layer thickness data (figure 6).
 219

18 corrosion depth based on 18- b)

EB boron leochate data
measured SIMS corrosion depth 16
E
14 E JSS-A gloss 14-
12- - 0 ABS-118glass 12

10 10 .2

2 "*' /. .
/.- 6-
4-
210 corrosion time 1d3 -2/ corrosion time Id3
o so '1 oo . 10 so I 160
o

Figure 6: SIMS analyzed corrosion depth versus leachate boron loss deter-
mined corrosion depth of distilled and silicate water leached
JSS-A samples (and its inactive model ABS-118) in function of
time.
Irrespective of which corrosion mechanism prevails, it is important
from the viewpoint of future surface analysis, that the surface topography
appears to be only marginally altered by corrosion, or drying following
corrosion. The surface precipitation and gel layer seem to be intact and
thus reflect the whole corrosion history even after leaching periods up to
182 days.
The corrosion depth for the analyzed matrices decreases in the series:
silicate water > distilled water > = silicate water + granite. Due to more
rapid Si saturation, experiments with SA/V ratios increased from 0.1 to
3 cm- 1 show a lower degree of corrosion. Compared to glass PNL-7668 leached
under analogous MCC-] conditions up to 182 days (3), the JSS-A glass re-
veals 2-3 times lower corrosion depth values.
If granite is present during leaching, the SIMS profiles indicate five
to seven times less corrosion after short term leaching experiments
(< = 28 days). It is suggested that granitic fines are responsible for this
behaviour, since high blank leachate concentrations are realized simultane-
ously. Some of the samples corroded in the presence of granite were covered
with a 10-20 Pm thick, white deposit, which proved to be alpha inactive and
seems to consist of granite reaction products. The same samples give rise
to false overall weight loss measurements.
Compared to its inactive model ABS-II8, the active JSS-A glass does not
indicate any direct or indirect activity enhanced corrosion. The corrosion
layer thickness and elemental in depth trends of both these glasses match
closely.

SUMMARY

- Even after 182 days of leaching, the glass sample surfaces still show
approximately their original topography including surface scratches.
Thin (< = 3 im thick) Zn, Mg and Si rich precipitations are deposited
only.
- Leachate calculated boron depletion layer thickness values match well
with SIMS corrosion depth data. The glass corrosion therefore reflects
the whole corrosion history.
220

- The accumulated SIMS surface analysis experience shows strong similari-

ties between the analogously composed corroded borosilicate glasses
PNL-7668 and JSS-A glass, with the latter being significantly more corro-
sion resistent.
- No systematic difference in corrosion layer composition was recognized
between the corroded active JSS-A glass and its inactive model ABS-118.
- With increasing corrosion time, the SIMS elemental in depth profiles de-
monstrate a) a progressive loss of highly soluble elements like B, Na,
Li and Mo, b) a relative increase of slightly soluble elements like Al,
Fe, the lanthanides, the alkaline earths, U and Pu.
- U and Pu show closely matching elemental profiles.
- The absence of boron in the gel layer indicates a complete network break
down.
- The surface precipitation and gel layer are strongly porous and of low
density. They do not seem to hinder additional corrosion.
- Granite, if present, presumably controls the early leachate Si concen-
tration, hence reduces the corrosion rate for short time (< = 28 days)
corrosion experiments.

ACKNOWLEDGMENT

The radioactive JSS-A glass was provided by CEA/Marcoule, France. Samples

for the corrosion experiments were cut and leached at Studsvik Energiteknik
AB, Sweden. Funding for the described surface characterization work was pro-
vided mainly by the JSS participants.

REFERENCES

(1)H.P. Hermansson et al
Scient. Bases for Nucl. Waste Management, VII,
ed. G. McVay, Elsevier, 671, (1984)
(2) G. Bart et al
Nucl. Instr. and Methods 180, 109, (1981)
(3)D. Strachan
Nucl. and chem. waste management 4, 177, (1983)
(4) D. Savage, N.A. Chapman
Chemical geology,36, 59, (1982)
(5)R. Grauer
"Synthesis of Recent Investigations on Corrosion Behaviour
of Radioactive Waste Glasses"
NAGRA technical report series, to be published