Microstructural Changes Due to

Elevated Temperature in Cement

Based Grouts
Daniell e Palardy,* Mari a Onofrei,t and Gerard Ballivy*
"Univetsite de Sherbrooke, Dep artement de Genie Civil, She rbroo ke, Quebec, Canada; and
t AfCL, Whiteshell Laboratories Pinawa, Pinawa, Manit oba, Canada

The durability of type K and H cement based grouts under

conditions potentially found to be in high level nuclear waste
repositories was studied. Tests have been carried out to determine
the effects of temperature on the hydraulic conductivity and the
leaching resistance of the grouts. Mea surements of merCilry intrusion porosimetry and scanning electron microscopy with energy
dispersive X-ray analysis have been used to investigate the changes
in the pore structures of both grouts as f unction of leaching and
permeating time. Type K and type H cement based grouts, made
with low water to cemeniitious materials ratio, silica f ume, and
superplasiicizer, were exposed to high temperature and pressure.
Preliminaru results indicate that both hydraulic properties and
leaching behavior of the grouts investigated are affected by the
increase in temperature. However, data show that leaching rate and
hydraulic conductivity of the grouts decrease with time. The results
showed clearly that chemical reactions, presumably accelerated by
tile elevated temperatures (100C), led to the [orma tion of a
precipitate ill the microcracks and on the surface of the leached
specimens. This precipitate is likely the cause of the observed
decrease in the hydraulic conductivity and leaching ra te.
ADVAN CED CEMENT BASED MATE RIALS 1998, 8, 132-138.
1998 Elsevier Science Ltd.
KEY WORDS: Cement bas ed gro u t, High temperature, Microstructure modifications, Perm eability, Static leaching, Typ e
K cem ent, Type H cement

u rrent repository design s for the disposal of

radioactive w as te env isage exten sive use of
cement ba sed materials (i.e., grouts, con crete )
[1-4] . The se materials ma y be used for the waste form
matrix, as construction materials for wa lls and floor, as
a grout to fill in gaps between wa ste pa cka ges, and to
seal bor eh oles, shafts, tunnels, and natural fractures or
frac tures gene rated during va ult excavation. The ce-

Andress correspondence (0: D r. Gerard Balli vy, Civil Engin eerin g Departm ent,
Un iversit6 de Sherb rooke. Rocks M echanics L rboratory, Sherbroo ke, Qu ebec J I K
2 Rl , Ca na da.
Received December 5, 199 7; Accepted M arch 20, 199 8.

1998 by Elsevier Science Ltd.

655 Av enue of the Americas, New York , NY 10010

ment based materials will fulfil different functions in

each of these applications. They are used in these
app lications due to inherent strength, durability, and
versatility.
Cement based grouts ha ve been identified as potential grou ting materials. The requi red performance of
ceme n t based grouts includes not onl y an ability for the
material to penetrate and seal ve ry fine fracture, but
also a potential for lon g-term mechanical and chemical
sta bility in disp osal va u lt envi ronment. Under man y
cond itions, the deteriorati on of cement ba sed materi als
is not attribu ted to an y sing le cause, but arises fro m the
combined action of a number of potentially destructive
age n ts. There ar e man y possible env ironme ntal factors
and processes by which the design properties of the
ceme nt based grouts may cha nge over long period s of
time. These include reac tion with the en vironment
through the aqueous phases, int ernal microstructural
changes, temperature, action of microorganism, and
radiation (i.e., radiolysis). It is comm only held that the
hydraulic performance of ceme nt based grouts w ould
chan ge as water passed th rou gh the pores in the material s. The cement will di ssolve in a saturated environment, and porosity and hydraulic conductivit y would
inc rease w ith tim e. The rates of change would be
influenced by spontaneou s cha nges in microstructure
of the material. It is obvious that the hydraulic d yn amics in the vicinity of the gro u t are an important factor in
estima ting the lon g-term durability of cemen t ba sed
gro u ts.
It is generally kno wn that th e durability of harden ed
cem ent exposed to aggressive aq ueous env iro nme nts is
related to permeability and, thereby, to the pore structure of the hardened ceme nt. Durability is an important
par ameter; it is defined as the capacity of a cementitiou s
mater ial to resist under given environmen tal con di tions
[5]. Th is article presents the results of laboratory studies
carr ied out to determine the effects of temperature, typ e
of cement, and harden ed gro u t porosity on th e hydrauISSN 1065-7355/98/$19 .00
PII S1065-7355 i9i:l)0001 6-9

Cement Based Grouts 133

Advn Cem Bas Mat

1998;8: 132-138

TABLE 1. Composition of grouts studied

Axial load

Mix

Type of
Cement

Ratio
W/C

Silica
Fume (%)

Super
plasticizer (%)

1
2

K
H

0.5
0.3

10
15

1
1

Pressure

(E x ter
,-,"n~_......

uppe r plate

lie conductivity and leaching behavior of cement based

grouts.

Experimental Procedures
Permeability Tests
The hydraulic conductivity tests were carried out in a
specially con structed permeameter (Figures 1 and 2)
[9,lD]. It is a radial flowing permeameter and allows the
study of samples under high temperature and pressure.
This permeameter permits the creation of medium
depth conditions. Cylindrical samples with a central
cylindrical opening parallel to the longitudinal axis

Sam?l e
- r od

~-fU---

t-JI-

Materials
Type K cement is the most common expansive cement
used today [6,7]. In this cement, the aluminate source
for the ettringite formation is calcium sulfoaluminate
(C4A3S ). An expansive cement normally is used in a
situation where shrinkage of the cement based material
cannot be tolerated [8]. In the case of cement based
grout, the required exp ansion is higher than the shrinkage to create a contact force between the grout and its
environment. This balance between expansion and
shrinkage reduces cracking.
Type H cement is an oil-well cement; specifications
were established by the American Petroleum Institute.
It is a slow-setting cement that is used to seal deep wells
under high temperature and pressure. Type H cement
can be used as a basic well cement from the surface to
depths of 2500 m . Its typical fineness is about 160
m 2 /kg. This cement is a high sulfate resistance cem ent,
as determined by C3A content (max imum 3%).
Two different grout mixes, one with type K cement
and the other with type H cement, were studied . The
mixes are shown in Table 1. Silica fume and a naphthalene based superplasticizer were added to each cement
to improve grout properties such as low permeability
and long-term leaching resistance. All the grout components (cement, distilled water, silica fume, and superplasticizer) were mi xed for 300 s at a speed of 40
rpm with a laboratory mi xer. After the mixing, the
grout specimens were cast in molds and placed in a
humid chamber for 24 hours. The samples were demolded and cured under a saturated Ca (OHh water at
20C for 28 days.

~thermocouple

r-

,.......:;~I~~t-NI~-- glue

I 50

msr

pl at e
Pres s u r e
(Intern)

"'-

FIGURE 1. Radial-typ e perrneametric cell [9,10].

wer e tested. The dimensions of the samples are 50 mm

in diameter and 110 mm in length with an axial hole
diameter of 13 mm. Before testing, the samples were
saturated, for at least 2 days, with deionized, deaerated
water. Tests were done by the convergent method,
which forces the flow from the outside to the inside. In
other w ords, the sample is subjected to a radial compressive stress field. The samples were tested at three
different temperatures (200, 500, and lDOC) in a sequential manner with a 10-MPa pressure differential. The
temperature wa s incr eased as soon as the hydraulic
conductivit y reached a constant value. In general, the
test at each temperature wa s carried out for approximately 30 days.

Static Leaching Tests

The full description of the experimental design and
method ha s been given elsewhere [11]. The test is used
sec urity vane

2
JJj

ret urn

ce r rs

V\l nc

securit Y ~
~
valve ~
Debit q

pn ewnatic
v ane

snocx
ab s orber

__
-

Atmospheric pressure
pressure of service

Water tan k

Pump

FIGURE 2. Environmental permeametcr [9,10].

134

D. Palardy, et al.

Advn Cern Bas Mat

1998;8:132-138

Analytical Method

TABLE 2. Nominal composition and pH of Whiteshell N-1

synthetic groundwater
Ion

Concentration
(mg/L)

Ca
Na
Mg
Sr
K

1890
1830
55
22
13

Characterization of the microstructure and the chemical

properties were done before and after the permeability
tests and the static leaching tests to find any changes in
the cement grouts attributable to different test conditions. Any changes in porosity, chemical composition of
the samples, or liquids deriving from the leaching tests
were determined. Optical, chemical, and microstructural methods were used to measure these changes
occurring as a result of the durability tests.

Concentration
Ion

(mg/L)

Si

4
5790
1000
40
7

cr

S042HC0 3
pH

Microstructure Characterization

to investigate the behavior of cement based grouts

under various conditions of temperature, water chemistries, and lengths of time in contact with the leachant.
The leaching tests were carried out at 25, 500 a n d 100C
in Teflon containers of 90-mL volume. The grout specimens were placed on Teflon grids at the bottom of each
container to ensure full contact between the sample and
the solution. Leachant was added to yield a sample
surface area to solution volume ratio of 0.1 cm- 1 .
Prismatic-shaped samples were cut to obtain a surface
area of approximately 6 ern", The amount of water used
in each container was about 60 mL. The leachants used
in this study included deionized distilled water and
Whiteshell N-l synthetic groundwater; they were not
renewed during the test. Table 2 shows the composition
and pH of the synthetic groundwater used. Leach times
of 7, 14, 28, and 35 days were used. The grout samples
were removed from the container at their predetermined leaching times.

Surface analysis of the test specimens at the termination

of the hydraulic conductivity and leaching tests were
performed by scanning electron microscopy (SEM).
Before the analysis began, the grout specimens were
impregnated with epoxy based resin and polished with
increasingly finer diamond powders (15, 3, and 1 urn).
The microscope used was a JEOL JMS 840A connected
to a microprobe LINK 10,000.
Techniques such as mercury intrusion porosimetry
have also been used to investigate the changes in pore
structure of both grouts. Before measurements, the
grout samples were dry by placing them in acetone for
4 hours and then in an oven at 60C for 12 hours.

Chemical Characterization
Crystalline phases were determined by X-ray diffraction (XRD). Samples were crushed under a controlled

1E-10

'ii

25 C

1E-11

100

50 C

r:

1E-12

.s; 1E-13
~
:::I

. Type H
.-TypeK

~ 1E-14

o
u

-,

.2 1E-15

_. -.. .

:::I

! 1E-16

-.. -

::I: 1E-17

Detection
limit

------------- ---o

500

1000

~.

1500

2000

2500

Time (hour)
FIGURE 3. Effect of percolating time and temperature on the hydraulic conductivity of the grouts studied.

Ce me nt Based Grouts

Advn Ce rn Bas Mat

135

1998;8:132-13 8

TABLE 3. Vilriation of wilter viscosity with temperature {12]

Temperature

Viscosity

(0C)

(v . 106 m 2/s)

20
60
100

0.995
0.480
0.290

(~ v =

(~v

-50%)

= - 70%)

nitrogen atmosphere to prevent carbonation and analyzed by a Rigaku DMAXB apparatus. Solution analyses were performed at th e termination of each static
leaching test. Calcium was analyzed by inductively
co uple plasma spectroscopy.

Results and Discussion

Permeability Tests
H ydraulic conductivity wa s assessed w ith grout specimen s under compression. Figure 3 p resents the effects
of p ercolating time and temperature on hydraulic conductivity of both grouts under in vestigation. A me an
hydraulic conductivity was calculat ed for each temperatu re.
The results show that, under the test conditions, both
grouts had a permeability lower than the detection
limits 10- 17 m / s) at 25C and even at 50C for the
type H cement based g ro u t (Figure 3). Type K cement
based gro u t has shown a moderat e flow at SOC and a

more important h ydraulic conductivity at lOOe. As a

comparison, the conductivity m easured for this grout at
100C (10- 12 m /s) corresponds to the conductivity at
25C of sound granite. The important fact to notice is
th e considerably low hydraulic conductivity of type H
cemen t based grout.
As exp ected , permeability increases along w ith the
temperature increases. The observ ed increase in hydraulic conductivi ty m ay be attributed to changes in
microstructure and th e decrea se in the vi scosity of
permeated water. The viscosit y of water is lower (Tabl e
3) and it moves easily through the grout samples.
A high permeability w as me asured at the initiation of
the tests. Temperature can bring thermal expansion that
crea tes fractures and crack s. Examination of the specimen s after the tests revealed th e presence of cra cks
p arall el to their longitudinal axis . The presence of these
cracks may explain the high permeability at the initiation of the tests. However, thi s inc rease in hydraulic
cond uctiv ity is observed for a shor t period of time, after
which the h ydraulic con d uctivi ty decreases with time.
Thi s w as attributed to the self-sealing properties of the
g routs. Microscopic examination of the grouts at the
termination of the test s showe d th at chemical rea ction ,
accelerated by the ele vat ed temperature, led to the
formation of a precipitate in the cracks in the gro u t
speci mens . Thi s precip itate is the likel y cause of the
temperature-induced d ecrease in the hydraulic conduc-

11 655

FIGURE 4. SEM/energy d ispersive X-ray analyses of the deposit in a crack from the type K cement based

grout.

136

Advn Cem Bas Mat

1998;8:132-1 38

D. Palardy, et al.

tivity of the grout. The mechani sm of self-sealing of

cracks in the cement ba sed materials is n ot well understoo d even though the phenomenon is we ll-establishe d .
Several au tho rs ha ve indicated that the mo st likely
mechani sms responsibl e for the crack sea ling ar e dep osition of calcium carbo nate and/ or formation of ne w
hydration products [13-15]. Under th e experimental
conditions used in th is study, the results sugges t that
the most likely process responsible for the crack sea ling
is continued hydration reaction. The SEM / energy dispersive X-ray an alyses of the fillin g material indicated
that it consisted main ly of Ca and Si (Figur e 4). The
morphology and th e che mical comp osition of the filling
material suggest CSH. Figure 5 show s a general view of
a fracture obser ved in the typ e K cement based grout
and filled up w ith rea ction product.
It is a kn own fact that the por e structure of cem ent
pa ste con tro ls to a lar ge extent the perm eab ility of the
material. There fore, any facto rs affecting either the total
p or osity or the pore size distribution of hardened grou t
sh ould affect the hydraulic properties of the mat erial.
Med ium siz e cap illary pore s (0.01 to 0.05 IJ-m) and large
p ores (0.05 to 10 urn ) control permeab ility [16]. As
shown in Figures 6 and 7, each gro u t ha s a low
percentage of lar ge capillary pores due to the use of
silica fum e ad mix ture . This may explain the very low
results obtained for p ermeability. Howev er, the typ e K
cem ent based gro ut contains a higher percentage of
med ium capillary pores, w hich may expl ain the higher
hyd rauli c cond uctivity in comparison wi th th e othe r
one . Classification use d in these figures comes from
[17].
An increase in tot al porosity is observed in both
grouts rel at ive to th e in itial va lu es obtained for the
control specimens: 6% for th e type K cemen t based
g ro u t and 4% for th e typ e H (Fig ures 6 and 7).
H owever, d espite th e fract ures ob ser ved, classes 1

l 30 ,..-- - - - - - - - - - - - - --,
5

:sD

25
20

:a

10

~ 15 + - - - - - - ~

(;

Q.

+-

5 +-- - - - - 0 +-- ---,-- ---,Class 1

Class 2

Class 3

Class 4

Total

FIGURE 6. Pore size dis tribution of type K grou t before and

after the permeability tests (see no menclatur e).

and 2 have not increased excessively : a slight increase

was ob served in typ e K cemen t p aste. Thi s ma y be
att ribu ted to th e formati on of precipitate. Class 3
shows n o change, w he reas for th e fourth one, an
increase of 5% is measured (Fig ure 6). The increa se in
class 4 m ay indicat e the in crease in th e CSH ge l as the
result of con tin ue hydrat ion. Finally, th e type H
cement based grout shows a low in crea se fo r cla sses
3 and 4 (Fig u re 7).
SEM in back scattered electro n induced mod e examinat ion s revealed the presen ce of unhydrated phases in
the harden ed grouts: approximately 10% of the matrix
for the typ e K cem ent based grout and 25% for the type
H grout. Some particles ha ve an hydrated layer on their
margin, w hereas othe rs show only a remnant of the ir
init ial struc tur e. The hyd ration of these unhydrated
ph ases w he n in contact wi th the p ermeating wa ter may
exp lain the delay before the water flowe d th rough the
gro ut. In the control sam ples, the initial unhydrated
phases represented approxi mately 20%, in the type K
cemen t based grout and 40')10 in th e type H gro ut.
The increase in classes 2 and 3 in type K grou t may be
attr ibuted to ett ringite [Ca6AI2(SO.jh (OH )12 25H 20 ]
deco m position above 60C. The se obse rva tions have
been confirmed by XRD ana lysis performed on the
spec imen after the pe rmeability tests. The results sh ow
the presen ce of katoite [Ca 3 Al2(SiO.j)(OH)8]' Th is min-

30 ..-- - - - - - - - - - - - - --,

25
20

:a

10

:s

~ 15
~

+-- -- - - - -- -- -- - +-

iii

+-- -- - --

+-----,-- ---,-

Class 1

FIGURE 5. Deposit in a cra ck from the typ e K cement based

grout (2,200X).

Class 2

Class 3

Class 4

Total

FIGURE 7. Pore size d istributi on of typ e H grout before an d

after the permeability tests.

Ce me nt Based Grout s

Advn Ce rn Bas Mat

1998;8 :132 -1 38

70

"-

~>o

60

0;-

50 I

__ 25 C

.2 30

40

--.- 50 C
___ 100 C

"04
..>0/

s
~
os

'0
~

Tempe rature

30

c 35

.,os

25
20
'6 15
~ 10
0
5
0
Co 0

.,

..

10

...J

r--

Control KD
K
2535

16

24

32

D Class 1
Class 2
Class 3
o Class 4
Total

e 20

.c

137

..I

KD
10035

KW
2535

--

KW
100-35

40
FIGURE 10. Porosity distribution in the type K cement based
grout after 35 days of leaching (see nomenclature),

Time (day)

FIGURE 8. Effect of leaching time and temperature on the

leach rate of calcium for the type K grout reacted with

deionized water.
era l and calci um sulfa tes, CaS04x H20, ap pear after the
decomposi tion of ettringite.

Static Leaching Tests

As for th e permeability test s, the increase in tem perature to lOODC brings more important changes in th e
gro u t in compa rison to 25C or SOc. In fact, at lOOe,
th e resu lts show higher calcium leaching ra tes, leac hing
depth, and p orosity. Fig ures 8 and 9 show th e calcium
leaching ra te for th e type K an d type H gro u ts submer ged in deionized water: leaching increases at high er
tem peratures. H ow ever , after a certain pe riod of time,
the system tends to approach a steady sta te attributed
to calcium concentration approachi ng solubility lim its
and/ or due to formation of a surface protective layer ,
SEM examination confirmed the form ation of a precipitate layer on the surface of th e leached specimens. This
layer "vas id entified, by XRD, as bein g in major p art
composed of calcium carbonate. Th e sam ples leached in

70

Vl

synt he tic groundwater also show traces of Mg(OHh on

the extern al surface. A solu tion with MgS0 4 or MgCl 2
leaches the calcium hyd roxide and brings th e formation
of bruci te deposits [18].
TIle calcium leachin g originates mos tly from the portlandite Ca(OHh, of which the decrease can be seen
semi-quantitatively by XRD. The d issolution of this mineral increases the porosity of the gro uts and may affect
their lon g-term durability . Figures 10 and 11 show the
pore size distribution in the type K and type H cement
based gro uts. The porosity doe s not change significantly
at 2SoC in compa rison with the control sample, bu t at
lOOC, a significant differe nce is observe d .
The decomposition of ettri ngi te at high temperature
also may contribute to th e increase in porosit y. Th is is
more importan t in the type K grout, beca use it contains
agglome rations of ettringite crysta ls. This m ay exp lain
the in crease of class 2 at lOOC for this grout.
Furthermore, few er differences are observed in the
porosity classes between 2Soand SOC; it is at lOO DC that
the cha nges are reall y importan t. At the tw o first
temperatures, the h ydra tion is mor e imp ortant, w hich
is rep resented by an increase for class 4. Howe ver , at
lOOe, it is class 3 (and 2) th at increases: leaching is
more important th an hyd rat ion .

E 60

OJ,

.:..:

Temp era ture

'b 50
~

___ 25 C

40

c
:J

.
'fi

os

20

os

10

.:1

~ 40

--.- 50 C
___ 100C

u'" 30
'-

~*

0
0

16

24

c 35
30
.& 25
~ 20
'6 15
~ 10

.g

:
32

ell

40

Time (da y)

FIGURE 9. Effect of leaching time and temperature on the

leach rate of calcium for the type H grout reacted with
deionized water.

s0

Q.

5
0

-i

Control HD
H
25-35

....

D Class 1
Class 2
Class 3
DClass 4
. Total

l-

H-W
H-D
100-35 2535

H-W
10035

FIGURE 11. Porosity distribution in the type H cement based

grout after 35 days of leaching.

Advn Cern Bas Mat

1998;8 :132-1 38

138 D. Palard y, et al.

Finally, SEM observations show that the leaching

depths increase with temperature, especially at 100C,
and duration of test. This results in higher porosity.

2.
3.

Conclusions
The study shows that both, hydraulic conductivity and
leaching properties of the grouts investigated, were
affected by the increase in temperature. However , the
results show that both leaching and hydraulic cond uctivit y of the grouts tend to decrease with time. The
observed changes were attributed to the formation of
new hydration products resulting from the increase in
the degree of hydration and associated reactions.
The work discussed here revealed that the porosity of
the grout does change with leaching time, but in the
limits that depend on grout composition, temperature
and initial porosity. The results confirm that the grouts
investigated have the potential to self-seal.

Nomenclature
Class 1 (%)
Class 2 (%)
Class 3 (%)
Class 4 (%)
K and H
D and W
25 and 100

35

300-0.9 urn
0.9-0.06 j.Lm
0.06-0.009 urn
0.009-0.003 urn
Cement type
Water type
Temperature (0C)
Test duration (d ays)

Acknowledgments

4.
5.

6.
7.

8.
9.
10.

11.

12.

13.

14.
15.

The authors w ish to thank Atom ic Energy of Canada Limited for

providing finan cial support du ring this proje ct.

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