UNDISPERSED GRANULATED SILICA FUME IN CONCRETE -

CHEMICAL SYSTEM AND DURABILITY PROBLEMS

BJORN LAGERBLAD * and PEETER UTKIN**

* Swedish Cement and Concrete Research Institute, 100 44 Stockholm Sweden.
"*Tallin Technical University, Building Materials Lab, Akadeemia tee 1, 200108 Tallin, Estonia.
ABSTRACT

Granulated condensed silica fume is not easily dispersed. In contact with the pore fluids
of the cement paste the granulates rapidly turn into alkali-silica gel nodules. With time this gel
absorbs Ca and at least the rim of the AS-nodules transforms into a C-S-H product. The gel by
itself does not cause expansion as it forms before the cement paste hardens. However, if exposed
to alkali salts the AS-nodules may become further enriched in alkalies, which in turn may trigger
an expansive reaction and cracking.

INTRODUCTION

Condensed silica fume (CSF), also known as microsilica, is widely used as an addition to
concrete. It is used to improve concrete properties, both in the fresh and hardened state. It works
both as a microfiller and a very active pozzolan.
On the market CSF is sold as a granulate and as a slurry. In several cases, when
analysing concrete we have observed undispersed silica granulates up to a size of a millimetre. In
concrete undispersed CSF will form a lump of amorphous silica and will thus be extremely
sensitive to alkali silica reaction (ASR). This report will mainly concentrate on chemical
interaction and durability problems. This has a bearing on the mechanism of the alkali-silica
reaction.

Condensed silica and disnersion

Silica fume is a by-product from the production of silicon or silicon alloys. When it
comes from the electric furnace it is a gaseous suboxide which in contact with air oxidizes and
condenses to very small particles of amorphous silica (SiO2).
Originally, silica fume is very light and thus difficult to handle. While the compact
3
density of CSF is around 2.2 g/cm 3 the bulk density of powder is only around 0.2 g/cm . This
makes it difficult to handle the material. Thus, the CSF is sold either in a water-based slurry or in
a granulated form as small pellets. The slurry is difficult and expensive to handle. Thus financial
and technological considerations often make the granulate form preferable.
The CSF can be granulated to different density and sizes. The granules also show a
tendency to become denser with time. The different granulated CSF available in Sweden that we
have tested have a bulk density from around 0.4 to 0.8 g/cm 3 and a maximum size of around 2
millimetre. Larger density and size makes the granulated CSF more difficult to disperse.
Granulated condensed silica fume (CSF) is not easily dispersed. The granules do not
disperse themselves. A series of tests with different mixing sequences show that a certain mixing
order is needed. Superplasticizers may help but are not essential. The data shows that mechanical
crushing is the most important factor. The fine fraction of the aggregate must be larger than the
size of the granule to achieve a good crushing. The tests indicated that the smallest aggregate
grain size should be twice that of the CSF granulates. The cement and water should always be
added late. The conditions for dispersion is discussed in Lagerblad and Utkin[1 ]

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Mat. Res. Soc. Symp. Proc. Vol. 370 @1995 Materials Research Society
DURABILITY INVESTIGATIONS

To find out if the undispersed CSF granules may cause durability problems, concrete
samples containing different amounts of CSF and different degrees of dispersion were tested by
accelerated alkali-silica reaction (ASR) and freeze/thaw (F/T) tests.
In the experiments a whole series of different concretes (Tab I) were prepared. Concrete
mixes 1 to 10 (series 1)were prepared in a 250 litre paddle mixer while samples 15 to 20 (series
2) were prepared in a smaller 50 litre paddle mixer. The mixer was kept running while the
ingredients were put into it during a short time period. Samples 15 to 20 were deliberately badly
mixed. Before testing all the concrete samples were water cured for at least 28 days.
All concretes contain 360 kg of binder (cement + CSF), 1000 kg coarse aggregate (8-16
mm) and 920 kg fine aggregate (0-8 mm). A high alkali (Na20 eqv = 1,1 wt. %) ASTM type I
cement was used in all mixes except nr 18 in which a low alkali (Na20 eqv < 0.6 wt. %) ASTM
type V (sulphate resistant) cement was used. The aggregates were granitoid of glaciofluvial
origin. They are not alkali-reactive. An air-entraining agent was used in all mixes. In mixes 9
and 10 a slurry (50 % water) was used. Mixes 5, 6, 15, 16, 19 and 20 contained a
lignosulphonate-based plastizicer (Rescon P). The bulk density of the granulated CSF was
around 0.7 g/cm 3 .

Table I.
Concrete mix design, kg/m 3 and measured properties

Abbreviations; B = bad air void system, A = acceptable air void system, VG = very good air
void system. NM = not measured. w/b = water/binder ratio. CSF disp = amount dispersed.

Mix CSF Water w/b Slump Air Frost CSF Mixing

No. wt. % in cm in % res. disp. in sec.

1 5 169 0.47 5.0 3.2 A 30 60

2 10 180 0.50 2.7 3.1 A 10 60
3 5 169 0.47 5.2 2.6 A 45 90
4 10 180 0.50 2.2 2.8 A 55 90
5 5 173 0.48 4.0 4.3 VG 90 320
6 10 180 0.50 2.4 5.1 VG 99 320
7 5 169 0.47 4.5 3.8 A 50 90
8 10 184 0.51 2.8 2.0 A 60 90
9 5 162 0.45 3.5 4.6 VG 100 90
10 10 162 0.45 3.0 5.0 VG 100 90
15 10 162 0.45 NM 1.8 B 22 45
16 10 162 0.45 NM 1.5 B 10 90
17 5 203 0.56 NM 1.9 B 18 90
18 5 203 0.56 NM 1.4 B 42 90
19 5 148 0.41 NM 1.8 B 69 45
20 5 159 0.44 NM 1.7 B 10 90

The first series (mix 1-10) was mainly done to investigate the effect of different mixing
order and mixing time on dispersion. The amount of undispersed CSF granules was obtained by
point-counting in thin-sections (25 x 40 mm). To get a reference for dispersion, samples were
made from gently mixed CSF (5 and 10 % by weight of cement) and Portland cement. Of this

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powder 10 mg was squeezed into a pellet and impregnated with water using slight
underpressure. The reference showed that 5 wt. % of CSF granulates in the cement paste give
slightly less than 4.5 % of the counts. Duplicate thin-sections, however, showed that the mixes
were inhomogeneous with areas rich and poor in undispersed granulated CSF. The amount
dispersed CSF is therefore only a rough estimate.
The amount of air and air void distribution was determined by point-counting and image
analysis in thin sections. The air content in Table I refer to air voids less than 1 mm in diameter.
In samples 15 to 20 the air void system was badly developed. The amount of air is small (Tab.I)
and there is a lack of very small pores. According to the air void system the concrete can not be
regarded as frost resistant. In mixes 1 to 10 the air void system is generally better developed with
smaller air voids. The spacing factor is less than 0.25 and the specific surface larger than
25 mm- 1 . Mixes 5, 6, 9 and 10 have a very good air void system with many very small air
voids.

Alkalisilica reaction

The ASR-method used was a modified Nordtest Method (NT BUILD 295). Instead of
the mortar prisms (40x40x160 mm) as prescribed in the method, concrete prisms (75x75x400
mm) were used. The prisms were cured in a humid environment for 24 hours, demoulded, and
then cured under water for 28 days at 20 oC. The length was measured and the prisms were put
in a warm (50 OC) saturated salt (NaCl) solution.
20-
E
E-15- -

C
0

C 4
LU 10-

5-
771

0 8-

-5
0 2b 60 8b 100 120 140
Time, days
Fig. 1. A SR-Expansion of concrete prisms with CSF.
Samples from mixes 1 to 10. Data of the concrete in Table I.

In the first test series (mixes 1-10) some (mixes 1, 2, 3, 4) but not all the samples with
badly dispersed granulated CSF rapidly developed a severe ASR-expansion (Fig. 1). In the
second test series (mixes 15-20) with badly mixed concrete only samples 17 and 18 expanded.
In the other samples no expansion could be found although they were kept in the salt bath for
more than 2 years. Samples 17 and 18 are those with the highest w/b ratio, which indicates that
permeability is an important factor, more important than the degree of dispersion. In batch 18 we
used a low-alkali cement which normally does not give rise to ASR. This indicates that the

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expansion is more a function of alkali ingress than the composition of the cement. Once started
the expansion was related to the amount of undispersed CSF granulates. Sample 2 with twice as
much CSF as sample 1 expanded the double. The CSF in samples 3 and 4 is better dispersed.
Freeze/thaw resistance

Concrete from different mixes was tested using Swedish standard test (SS 13 72 25, frost
testing with salt solution). In this test a standard cured cube is taken and cut in half. The sides are
sealed with silicon rubber and the surface is covered by a solution containing 3 % of salt (NaC1)
by weight. The test sample is put in a freeze/thaw cabinet were the temperature varies between
+20 and -18 oC with one cycle per day. The test stipulates 56 cycles and the result is measured in
amount of lost material per square meter. More than 1 kg/m 2 is not acceptable.
The test gave very peculiar results (Fig. 2). The concrete mixes that expanded in the ASR
test disintegrated very rapidly while others with undispersed granulated CSF behaved surprising
well. A normal concrete behaves like samples 6 and 10. However, some of these samples, like
nr 4 and 7, suddenly after 56 cycles started to scale very fast. Material analyses showed that the
rapid flaking was caused by ASR. The concrete contained expanded CSF nodules and cracks
filled with ASR-gel (Fig. 4). Thin section analysis in microscope of sample 5 and 8, that did not
scale at all, showed that the surface had microcracks filled with ASR-gel. Presumably this sealed
the surface and protected the concrete from salt water ingress and F/f1 scaling
In the second test series (Fig. 3, sample 15 to 20) all the samples scaled quickly in NaCl
solution. The samples with the highest w/b ratio and bad mixing, batches 17 and 18, scaled
fastest and developed extensive ASR. In this series we did not observe the phenomena of
excellent behaviour prior to a collapse as in the former series. This is probably the result of the
poor air void system which give bad frost resistance.
With the surfaces were covered with pure water instead of salt solution nothing happened.
When samples were covered by 3% CaC12-solution, however, concretes with badly dispersed
CSF developed ASR. The concrete with low-alkali cement (nr 18) did not develop ASR when
exposed to CaC12. Sample 18 in contrast to 17 (Fig. 3) behave normally when exposed to CaC12.
1 3 2 7A 7 4A 4 7B

1,5-

03
.1,0 -

//

0 14 28 42 56 70 84 98 11'2 126 14'0 154 168 182 196 210

Number of F/T cycles

Fig. 2. Results from freeze/thaw tests.

Mixing series nr 1, samples 1 to 10. The numbers give the intermediate value of scaling from
two halves of a concrete cube. When the sample is noted A and B they show the value of the
individual half.

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 E9 20 7j
1 I( V
I= I

(13
/ I
20/
/
2I / /
2
I / Ii l
I I/
I / ,/"
/1,1",7
S,
/ 16
S.~~~~I /..1'.."

o -,- - " , , ,- -~
0- 84 98 112 126 140 156
0 14 28 42 56 70
Number of FIT cycles

Fig. 3 Results from freeze/thaw tests.

Mixing sequence 2, sample 15-20. One half of the sample was subjected to a normal test as in
those samples in Fig.1. The second sample was first subjected to pure water for 42 cycles. The
pure water was then replaced by a solution with 3 % CaC12 by weight, and the F/T test continued
up to 156 cycles. The numbers on the top marks the amount of cycles the individual sample was
opposed to and the amount of material that scaled.

Fig. 4. Microscope photo in thin-section of silica granulates in expanded concrete.

Fluorescence light. Two of the granules have expanded while one small remained intact. A solid
shell (dark as it do not absorb fluorescens dye) can be observed around the bright expanded gel.

93
Destruction mechanism

After the different tests the material was analysed. Based on the crack pattern it could be
concluded that the cracking and rapid disintegration was caused by the formation and expansion
of ASR-gel. In thin-sections (Fig. 4) it is possible to observe cracks radiation out from
expanding undispersed granules. The crack pattern is, however, uneven. In some parts of the
concrete all the granules have expanded and formed cracks that are filled with gel while in other
parts the undispersed granules remain intact. In the samples with undispersed granules that did
not flake at all i the F/T-test, AS-gel could be found at the surface and filling microcracks in the
surface.
In concrete the granules develop a shell. In the expanded and cracked concretes one can
notice that this shell remains intact while the interior expands (Fig. 4). When analysed in the
scanning electron microscope (SEM) we can only observe a small ball of gel in a shell. This
must be due to the high vacuum in the SEM and that the expanding gel, in contrast to the shell, is
very rich in water.
The test data indicate that external salt is needed to trigger the expansive reaction. The F/T
results with a stagnant period followed by an accelerating indicate that the destruction mechanism
is kinetically controlled. We can find that the permeability and homogeneity, apart from the alkali
content of the cement, are controlling factors. The shell is probably also an important factor
firstly by protecting the interior secondly by mechanically hindering the interior from imbibing
water and expand. We will come back to this later after presenting the chemical system.

CHEMICAL SYSTEM

In a normal concrete the AS-gel is formed by the dissolution of silica from aggregates
which is a kinetically slow process, controlled by the grain size and order of crystallinity of the
quartz. The destruction by ASR is the result of expansion caused by absorption of external water
in the AS-gel. The situation in the test samples is different.
To understand the mechanism behind the expansion we must look closer into the
chemical systems and the physical properties of the concrete. The chemical composition of the
AS-nodules has been determined by energy dispersive X-ray spectrometry (EDS) in SEM.
These chemical analysis, however, do not give the amount of water, firstly because the technique
do not give it, secondly because the analysis are performed at high vacuum which result in
evaporation of water and drying shrinkage of the gel. Thus, in table II and III, the water content is
disregard and the compositions are normalized to 100 % based on the weight of oxide.
Repeated analysis showed that with time and in contact with the atmosphere the gel
became enriched in calcium and carbonated. Thus the analyses were done on fresh broken
surfaces. When possible the analysis were made with a defocused beam as otherwise especially
the alkalies evaporated from the loose structure by the energy from the beam. The EDS analysis,
are calibrated against cement clinker grains and minerals. In all the alkali-silica nodules, former
granulates of CSF, we can detect Ca, Na, K and Si. In the nodules subjected to salt we can detect
some Cl.
Micro-analysis in scanning electron microscope (SEM) shows that the undispersed CSF
granulates are transformed into an AS-gel very rapidly. Table II presents the composition of the
undispersed granules at different times after mixing. Already within 24 hours the gel has
absorbed significant amounts of Ca and some alkalies. Within 96 hours it is an AS-gel (in the
normal case an AS-gel always contain a substantial amount of Ca). This implies that the AS-gel
is formed before the concrete is properly hardened. Thus the AS-nodules will not imbibe more
water and cause expansion unless the chemical composition of the gel is changed. This is
probably the reason why no freeze/thaw scaling can be observed with the samples in pure water.
An alkali ingress is needed. Expansion is a matter of timing.

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 Table II
Typical compositions of undispersed CSF in mortars at different times after mixing.
High alkali cement (1.1 Na20 equivalent). Granulated CSF = 5 % of cement weight. The
mortars are badly mixed with almost all granulates remaining undispersed. Data normalized to
100 %. As water is missing the data only show the relative amounts of the different oxides.

Hours 24 24 96 96 264 264

Pos. core shell core shell core shell

SiO2 92 87 70 61 70 68
CaO 7 11 11 15 7 29
K20 <1 1 17 13 20 3
<1 <1 2 2 3 <1
Na20

Table HI
Typical compositions of undispersed CSF granulates in well cured concretes.
The first sample is with a high alkali cement (HAC, 1.1 % Na20-eqv.). The second analysis is
from a concrete with a low alkali cement (LAC, 0.5 Na20-eqv). The third concrete (analysis 5
and 6) is from a concrete which has been stored for two years in hot salt bath (ASR-test). The
last analysis are from a concrete that expanded in the salt bath. Analysis nr 7 is from an AS-
nodule and analysis nr 8 is from AS-gel in crack. Data normalized to 100 %. As water is
missing the data only show the relative amounts of the different oxides.

Analys 1 2 3 4 5 6 7 8
Curing water water water water salt salt salt salt
Cement HAC HAC LAC LAC HAC HAC HAC HAC
%CSF 5 5 5 5 5 5 10 10
Pos. core shell core shell core shell core crack

Si02 72 50 82 48 67 51 75 59
CaO 3 48 13 52 15 45 16 33
K20 21 2 5 <1 2 1 <1 <1
4 <1 1 <1 15 2 13 7
Na2O

Chemical analysis were done on most of the test samples. Representative analysis are
presented in Table Ill. They all reveal a complicated zonation pattern with a core rich in alkalies
and a rim rich in calcium. A similar zonation was recognised and is described by Shyan et al [2].
The outermost rim contain very little, often no, alkalies but a gel with a Ca/Si ratio of 1/1. The
product with equal amounts of CaO and SiO2 is repeated with such a regularity that it must be a
distinct product. We can find the same composition in old ASR-gel from damaged structures
(Lagerblad & Trligrdh [3]). It is linked to a depletion of portlandite close to the gel. In the high

95
vacuum of the SEM this shell, in contrast to the normal AS-gel, does not shrink. The
composition of this gel is reminiscent of and probably is a CSH (I)-gel, the typical product of the
pozzolanic reaction. The volume stability, distinct appearance and total lack of alkalies suggest a
semicrystalline structure.
From this shell toward the core the relative content of silica increases. At the same time
the content of alkalies increases while that of Ca decreases. Sometimes it is possible to observe
distinct layers showing jumps in composition like with the outer shell. We have, however, not
been able to pin-point specific compositional gaps where the the jump occur. The zoning is a
general feature. The exact composition of the gel, however, depends on several factors. We have
not been able to identify exact correlations but several compositional trends. They are indicated
in Fig. 5.
A

/ so

Shell in re /ndo

inold
concrete

\ \/

alold
10 40 concrent

oceen CS Sutaersore

Incrreasinn
60res 0 7ncn- 80 0 -S C

ALlies
as N 0 - equivalent

Fig. 5. Schematic triangular diagram

showing the chemistry and the changes of chemistry of the undispersed CSF in concrete.
The data is based on a concrete with a high alkali cement and 5 % undispersed CSF by weight.

DISCUSSION
To understand the composition of the AS nodules we have to look into the chemistry of
the young concrete. When cement clinker grains are mixed with water a cement-gel is formed
and calcium hydroxide is released to the liquid phase. Within the first hours the pH is increased
to more than 13. Successively the alkali ions are released and the portlandite start to crystallize. In
the first instance the Si-O-Si bridges are broken under the action of the hydroxide ions in the pore
fluid and form silanol groups (Wang & Gillot[ 4 ]). This probably happens quickly in the granules
as they are porous and contains millions of individual small amorphous balls. Follow this, the
calcium and alkalies exchange for the protons of the silanol group and form an alkali-silica gel.
The calcium is, as the data (Tab. I) show, presumably the first to bind as they are more

96
available in the pore solution. Later when the contents of alkalies increase they will be the
dominant ions. Much later when the system is stabilized, the alkalies will be replaced by calcium
as the Ca-gel is energetically preferable (Wang & Gillot[5 ]). This will explain why the AS-
nodules are zoned with Ca-rich rims. With well dispersed silica fume like in the normal case the
gel immediately turns into Ca-gel the pozzolanic product. A comparison can be made with alkali
reactive rocks. Corse sand and stones give rise to ASR and expansion while finely ground they
are pozzolanes.
When the concrete is subjected to salt solutions, as in the ASR-test and the F/T-test, this
increases the content of sodium in the AS-nodules (Table II). From the beginning the AS-
nodules are rich in potassium as this is the main alkali ion in the cement we used. The expansion
is probably induced by the increased alkali content that allows the gel to imbibe more water.
However, not all the concretes with undispersed CSF granulates expanded. Even more than one
and a half years of hot salt bath did not result in expansion of most of the concrete mixes
although the AS-nodules were enriched in Na. One problem is that it is almost impossible to find
out the composition of the gel actually extruded from the AS-nodules as it in contact with the
cement-paste has changed composition. However, one would expect that an AS-gel with a
composition like that in the samples stored in the salt bath would absorb water and expand.
Presumably an intact C-S-H shell is fairly impermeable to water and resists cracking. In
thin-section it is possible to observe strings of expanded AS-nodules which indicates that once
cracking has occurred the salt solutions can penetrate and trigger more nodules to expand and
continue the crack front. This indicates that the AS-nodules have to be mechanically ruptured to
allow the interior to expand. Once the cracking start it will trigger more granulates to expand
which will result in the fast detoriation. At a first impression this theory described above is
contradicted by the fact that the reaction also occurs with CaC12 solution during the F/T test.
However, as shown by Wang & Gillot[ 5 ] excess Ca releases alkalies which allow the remaining
gel to be enriched in alkalies.

Acknowledgement
The research has been financed by the Swedish Foundation for Concrete Research, the
Swedish Counsil for building Reserch (BFR) and the Swedish National Board for technical and
Industrial Development (NUTEK).

REFERENCES

1. B. Lagerblad & P. Utkin " Silica granulates in concrete-dispersion and durability

aspects. CBI-report 3:93, 44 p, (1993).

2. A. Shayan, G.W. Quick & C.J. Lancucki,"Morphological, mineralogical and

chemical features of steam-cured concretes containing densified silica fume and varios
alkali levels", Advances in Cement Research, 5, No 20, 151-162, (1993)

3. B. Lagerblad & J. Trighrdh, " Slowly reacting aggregates in Sweden,"Mechanism

and conditions for reactivity in concrete", Proceedings, 9th International conference on
alkali-aggregate reactions, London, 570-578, (1992).

4. H. Wang & J.E. Gillot, "Mechanism of alkali-silica reaction and the significans of
calcium hydroxide", Cement and Concrete Research, vol 21, 647-654, (1991)

5. H. Wang & J.E. Gillot, "Effect of Ca(OH)2 on the alkali-silica reaction, Magazine
of Concrete Research, 43, 156, 215-218 (1991)

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