SURFACE COATING OF

SILICEOUS PARTS OF
AGGREGATE GRAINS
BY ALUMINA
CONTAINING SCM`S IN
ALKALINE SOLUTIONS 15TH INTERNATIONAL
CONFERENCE ON ALKALI
AGGREGATE REACTION IN
CONCRETE
July 04-07, 2016 ,
Sao Paulo, Brazil

Prof. Dr. Dr. Klaus-Jürgen Hünger

Dipl.-Ing. Mario Kositz
Summary and conclusions there = Starting point here

1. Aggregates which provide by themselves relatively high concentrations of aluminium

compared with the corresponding SiO2 concentration to alkaline solutions are less
expansive in concrete prism test than Al poor aggregates (self inhibition process).
2. A useful value of SCMs is the calculated molar Si/Al ratio based on dissolution
experiments which characterize the formation of alumino silicates in the alkaline
solution. MK with a ratio Si/Al < 1 has an aluminium excess and consequently a higher
potential for preventing ASR than FA.
3. Calcium ions which are always present in pore solutions lower the capacity of the SCMs
because competitive reactions proceed, also consuming dissolved aluminium.
4. Obviously by using special alumino silicate containing SCMs (e.g. MK) enough „free“ Al
left for reducing ASR potential.
5. The optimal combination of aggregate and SCM depends on the dissolution behaviour of
both the SCM and the aggregate.
The question is how do such Al containing SCMs with an amount of enough
“free” Al work?
To give answers the interactions between SCMs and the surfaces of aggregate
grains were investigated by using chemical and different structural methods.
huenger@tu-cottbus.de 2
INTRODUCTION

Content

• Starting point

• Materials and Methods

• Results of dissolution experiments

• Results of structural analyses of the surfaces

• Conclusions

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 Materials and Methods

For our experiments always the same rock material was used:

- a quartzitic rock, which was special prepared for our investigations

- it consists mainly of quartz (approx. 98 wt.%), the rest is muscovite

Embedded in a resin for IR and XRD Thick section for dissolution and XPS (2 mm thick)

For the coating experiments two SCMs were used: Metakaolin and „Al-hydroxide“
Phase Metakaolin Al(OH)3

Amorphous 68.1 81.7

Boehmite 1.6 17.2
Kaolinite 25.1 -
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Quartz 5.1 -
Materials and Methods – ICP-OES

Dissolution experiments in highly alkaline solutions

- Thick section samples with a thickness

of approx. 2 mm and a diameter
according to the original grain size of
the aggregate grains were prepared.
- Each sample was stored separately in
a bottle with 0.1M KOH at 80°C for 14
days
- The added amount of SCMs was 0.25
g related to 200 g KOH solution
- The added amount was varyied in
relation to the surface of the stored
samples.

ICP-OES-method

SiO2 and Al2O3 concentrations in the alkaline

solution were measured at certain days by
using ICP-OES method.
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Materials and Methods - structural investigation methods

- ATR-FTIR spectroscopy (attenuated total reflection IR spectroscopy) is a special method

to investigate layered surface areas of solid materials.
The penetration depth of
the IR-beam is approx. 1 µm.

- XRD-GID (gracing incidence diffraction) is a special mineralogical method to characterize the

surface composition. The incidence X-ray beam is fixed at small angles (0.5°, 0.25° and even
0.1°) while the reflection beam is detected at a range of 4 – 60° 2Theta.
The penetration depth of the X-
ray-beam is approx. 100-120 nm.

- XPS (X-ray photoelectron spectroscopy) is a special method to determine the chemical

composition of solid state materials especially of their surfaces. It based on the fact that X-rays
with different energies are produced by electromagnetic excitation.
 Result: - overview spectra of elements in a surface area of approx. 1 mm2.
- depth profiles of different elements, 1 min sputtering time is equal to 1 nm
ablation depth.
The penetration depth of the XPS
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is approx. 1-10 nm. 6
 Results - dissolution of starting materials

Solubility of Q1 Solubility of pure Al(OH)3

100 100 400 800
90 90 350
80 80

Al2O3 [mg/l]

Al2O3 [mg/l]
300 600
SiO2 [mg/l]

SiO2 [mg/l]
70 70
250
60 60
50 50 200 400
40 40 150
30 30 100 200
20 20
50
10 10
0 0 0 0
0 2 4 6 8 10 12 14 16 0 2 4 6 8 10 12 14 16
storage time [d]
storage time [d]

Solubility of metakaolin (MK)

400 800
- Q1 provides SiO2 only into the alkaline
350
solution

Al2O3 [mg/l]
SiO2 [mg/l] 300 600
SiO2
250
- Al-hydroxide: Al2O3 only (how expected) 200
Al2O3
400

150
- MK: both SiO2 and Al2O3, but a little bit 100 200
changed to the experimental results under 50
conditions 40°C and 1 m KOH solution 0 0
0 2 4 6 8 10 12 14 16
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 Results - dissolution after SCM addition into the solution

Dissolution curves of Q1 with presence of SCMs in the alkaline solution

What happens in comparison to the starting material?

Q1 with Metakaolin Q1 with Al(OH)3
400 800 400 800

350 350

Al2O3 [mg/l]

Al2O3 [mg/l]
300 600 300 600
SiO2 [mg/l]

SiO2 [mg/l]
SiO2
250 250
Al2O3
200 400 200 SiO2 400
150 150 Al2O3

100 200 100 200

50
50
0 0
0 0
0 2 4 6 8 10 12 14 16
0 2 4 6 8 10 12 14 16
storage time [d] storage time [d]

It seems that only the dissolution curves of the pure materials can be measured.
To confirm this assumption:
The difference of the dissolution curves between pure Q1 and of pure MK were calculated.

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Results - dissolution after SCM addition into the solution
Here are the difference curves between solubility of pure Q1 and of pure MK.
Q1 minus Metakaolin
50 50

40 40

30 30

20 20

10 10

Al2O3 [mg/l]
SiO2 [mg/l]

0 0
0 2 4 6 8 10 12 14 16
-10 -10

-20 -20
SiO2 Al2O3
-30 -30

-40 -40

-50 -50
storage time [d]

The differences are approx. zero (between -10 and +15 mg/l).
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Results - dissolution after SCM addition into the solution

Alkali attack – what can we see? Alkali attack with presence of MK in the
solution– what can we see here?

Here changes can be seen! Obviously nothing happens!

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Results - dissolution after SCM addition and after coating

100 100
SiO2 without coating
90 90 But what happens if
80 SiO2 with metakaolin 80 we store the coated
70 SiO2 with Al(OH)3 70 samples in an
alkaline solution
SiO2 [mg/l]

60 60

Al2O3 [mg/l]
Al2O3 for all
again?
50 50

40 40

30 30
There is a reduction
from 93 mg/l SiO2 to
20 20
60 mg/l by using
10 10
Al(OH)3
0 0 And a reduction from
0 2 4 6 8 10 12 14 16
93 mg/l to 57 mg/l by
storage time [d]
using MK,
approx. 40 %.

The effect of Al on the dissolution behavior can be clearly measured!

huenger@b-tu.de But what can be the reasons for this? 11
Results of structural analysis- XRD-GID and FTIR

ATR-FTIR spectra of Q1 samples: XRD pattern of sample Q1 in comparison

(a) Q1 starting material, between starting material (red) and metakaolin
(b) coated with metakaolin. after 7 (black) and after 20 days (green).
• There are no important differences between the results of the starting material and the
coated material by using such methods, exept the intensities decrease by using XRD.
• The reason for this can be the large penetration depth of both methods, which does not
allow to find differences.
• This means that the assumed coated layer on the surface of grains should be very thin.
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Results of structural analysis- XPS method

a) a) b) c)

XPS overview spectra of samples Q1 Atomic Concentration

sample N O Na Al Si F K Ca
a) starting material Q1, starting 2,32 69,45 0,06 0,71 27,44 0,00 0,00 0,00
b) 7 days coated with metakaolin, VII (7 days) 0,00 66,86 0,96 4,68 21,78 0,66 4,67 0,37
XII (20 days) 0,52 70,64 0,94 5,04 21,03 0,00 1,83 0,00
c) 20 days coated with metakaolin
Results without carbon

There are differences in the Al concentration on the surface areas of samples coated with
metakaolin at different days.

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 Results of structural analysis- XPS method

1.0
depth profiles of samples measured by XPS
0.9 method
0.8
a) a) starting material Q1
 Figure shows a normal XPS spectra without any
counts (normalized)

0.7
C1s
0.6
O1s surface influencing.
0.5
0.4
Si2p • Carbon is always present.
0.3
Al2p • Al and Si concentrations on the surface are low
K2p and increase in deeper areas. Both have the
0.2
0.1 same tendency (normalized results!).
0.0
0 5 10 15 20
b) coated with metakaolin for 14 days,
sputter time [min]
 With presence of Al on the surface the spectra
1 changes dramatically:
0.9
• C is measured until a depth of 1-2 nm (red line).
0.8
b) C1s
• In this area Si is reduced and Al shows a
counts (normalized)

0.7 O1s
0.6 Si2p maximum.
0.5 Al2p • Without carbon influence Si is always reduced but
0.4 K2p
0.3
increases slowly to 100 % until a depth of approx.
0.2 10 nm (green line).
0.1 • Al decreases slowly with an opposite tendency to
0
0 5 10 15 20
Si but can be measured in higher concentrations
sputter time [min] also until a depth of approx. 10 nm.
huenger@b-tu.de
sputter time calibrated by quartz means that 1 min is equal to 1 nm. • Potassium must be concentrated because of14KOH.
Conclusions

Solubility investigations:
• With presence of both Al(OH)3 and metakaolin (MK) the SiO2 solubility of aggregates can
be strongly reduced. Prepared with Al containing SCMs on the surfaces additionally a
40% decrease of the solubility of aggregates can be measured.
• All these are directly chemical proofs for the inhibitory effect of Al containing SCMs.

Structural investigations:
XPS-method:
• Obviously this method is the only one to find evidences for an aluminum enrichment on
the surface areas of the quartzite samples.
• Is the Al concentration in the starting material under 1 at.%, with presence of aluminum
containing SCMs the Al content increases three to eight times higher.
• Depth profile investigations can be carefully evaluated that probably Al is concentrated
until a depth of in maximum 10 nm on the surface.
• The results of the XPS method can reveal the disadvantages of the other characterization
methods used here because of their large penetration depths.
Further investigations have to be done to find
more and more evidences for the existence
and especially the structure of this layer on the
surface of siliceous rock materials, which are
huenger@tu-cottbus.de 15
used as an aggregate in concrete.
Thank you very much
for your attention!

Prof. Dr. Dr. Klaus-Jürgen Hünger

huenger@b-tu.de
0049/(0)3 55 / 69 27 58