1

31
st
Cement and Concrete Science Conference Paper Number XX
Novel Developments and Innovation in Cementitious Materials
12-13 September 2011
Imperial College London, United Kingdom

Magnesium phosphate cement as a potential alternative for
encapsulation of nuclear wastes containing aluminium

McCague, C., Wang, L. and Bai, Y.
School of Planning, Architecture and Civil Engineering, Queens University Belfast, U.K.

ABSTRACT

Currently in the UK, Portland cement (PC) based systems with high replacement of blast furnace slag (BFS)
or pulverized fuel ash (PFA) are the accepted formulations for the immobilisation of low and intermediate
level nuclear wastes (LLW and ILW). However due to the high internal pH (usually around 12), certain waste
metals such as aluminum can corrode, causing the formation of expansive corrosion products and the
generation of hydrogen gas. A potential alternative to the PC based system is magnesium phosphate cement
(MPC). MPCs are formed through an acid-base reaction between dead burnt magnesium oxide and
phosphate salts. This particular cement has a much lower pH (~7) and could potentially be suited to the
encapsulation of aluminium since Al is passive between pH 4 and 8.5. However, the rapid nature of the
hydration reaction generates considerable heat, potentially leading to cracking in larger pours.

In this paper, the effect of replacing MPC with supplementary cementitious materials (SCMs) such as ground
granualated blast furnace slag (GGBS) and PFA has been studied by monitoring the heat output and pH over
a 48hr period. The main hydration products formed were identified using X-Ray diffraction (XRD) analysis
after 24hrs. The short term corrosion of embedded aluminium was also monitored using a newly developed
corrosion test setup. It was found that the corrosion rate of Al in the MPC systems was very low in
comparison to the PC based systems and the replacement of SCMs caused a considerable reduction in the
heat generation rate, while also maintaining the low rate of corrosion.


1. INTRODUCTION

In the UK, formulations based on Portland cement
(PC) with high replacement of blast furnace slag
(BFS) or pulverized fuel ash (PFA) are currently
used for immobilization of low and intermediate
level nuclear wastes (Milestone, 2005). The
incorporation of supplementary cementitious
materials (SCMs) offers many advantages over
pure PC, mainly to reduce the high heat output that
can arise from large pours. Problems arise,
however, with the corrosion of certain waste metals
such as aluminium and uranium causing cracking
of the wasteform and the release of hydrogen gas
(Setiadi, et al., 2006). Since aluminium is only
passive in the region of pH 4 to 8.5, in the alkaline
environment of PC-based systems, aluminium will
corrode. While the pH is somewhat reduced by
high replacement of the SCMs, the rate of
corrosion is still considered to be unsafe for long
term cemented wasteforms (Milestone, 2005).
In recent years, the use of alternative low
pH cement binders has attracted interest in the
nuclear industry for coping with reactive ILW such
as scrap aluminium. One such cement is
magnesium phosphate cement (MPC) which has
been reported to have a much lower pH than PC
systems (in the range of 5-7) (Hall, et al., 1998).
MPCs have many improved properties over PC
such as rapid setting, high early and long term
strengths (Seehra, et al., 1993), lower permeability
and greater resistance to sulfate attack (Wang, et
al., 2010). In civil engineering, they are very suited
to rapid repair of concrete structures such as
pavements, airport runways and bridge decks
(Yang, et al., 2000). MPCs can be formed at room
temperature through an acid-base reaction
between magnesium oxide (MgO) and an acid
phosphate source such as ammonium or
potassium phosphate. In recent years,
considerable work has been focused on the use of
potassium dihydrogen phosphate, KH
2
PO
4
(KDP),
particularly in the field of radioactive waste
encapsulation (Wagh, et al., 1999). Unlike
ammonium phosphate, KDP does not liberate
ammonia gas during hydration and is much more
suited to larger scale applications (Wagh, 2004).
The reaction of MgO with KDP yields a hard,
dense ceramic material with very low solubility.
This rapid, exothermic reaction is represented in
the equation below:

MgO +KH
2
PO
4
+5H
2
O MgKPO
4
.6H
2
O Eq.1

The hydration product, MgKPO
4
.6H
2
O (MKP) is
known as k-struvite which is an analogue of
struvite (MgNH
4
PO
4
.6H
2
O) formed in traditional
MPC using ammonium dihydrogen phosphate.
Due to the rapid nature of the acid-base
reaction, dead burnt MgO of low reactivity is
generally used. However, the reaction rate can still
2

be too high for mixing larger volumes, potentially
leading to thermal stresses and cracking. As a
result, retarders are employed with the most
common being the oxy-boron type (Stierli, et al.,
1976). These retarders can decrease the reaction
rate to achieve practical setting times, however,
the heat output is still considered unacceptable for
waste encapsulation.
To date, very little work has been carried
out to assess the suitability of MPCs for the
encapsulation of wastes containing aluminium.
Preliminary studies have assessed the corrosion
by monitoring the pressure increase due to
hydrogen (Hayes and Godfrey, 2007) however a
proper assessment of the corrosion is still required.
In this study, the corrosion of aluminium in MPC
was evaluated using a quantitative electrochemical
method in order to address the errors that can
result from pressure measurement. The effect of
ground granulated blastfurnace slag (GGBS) and
PFA additions on heat output, hydration properties
and corrosion rate has also been assessed.


2. Materials and methods

MgO (DBM 90) was acquired from Richard Baker
Harrison UK. DBM 90 is a dead burnt magnesium
oxide manufactured from calcining magnesite at
1200c . It contains at least 90% MgO and trace
amounts of SiO
2
, CaO and Fe
2
O
3
with an average
particle size of <65microns. Food-grade potassium
dihydrogen phosphate (KDP) was supplied by
Prayon UK. According to Eq. 1, the molar ratio of
MgO to phosphate (M/P) required for full hydration
is 1. In reality, a higher M/P ratio (between 5-10) is
usually recommended as only the outer surface of
the MgO grains react to form MKP (Chau, et al.,
2011). In this study, a relatively low M/P ratio of 1.5
was employed in an attempt to keep the reaction
rate as low as possible. GGBS was supplied by
Hanson Cement with Class F PFA locally sourced.
Based on trials, boric acid was added to all
samples at 8wt% of MgO to reduce the reaction
rate further. For comparison purposes, GGBS/PC
9:1 and 100% PC samples were prepared for all
tests. The water:solid (w/s) ratio was determined
by mini slump trials to achieve comparable
flowability to the control GGBS/PC 9:1 sample. It is
considered that a matrix with a mini slump value of
70 5mm would give sufficient flowability to meet
the industry requirements for waste immobilisation.
The determined w/s ratios of the mixes are listed in
Table 1.

Table 1- Material ratios






The aluminium investigated in this study was
Grade BA1050A H14, consisting of 99.5% Al,
0.25% Fe, 0.1% Si and trace amounts of Zn, Ti, Cu
and Mn (recommended by the National Nuclear
Laboratory, UK). For this work, a corrosion setup
was devised based on electrochemical
measurement of linear polarisation resistance
(LPR), and pressure measurement due to
hydrogen evolution (Figure 1). This consists of a
sealed Teflon coated aluminium cell incorporating a
1bar pressure transducer, with suitable
connections to working, counter and reference
electrodes. A potentiostat was connected to two
embedded Al plates (each 50x30x5mm) and an
embedded stainless steel reference electrode.
Polarisation scans were carried out at a rate of
100mv/min (50mv of the open circuit potential).
Using the values of LPR, the Stern-Geary
relationship was applied to calculate the corrosion
rate in mm/year (Andrade and Gonzlez, 1978).

Figure 1. Photo of corrosion cell connected to potentiostat
The pH of the fresh cement pastes were measured
using a standard glass electrode pH meter. A
perforated PVC tube wrapped in filter paper
(10micron pore size) was inserted into the cement
so that the pH of the liquid could be measured
before it was consumed in the hydration reaction.
For pH measurement of the hardened samples,
distilled water was added to the powder of crushed
cement cubes (as described below for XRD
analysis) in the ratio 10:1. After 24hrs in a rotating
stirrer, the liquid was separated by centrifuge and
the pH was measured.
Isothermal conduction calorimetry (ICC)
tests were carried out on all cement samples over
a 48hr period using a TAM-Air calorimeter at 20c.
Samples for X-Ray diffraction (XRD) were
prepared from the crushed cement cubes.
Hydration was stopped by storing in acetone for at
least 3days and vacuum drying for a further 3
days. These were then ground to a powder using a
pestle and mortar and particles passing through a
63micron sieve were used for XRD analysis.

3. Results and discussion

The graphs of heat generation rate and total heat
are shown in Fig. 2. From Fig. 2 (a) it can be seen
that, compared to conventional PC, the rate of heat
generation of MPC is very high. However, after
~1hr 30mins there was a rapid deceleration in heat
flow, with values lower than PC observed after
Cement w/s ratio
100% MPC
MPC/GGBS 1:1
MPC/PFA 1:1
100% PC
GGBS:PC 9:1
0.18
0.23
0.23
0.4
0.46
3

~6hrs. The addition of GGBS and PFA caused a
considerable reduction in heat flow, with peak
values comparable to PC. The peak reaction rates
were also shifted up to approximately 10hrs when
compared to the 100% MPC, suggesting a
retardation effect caused by the SCMs. GGBS/PC
had a significantly lower peak rate than all other
systems. Interestingly, GGBS/MPC and
PFA/MPC yielded a higher total heat after 48hrs
when compared with 100% MPC. This correlates
with a study by Hall et. al. (1998) who reported that
there was an increase in peak temperature with
MPC mortar of greater water content; however the
rate of heat evolution was decreased. Conversely,
Ding reported that the total heat was reduced by
the addition of PFA at 40%, (however a greater
M/P ratio of 4:1 was employed) (Ding and Li,
2005a). The reason for the higher total heat in the
current MPC composites could be attributed to the
continuous slow reaction between MgO and KDP
in the presence of excess water as demonstrated
in Fig. 2(a). As shown in Table 1, with 50% of
powder replaced by SCMs, the water-cement (w/c)
ratio is higher than the pure MPC therefore more
water was available to allow further reactions.
Future studies are necessary to investigate
whether a reduction in total heat can be achieved
by using higher replacement levels of PFA and
GGBS.

Figure 2(a). Rate of heat evolution of cement samples
Figure 2(b). Total heat evolution of cement samples
The XRD traces of the hydrated cements are
shown in Fig. 3. In the pure MPC system, MKP
was formed as the main hydration product,
however strong peaks of unreacted MgO and KDP
were still evident after 24hrs. The residual traces of
the reactants could be attributed to the low M/P
ratio of 1.5. Based on stoichiometry, a molar ratio
of 1 is only required for full hydration however this
is not the case in reality. Chau et al. reported that a
high M/P ratio of at least 5 would produce a
cement matrix with better MKP formation leading to
improved strength development, with only MgO
present as a residual reactant (Chau, et al., 2011).
As higher strength is not the main driving force for
waste encapsulation, a higher M/P ratio may not
be necessary, however, it was found that the
cement with unreacted KDP led to issues with
cracking and expansion. This was evident when
the hardened cement pastes were cured after
24hrs using wet hessian. The additional moisture
caused further reaction between the unhydrated
MgO and KDP leading to excessive expansion and
cracking of the hardened cement. After
demoulding, the cubes could easily be broken up
by hand. This behaviour was also noticed by
Iyengar after curing at high RH using a low M/P
ratio (Iyengar and Al-Tabbaa, 2007).


Figure 3. XRD of (a) 100% MPC (b) PFA/MPC (C) GGBS/MPC
after hydration for 24hrs
MKP was also found as a main hydration product
in the MPC composites. The PFA/MPC trace
shows greater peak intensities than both 100%
MPC and GGBS/MPC. Peaks for quartz and
mullite were clearly identified in the PFA/MPC
sample. An amorphous hump characterising the
glassy phases in GGBS, along with some
gehlenite, was found in the GGBS/MPC sample. It
appears that no new crystalline minerals have
been formed in the MPC composites based on the
XRD traces. It can also be seen from Fig. 3 that
with the MPC composites, the main peak
intensities for residual MgO and KDP are much
reduced compared to the pure MPC. This can be
attributed to the 50% reduction in the solid
reactants due to the SCM replacement. With 50%
MPC replacement, there is also a higher amount of
water available allowing more KDP and MgO to be
2
0
0 10 20 30 40
100% MPC
50
4
6
8
10
12
PFA/MPC 1:1
100% PC
GGBS/PC 9:1
GGBS/MPC 1:1
20
0
0 10 20 30 40
100% MPC
50
PFA/MPC 1:1
100% PC
GGBS/PC 9:1
GGBS/MPC 1:1
40
60
80
100
120
140
160
180
H
e
a
t

f
l
o
w

(
W
/
k
g
)

Time(hrs)
T
o
t
a
l

h
e
a
t

(
K
J
/
k
g
)

Time(hrs)
15 25 35 45 55
MKP
MgO
KDP
Mullite
Quartz
Gehlenite

(a)

(b)

(c)
Degrees2
*
*
4

consumed in the reaction. A similar observation
was made by Ding where an increase in water
content saw greater intensity in peaks of MKP in
MPC with 40% PFA replacement (Ding and Li,
2005b). Based on stoichiometry, a molar ratio of
1:1:5 (MgO:KDP:water) is necessary for a full
reaction to occur, giving a w/c ratio of 0.51. While
the w/c ratios in the MPC composites were still
lower than this theoretical value (but higher than
the 100% MPC), the formation of MKP was still
improved when compared to the pure MPC. As
with pure MPC, the cube samples for the MPC
composites also experienced considerable
expansion when cured at high RH. Further work on
the development of a suitable formulation should
focus on a range of M/P ratios.

Table 2. pH of cement samples over 48hrs
Cement Curing time
Initial value 1 day 2 days
100% MPC
MPC/GGBS
MPC/PFA
100% PC
GGBS:PC 9:1
5.142~6.471
5.349~6.354
5.411~5.976
12.987~13.347
12.539~12.762
8.214
9.155
8.662
12.851
12.281
8.215
9.619
8.814
12.731
12.278

The initial pH values for pure MPC was
found to be similar to those quoted in literature
(Hall, et al., 1998). However, the pH of the
hardened sample was found to be significantly
higher than the wet paste. This observation was
also made by Iyengar et al. (2007) for hardened
MPC at 24hrs. After 2days the value rose to 8.215
but remained within the passive range for
aluminium. The initial pH values of the MPC
composites were similar to the pure sample but
after 2 days, the values had increased to values
outside the Al passive range (see Table 2). This
increase is likely to be linked to the higher alkali
content of the SCMs in comparison to pure MPC.

0
0 5 10 15 20 25 30 35 40
0.2
0.6
1
100% PC
GGBS/PC 9:1
GGBS/MPC 1:1
PFA/MPC 1:1
100% MPC
0.4
0.8
25 30 35 40
0
0.1
0.2
0.5
1.5


Figure 5. Corrosion rate of Al in cement samples over 48hrs
According to the results from LPR (Fig. 5),
the aluminium in all MPC mixes demonstrated very
low corrosion rates in comparison to the pure PC
and GGBS:PC 9:1 samples. However, from Fig. 5
it can be seen that the MPC composites produced
a slight increase in corrosion rate between 25-
30hrs. This is thought to be linked to an associated
pH increase, where values had risen above the Al
passive range after 24hrs. Interestingly, the
aluminium corrosion rate in GGBS/MPC is lower
than that in PFA/MPC, although the pH of the
former is higher. This could be partly attributed to
the reducing environment of the slag (Naik and
Ramme, 1989) which could potentially reduce the
corrosion of aluminium. Further work will be
necessary to investigate this.
The results of pressure are shown in Fig.
6. As expected, the pressure increase of the PC
samples was quite rapid, demonstrating a high rate
of hydrogen evolution. MPC showed almost no
change in pressure with a slight increase between
0-5hrs. Based on the data from pH, LPR and
observation of Al plates, the corrosion in all MPC
samples after 2 days was almost negligible in
comparison to the PC and GGBS/PC 9:1 sample.
The comparison between the pressure results and
the corrosion rates in Fig.5 would suggest that
although the pressure test can give some
indication to the corrosion of aluminium, it is
insufficient to differentiate the small difference in
corrosion. On the other hand, whilst the corrosion
in MPC composites started to increase slightly
after 25 hours as observed from LPR results, the
accumulative pressure in the MPC composites
decreased. Therefore, the reliability of using
pressure measurement as an indication of the
corrosion is questionable and further research is
needed.


0.2
0
0 5 10 15 20 25 30 35 40
0.4
0.6
0.8
1
100% PC
GGBS/PC 9:1
GGBS/MPC 1:1
PFA/MPC 1:1
100% MPC



Figure 6. Measured pressure in corrosion cell up to 40hrs

4. Conclusions

The magnesium phosphate cement (MPC)
formulated for this study was found to have
a low pH and much reduced corrosion of
aluminium in comparison to the standard
GGBS/PC 9:1 and pure PC formulations.
However, high heat generation and
unexpected expansion over 48hrs suggest
C
o
r
r
o
s
i
o
n

r
a
t
e

(
m
m
/
y
r
)

Time(hrs)
P
r
e
s
s
u
r
e

(
b
a
r
)

Time(hrs)
Time(hrs)
C
o
r
r
o
s
i
o
n

r
a
t
e

(
m
m
/
y
r
)

5

that modifications are necessary to achieve
a suitable matrix for waste encapsulation.
Additions of GGBS and PFA at 50%
replacement significantly reduced the rate of
heat evolution but led to a higher total heat
than pure MPC. Future studies at
replacement levels up to 90% is needed to
determine if the heat of hydration can be
reduced further.
MKP was found as the main hydration
product after 24hrs in all MPC samples with
higher amounts of unreacted MgO and KDP
in pure MPC. It is thought that the residual
unreacted material was a result of a low M/P
ratio, causing delayed hydration and
excessive expansion when cured at a high
RH.
With the SCM additions, the pH of MPC was
increased above the passive range for
aluminium however the corrosion was still
much lower than the GGBS/PC 9:1 control
sample after 48hrs. The polarisation
measurements confirmed that Al corrosion
was almost nonexistent in all MPC samples,
although a slight increase was observed in
the GGBS/MPC and PFA/MPC samples
after 24hrs. The method of pressure
measurement was found to give a
reasonable assessment of the different
cements tested, however, further work is
necessary to identify any potential errors
due to changes in volume and temperature.

Acknowledgements

The authors would like to thank Prayon UK,
Richard Baker Harrison and Hanson Cement for
supplying the materials for this study. The
guidance from ACM UK on the corrosion setup and
discussions by Dr Martin Hayes and Dr Nick Collier
from National Nuclear Laboratory, UK are also
gratefully acknowledged.

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