CEMENT and CONCRETE RESEARCH. Vol. 22, pp. 1192-1200, 1992. Printed in the USA.

0008-8846/92. $5.00+00. Copyright © 1992 Pergamon Press Ltd.

Mechanical Behavior and Microstructural Development in Phosphate

Modified High Alumina Cement

Weiping Ma and Paul W. Brown

Materials Research Laboratory
The Pennsylvania State University
University Park, PA 16802

(Refereed)
(Received Oct. 2, 1991)
Abstract

High alumina cement was modified by phosphate-based reactants and the variations in
mechanical properties were investigated. The flexural strength is greatly improved by
addition of various sodium-based inorganic polymers and calcium phosphate. The short-
term flexural strengths of samples containing 20 wt.% of these constituents can reach over
40 MPa, while that of corresponding pure cement cured under the same conditions is
approximately 14 MPa. After ten months of curing, the strengths of the modified samples
continue to be more than twice as high as that of pure cement. The mechanism responsible
for strength increase in this material was studied by X-ray diffraction and mercury intrusion
porosimetry. Experimental results indicate that these phosphate-based compounds do not
form crystalline hydration products but provide structural integrity to high alumina cement
by decreasing the porosity.
Introduction

High alumina cement (HAC) rapidly develops strength and offers modest strength and
stiffness in compression but is weak in flexural and impact strengths [1]. It is also well established
that HAC shows strength losses at normal and elevated temperature [2,3]. The reason is that the
hydration of HAC results in the formation of hydration products CAH10 and C2AH8, which are
chemically unstable at normal and higher temperature, transform into cubic C3AH6 and alumina
gel. This change is known as conversion and it results in an increase in porosity and in strength
loss. One approach to improvement of the properties of HAC is the addition of secondary
constituents.
A class of cements containing secondary constituents are high strength cement pastes called
macrodefect free cements (MDF cements). These have generated a high level of interest recently.
MDF cements were produced initially with high alumina cement, and then with ordinary portland
cement, in combination with a water soluble organic polymers of low molecular weight [4,5,6].
However, their applications in civil engineering are very limited because MDF cements are
unstable when immersed in water or even when exposed to high humidity [7,8]. A different
approach to improve the properties of cementitious materials is the addition of phosphatic
materials. The purpose of this study was to build on the general concepts from MDF cement
technology by identifying cement-based composites eliminating organic polymer as an admixture.

1192
Vol. 22, No. 6 MECHANICALPROPERTIES, MICROSTRUCTURE, HIGH-ALUMINACEMENTS, PHOSPHATES 1193

Experimental
1. Materials

The high alumina cement used in this study is Secar 71 cement (Lafarge). A typical chemical
analysis is shown in Table 1. X-ray powder diffraction indicated that it consists of CA, CA2 and
C12A7. It is difficult to quantitatively measure the relative proportions of these phases because
variations were observed from one sample to another. Bushnell-Watson and Sharp [9] suggested
this to be associated with different particle size distributions of the various phases. The chemical
analysis of silica fume used in some experiments to replace a portion of the cement is given in
Table 1.

The phosphate materials used include four sodium phosphates and one calcium phosphate:
sodium hexametaphosphate (NaPO3)n, sodium metaphosphate (NaPO3)n.Na20, sodium
tripolyphosphate Na5P3010, sodium trimetaphosphate (NaPO3)3 and dicalcium phosphate
Ca2P207. The latter compound is an orthophosphate.

2. Sample Preparation

To prepare the cement pastes, HAC and phosphate were mixed with deionized water by hand
in a beaker for about 30 seconds. The mixture was then placed in a high-shear mixer (Brabender)
and mixed for about 3 minutes with a mixing speed of 60 RPM. After mixing, the mixture was
pressed at 28 MPa for about 1 minute. Samples were then sealed in plastic bags and cured for
about 12 hours at room temperature. The samples were then cured under both dry and wet
conditions. After curing they were cut into bars with the dimensions of about 0.2 x 0.2 x 0.8
inches for flexural strength measurements using a low speed diamond saw [10]. Cylindrical
specimens 0.5 inch in diameter were made for splitting tensile strength measurements.

Table 1. Chemical analysis of Secar 71 cement and Silica Fume.

Compounds Secar 71 Silica Fume

Wt% SiO2 0.68 95.32

Wt% A1203 71.30 0.02
Wt% Fe203 0.09 0.08
Wt% CaO 26.80 0.38
wt% TiO2 0.01 <0.01
Wt% MgO 0.46 0.19
Wt% Na20 0.37 0.08
Wt% K20 0.02 0.55
Wt% L-O-I 0.70 3.05
Wt% SO3 0.04 0.24

Total % 100.47% 99.92%

3. Test Methods

Three point bend load determinations were made using an Instron testing machine at a loading
rate of 0.01 cm/minute. The flexural strength or modulus of rupture (MOR) was calculated using
the expression
M~- 3LP
u K = 2-if--D2
1194 W. M a and P.W. B r o w n Vol. 22, No. 6

where P is the maximum load, L the distance between the supports (0.377 inch). B and D the
width and depth of the specimen, respectively. The splitting strength was also measured on an
Instron machine. The splitting strengths were calculated using the expression
2P
S.S.-
xdt
where d is the diameter and t the thickness.

X-ray diffraction analyses were performed on a Scintag automated X-ray diffractometer

interfaced with a microVAX computer. Preparation of hardened samples consisted of grinding in a
mortar and pestle, and mounting on a glass slide. Samples taken after short times of hydration
were put in acetone to stop reaction and then mounted on a glass slide until the acetone evaporated.

Porosity analyses were performed by scanning mercury porosimetry. Preparation of samples

consisted of cutting the samples into 4 mm pieces and freeze drying for 16 hours.

Results a n d D i s c u s s i o n

1. Mechanical Properties

a) Flexural strength of HAC modified bv sodium ohosDhate. The flexural strength of the
hardened cement pastes was measured after curing for-up to 10 months at room temperature.
Figure 1 shows the results for pure Secar 71 and modified samples using four sodium phosphate
compositions. All samples were hydrated at a water/solid ratio of 0.182 and a phosphate/cement
ratio of 0.1. The phosphate modified cements have higher strengths than pure one.

50 1 Pure Secar 71 {I
---a-- (NaPO3)n'Na20
.-¢0 • ......~ .... Na5P3010
•. _..~,.. (NaPO3)n
q"
. .~l.'-,o - "~- (NaPO3)3 ,. ~,---,~ .........
30 , ~X • • ,i -x:'_" . . . . .
,i ..... .,, .....
20
..... ~"~ ..............
. . . uvwv- . .. . . . . .
. ..m." n:..'.:..'.:..'.L.'.'..=
. .~'7 ......
©

10

, • , , , , • , , • , ,ll, , • , , • ,

10 20 30 40 50 60 70 80 90 260 270 280 290 300

Days

Figure 1. Flexural strength for pure Secar 71 and sodium phosphate modified samples with curing
time.
As shown in the figure, strengths increased very rapidly with age for about 3 to 7 days for
both pure HAC and the modified cements. After 7 days, the strengths began to decrease until 28
days of hydration. The strengths then slowly increased again. The differences between pure HAC
and the modified cement are significant. The maximum strength of pure HAC was 14 MPa at 7
days, while the (NaPO3)n-Na20, (NaPO3)n and (NaPO3)3 modified samples attained maximum
strengths of 35, 40, 29 MPa, respectively, at 3 days (the Na5P3010 modified sample reached a
maximum strength of 34 MPa at 7 days). The modified samples had strengths between 2 and 3
times that of the pure cement. However, the modified cements followed the same trend as pure
Vol. 22, No. 6 MECHANICALPROPERTIES, MICROSTRUCTURE, HIGH-ALUMINA CEMENTS, PHOSPHATES 1195

cement, in that their strengths began to decrease after reaching maxima. Between one month and
three months of curing, the strengths for all the samples were lower than the strengths exhibited
during the first thirty days. The reason for the loss in strength is probably related to the same
mechanism in all cases. The initial products of HAC hydration under room temperature are
hexagonal calcium aluminate hydrates CAH10, C2AH8, and alumina gel AH3. These calcium
aluminates are all metastable. With time, both CAH10 and C2AH8 slowly convert to C3AH6 and
alumina gel with consequent increase in porosity and strength loss [11]. After ten months of
hydration, (NaPO3)n.Na20, (NaPO3)n, Na5P3010 and (NaPO3)3 modified cements attained
strengths of 35, 27, 29 and 28 MPa, respectively, while the pure cement only reached 12 MPa.

b) Flexural and snlittin~ strength of HAC modified bv calcium ohosohate. The effects of
calcium phosphate additions were also studied as shown in Table 2. A-mounts of phosphate used
were: 10%, 25% and 40%, and samples were cured in air or water at room temperature. As seen
in the table, no matter how much calcium phosphate is added, the effect on the flexural strength at
early ages is small. However, in the long term, the more calcium phosphate that is added initially,
the higher the strength. The splitting strengths showed the same trend as shown in Table 2. It was
found that calcium phosphate was not as effective as sodium phosphate in achieving increases of
strength of HAC. For samples cured in water, strengths were reduced significantly. This
indicates that calcium phosphate modified HAC composite is sensitive to water.

Table 2. Flexural strength and splitting strength of HAC modified by calcium phosphate.

Samples I Materials Amount Flexural Strength ( MPa ) Splitting Strength ( MPa )

(g) 1D 3D 7D 28D 1D 3D 7D 28D
57 Secar 71 85 15.0/11.2 14.7/13.9 18.3/10.5 22.9/11.2 5.6 6.1 8.0 11.8
DI Water 24
Secar 71 85
55 Ca2P207 8 15.0/27.5 10.9/10.5 16.9/10.1 25.1/12.5 5.3 7.6 7.8 11.9
DI Water 24
Secar 71 85
56 Ca2P207 20 14.6117.9 14.0/11.7 15.5/11.6 28.1/13.0 6.1 5.9 9.0 13.1
DI Water 24
Secar 71 75
58 Ca2P207 30 11.0/10.1 14.0/9.2 27.0/9.1 35.0/10.1 6.3 7.2 10.1 17.5
DI Water 29
For flexuralstrength data, the numeratorrepresents the samples cured at room temperatureand room humidity,
and the denominatorrepresents the samplescured in water at room temperature.

c) Effects of addition of silica fume. Ten percent silica fume was used to replace the same
amount of HAC. The resultant strength of the samples exhibited the same trend as shown before.
The strength is very high at early ages as shown in Figure 2, but the flexural strength decreased
from 48 MPa to 24 MPa between one and three days. Figure 2 compares the pure Secar 71,
(NaPO3)n modified cement and (NaPO3)n modified cement but with about 10% Secar 71 replaced
by silica fume. In the phosphate modified cement, the strength is higher than that of pure Secar
71. After ten months of curing, the strength of silica fume replaced sample was still twice as high
as that of pure cement. Furthermore, strength loss in silica fume replaced samples is less than in
samples without silica fume, although they have the approximately same strength at the end of ten
months of curing. Thus, adding silica fume retards the loss in strength.

d) Effects of W/C ratio. It was found that fluidity increased by adding the sodium phosphate
to Secar 71 during sample processing. Therefore a lower W/C can be used to obtain the same
fluidity. It can seen in Figure 3 that samples with a lower W/C (W/C = 0.17) exhibits lower
strengths than samples with a higher W/C (W/C = 0.20) during the early stages. However, with
time, the lower W/C samples develops higher strengths than samples with the higher W/C. After
about seven days of hydration, the strengths of samples with the higher W/C decrease while those
1196 W. Ma and P.W. Brown Vol. 22, No. 6

with the lower W/C maintain their strengths and show minimal strength loss. This indicates that
using a lower W/C is an effective way to minimize the conversion reaction and to retard the loss in
strength.

e) Effect of nhosDhate addition level In order to determine the effect of addition level on
strength, sodium l~exahaetaphosphate (NaPO3)n was added to HAC in 5 Wt.% increments from 5
Wt.% to 30 Wt.%. The effect on strength is shown in Figure 4. As shown in the figure, the one
and seven days strength increased with amount of added phosphate until 20%, and then decreased
rapidly at higher addition levels. It can be concluded that amount of phosphate strongly affects the
mechanical properties of HAC.

50
- PureSecar71 II 1
40 __~ (NaPO3)n

r~ 30

© 20

Ill
I0

0 , . , , , • , , • , , ,1t- , , . , , .

0 10 20 30 40 50 60 70 80 90 260 270 280 290 300

Days

Figure 2. Effect of silica fume addition on flexural strengths.

2. X-ray Diffraction Analysis

This section will focus on how phosphate affects the cement. The mechanism by which
strength increased was studied by x-ray diffraction (XRD). Figure 5 shows four x-ray diffraction
patterns; pure Secar 71 and three modified samples with 10 Wt.%, 20 Wt.% and 30 Wt.%
(NaPO3)n additions, respectively. All samples were cured in air for one day at room temperature.
Although there were large differences in the mechanical properties among these samples, as
discussed previously, the differences in the x-ray diffraction patterns are minimal. Figure 6 shows
the patterns obtained after six hours of hydration of pure Secar 71 and a modified sample
containing 20 Wt.% (NaPO3)n'Na20. The positions of the peaks do not change, but only differ in
intensity. The highest peak in the figure refers to calcium aluminate (CA). It can be seen that the
modified samples consume more CA, and further confirms that phosphate addition accelerates the
hydration reaction.

Figure 7 compares the diffraction patterns obtained from pure Secar 71 and modified sample
with a calcium phosphate addition of 40 Wt.% 2CaO.P2Os. The samples were cured in air for 28
days at room temperature. A similar conclusion can be made as before: CA consumption is
accelerated, however, a new crystalline reaction product does not appear to form. Thus, the
increase in strength may be related to formation of an amorphous phase which may be an
aluminate-phosphate gel. If so, such a gel may be stronger than the aluminate gel which produced
by pure high alumina cement.
Vol.22, No. 6 MECHANICALPROPERTIES,MICROSTRUCTURE,HIGH-ALUMINACEMENTS,PHOSPHATES 1197

,° I
30

© [] PureSecar71
20 • (NaPO3)n'Na20
w/C = 0.20
• (NaPO3)nNa20
10 W/C = 0.17

0
0 10 20 30
Days

Figure 3. The loss in flexural strengths is reduced by a low W/C ratio.

50

40
v

30

20

10

0
0 5 10 15 20 25 30
Content of (NaPO3)n ( wt.% )

Figure 4. Flexural strengths depending on the amount of phosphate added.

3. Mercury Intrusion Porosimetry Results

Figure 8 shows the cumulative percentage of pore volume with respect to the total pore
volume, for pure Secar 71 and for two modified samples containing 10 Wt.% and 20 Wt.%
(NaPO3)n.Na20. All samples were cured for one day at room temperature and room humidity. It
is observed that modified cements have lower total porosity and pore distribution consisting of
smaller pores than the pure cement. The sample with 20 Wt.% (NaPO3)n.Na20 addition exhibits
the lowest total porosity and the smallest pores. These porosity results are in accord with
mechanical properties observed.

Conclusions
High strength can be achieved by high alumina cement with phosphate-based additions.
Sodium phosphate and calcium phosphate have different effects on mechanical properties. Silica
fume replacement offers advantages in reducing the loss in strength. A low water:cement ratio is
required to achieve high strength in the long term. Mechanical properties varied depending on the
phosphate addition level. The increase in flexural strength is related to the decrease in pore size
and in porosity.
1198 W. Ma and P.W. Brown Vol. 22, No. 6

The phosphate-based materials do not form the crystalline products during the hydration of
high alumina cement. An aluminate-phosphate gel may be produced, which provides greater
structural integrity to high alumina cement. Further studies are underway to establish the
mechanism of strength increase in these materials [12].

._...~--- ~
Pure Secar 71

I I I l I I I I 1 I I I I I 1 I I 1 1 1 r F I 1 7 F T F 7 7 - -

15 20 25 30 35 40 20
Figure 5. XRD of pure Secar 71 and three different amount of (NaPO3)n modified samples curing
in air for one day at room temperature.

Pure Secar 71

6 16 26 36 46 56 20
Figure 6. XRD of pure Secar 71 and 20 Wt.% (NaPO3)n'Na20 modified samples after curing in
water for six hours at room temperature.

Acknowledgement

The authors gratefully acknowledge the support of the Air Force Office of Scientific Research,
Aerospace Sciences Directorate.

References

1. H. F. M. Taylor, Cement Chemistry, Academic Press Inc. (1990) pp. 316-30.

2. R. N. Edmonds and A. J. Majumdar, "The Hydration of Secar 71 Aluminous Cement at
Vol.22, No. 6 MECHANICAL
PROPERTIES,MICROSTRUCTURE.HIGH-ALUMINACEMENTS.PHOSPHATES 1199

6 16 26 36 46 56 20
Figure 7. XRD of pure Secar 71 and 40 Wt.% 2CaO'P205 modified samples cured in air for 28
days at room temperature.

!.0

0.B

.t~ 0 . 6
\ \
~D ~ \ " ,Pure Secar 71
>

o4 20% P ~ ~ , , ' ' ,

E
10% P ~ X x ' , \ \ x\
0.2
P -- (NaPO3)n.Na20 ~ x\ x " I

0.0 i I
I0 I00
Pore Diameter (nm)

Figure 8. Cumulative probability distributions for pure Secar 71 and (NaPO3)n.Na20 modified
samples.

Different Temperatures," Cem. Concr. Res., 19 (1989) pp. 289-94.

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Temperatures," Cem. Concr. Res., 18 (1988) pp. 311-20.
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Ed. P. I-~sch, et al. (1983) pp. 31-51.
1200 W. Ma and P.W. Brown Vol. 22, No. 6

8. C. S. Poon and G. W. Groves, "The Microstructure of Macro-Defect-Free Cement with

Different Polymer Contents and the Effect on Water Stability," J. Mater. Sci. 23 (1988) pp.
657-70.
9. S. M. Bushnell-Watson and J. H. Sharp, "The Effect of Temperature upon the Setting
Behaviour of Refractory Calcium Aluminate Cements," Cem. Concr. Res., 16 (1986) pp.
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11. A. M. Neville, Prooerties of Concrete. Pitman Publishing Inc., (1981) pp. 92-99.
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preparation).