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Particle size distribution of cement and concrete

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Faculty of science
Chemistry department

Graduation Project
In
Particle size distribution of cement and concrete

Presented by

Reda Gabra Sidky Abdel Hakim

4th year applied chemistry

Under the supervision of

Prof. Dr. Hanaa Y. Ghorab

2019

i
 Table of Contents

ABSTRACT ........................................................................................................... 3

INTRODUCTION ................................................................................................ 4

1.1 HOW TO MEASURE PARTICLE SIZE DISTRIBUTION?............................................ 5

CHAPTER 2 .......................................................................................................... 8

2-PARTICLE SIZE DISTRUBTION OF Α-CALCIUM SULFATE HEMIHYDRATE PASTE ..... 8

3-RELATIONSHIP BETWEEN PARTICLE SIZE DISTRIBUTION OF Α-CALCIUM SULFA..11

4-PARTICLE SIZE DISTRIBUTION OF CLINKER ........................................................ 13

5-EFFECTS OF SIZE FRACTION ON COMPOSITION AND FUNDAMENTAL PROPERTIES

OF PORTLAND CEMENT .............................................................................................. 15

6-THE EFFECT OF PARTICLE SIZE DISTRIBUTION ON THE PROPERTIES OF BLENDED

CEMENTS INCORPORATING GGBFS AND NATURAL POZZOLAN (NP) .......................... 16

7- PARTICLE SIZE DISTRIBUTION OF LIMESTONE ................................................... 20

8- NEW GAP-GRADED PARTICLE SIZE DISTRIBUTION ............................................. 24

9.PSD EFFECT ON OTHER PROPERTIES OF CEMENT ............................................... 25

1-Packing Density .......................................................................................... 25

2- Fluidity of cement ...................................................................................... 26
3- Setting Time ............................................................................................... 26
4- Heat Release .............................................................................................. 28
5- Capillary Porosity Percolation.................................................................. 29

10.IMPROVING PARTICLE SIZE DISTRIBUTION IN CEMENT PASTE ........................ 31

REFERENCES .................................................................................................... 32

ii
 Abstract

Particle size distribution (PSD) is an essential property of cement. The

only standard method to measure the PSD of cement, namely ASTM C115
is limited in scope; this standard describes a method for determining
―fineness‖ with a lower size detection limit of 7.5 µm. As there is no
standard procedure covering the whole range of cement PSD, the
implementation of different measurement methods varies widely within
the industry. In general, the round-robin results summarized here have
demonstrated the high variability between participants using instruments
based on the same physical principles. ASTM committee C01.25.01
sponsored a round-robin test to measure the PSD of cement. The aim of
the current report is to analyze the data generated during those tests and to
summarize the various approaches available to measure the PSD of
cement. The analysis of the data is conducted in two parts. In the first part,
an attempt is made to establish a reference distribution using a standard
cement powder (SRM 114p). This is followed up by a comparison of the
round robin data in order to initiate discussion on developing a standard
test method for cement PSD to be submitted for ASTM consideration. The
report provides all raw data collected during the round robin tests, and the
results of a statistical analysis of the collected data.

3
1. Introduction

Regarding the fineness and particle size distribution of the cement, the
most frequently followed parameters in the cement are 45 and 90 micron
sieve residue and Blaine (specific surface area) values. Blaine value is a
numerical value of the area covered by 1g material. It is impossible to
interpret the performance of cement with these two values. For this
reason, particle size distribution is performed with automatic devices via
distribution curves.

The effect of the particle size distribution on its performance is also

influenced by the grain size of the mineral admixtures. It is an important
parameter that must be taken into consideration during the selection since
the mineral admixtures can have different particle size distribution.

The grain size distribution curve for the cement needs to be 'S‗ shape.
The meaning of 'S' is that the particles are distributed homogeneously in
different dimensions within the sample. While investigating properties of
cement grain not only the size but also the shape parameter is important
because these two variables are essential to determine total surface area.

The Main cement properties affected by the particle size distribution:

A- Strength
B- Setting Time
C- Permeability
D- Hydration Temperature
E- Water Demand
F- Microstructure

4
2. How to measure particle size distribution?
Currently, the most widely used technique for PSD determination is that
of laser light scattering. There are two variations: dynamic light
scattering (DLS) and Fraunhofer diffraction (FD) .

Figure 1. . Laser light scattering

Laser diffraction measures particle size distributions by measuring the

angular variation in intensity of light scattered as a laser beam passes
through a dispersed particulate sample. Large particles scatter light at
small angles relative to the laser beam and small particles scatter light at
large angles, as illustrated above. The angular scattering intensity data is
then analyzed to calculate the size of the particles responsible for
creating the scattering pattern, using the Mie theory of light scattering.
The particle size is reported as a volume equivalent sphere diameter.
Particle size distribution (PSD) of cementitious materials influences the
packing density and the hydration process of powders, and thus greatly
affects the characteristics of the materials, such as setting time, water
requirement .fluidity, microstructure and strength. Many efforts have
been focused on the analysis of the relationship between PSD and
properties of materials in cement and concrete .α-Calcium sulfate
hemihydrate (α-HH), another important class of cementitious materials,
has been widely used in many areas such as precision instrument molds,

5
ceramics, industrial arts, and architecture due to its superior workability
The PSD of α-HH is believed to be one of the most important parameters
that control the hydration of plaster and the compressive strength
development of paste. The particle fraction has been divided into two
groups, one works with a positive effect, the other with a negative effect.
However, the effect of the PSD on the properties of α-HH paste is still
not well known. A mathematical function offers opportunities for a
direct comparison of PSD among particle systems. More useful
information can be revealed if the parameters of the function can be
related to the properties of the system. One of the widely adopted
mathematical models is the Rosin–Rammler–Bennett (RRB) distribution
function. The function can be described in two forms [1, 2]:

* + (1)

, ( )- (2)

Where R is the percentage of residue by weight (%), D is the particle

size (μm), De is the characteristic particle size describing the particle
fineness and equals to D at R=36.8%, and n is the uniformity coefficient
describing the distribution width.

Eq. (1) is the original form and Eq. (2) is the logarithmic form. However,
Eq. (2) cannot provide a good linear relationship at both ends of the line.
To minimize errors, Eq. (1) is taken by nonlinear least square fitting
(NLSF) to calculate the RRB parameters, De and n. R is selected as a
dependent variable for independent D. Then, the corresponding fitting is
performed until the quadratic sum of errors between the theoretic value
(R) and experimental one (Re) is minimized.

6
NLSF has obtained a significantly better fitting in cement and aerosol
system for the analysis of the PSD. The RRB function is particularly
suited for describing powders made by grinding, milling and crushing
operations. It has been used to analyze the effect of PSD on the
properties of cement, and many results and conclusions have been
provided from different perspectives.

Olorunsogo and Kuhlmann proposed that an increase in De of cement

decreased its reactivity with water and thus gave a lower compressive
strength.

Wang observed that the hydration was accelerated as n increased if

powders had the same specific surface area.

Kuhlmann and Wang presented that a smaller n indicated a higher

packing density of the powder and thus a lower water requirement for
standard consistency.

Lee concluded that the fluidity of cement paste increased as n decreased.

To make a comparison among these investigations is somewhat difficult.
Furthermore, application of the RRB distribution function in gypsum
plaster largely lags behind.

The hydration and compressive strength development of α-HH are

obviously different from that of cement, thus the characteristic influences
of the RRB parameters of the two materials are probably not the same. In
this study, an attempt was made to correlate the RRB parameters of
plaster with the hydration and compressive strength development of
paste, focusing on the singular effect of particle fineness (De) and
distribution

Width (n) of α-HH on the water– hemihydrate weight ratio (W/H) for
standard consistency, hydration rate, compressive strength and

7
microstructure of paste. Such a study will contribute to the optimization
of the PSD of α-HH plaster and other cementitious materials.

2-Particle size distrubtion of α-calcium sulfate hemihydrate paste

The particle fineness (De) and distribution width (n) play a great role in
the W/H for standard consistency of α-HH paste. The coarser plasters
require less water while plasters with narrower PSD require more water
for standard consistency. The particle fineness has a great effect on the
hydration rate of α-HH plaster at n≈0.82.

The finer plasters hydrate faster while the coarser plasters hydrate more
slowly. Plasters with different n at De ≈35 μm present a slight difference
in the hydration rate. The particle fineness is also very important for the
compressive strength development. For pastes of standard consistency,
plaster with De ≈35 μm obtains the highest compressive strength with
different D e at constant (n ≈0.82). But the varying of n at constant De
(≈35 μm) results in little difference in compressive strength. The
microstructure details are in general agreement with the impact of PSD on
the hydration and the compressive strength development of paste.

Figure 2. Compressive strength of pastes prepared from α-calcium sulfate

Hemihydrate (α-HH) plasters with different particle finenesses (a) and distribution
widths (b)

8
Plaster with the optimum PSD hydrates completely without a hydration
barrier at a relatively lower W/H Then, homogeneous and well-grown DH
crystals and a more compact structure are obtained, giving a higher
compressive strength. For pastes of standard consistency, an optimum
PSD is characterized by De≈35 μm and n≈0.82. The hydration and
compressive strength development can be correlated with the RRB
parameters and the plaster with the optimum PSD could be obtained by
adjusting the parameters.

Figure 3. . Scanning Electron Microscope (SEM) images of pastes with

different particle finenesses

The compressive strength measurement results of cement mortar with α

HH are shown in Figure 4.The compressive strength of the cement
mortar decreased with increasing replacement ratios of α HH When OPC
was used, the compressive strengths of the OPC- α HH10, OPC- α

9
HH20, and OPC- α HH30 specimens at the age of 1 day were 10.43
MPa, 10.39 MPa, and 9.96 MPa, respectively, which are approximately
57–59% that of the OPC specimen (17.62 MPa). At 28 days, the
compressive strengths of the OPC- α HH10, OPC- α HH20, and OPC- α
HH30 specimens were 22.31 MPa, 18.79 MPa, and 17.81MPa,
respectively, which are approximately 44–55% that of the OPC
specimen (40.88 Mpa).

Figure 4. Compressive strength measurement results of αHH replaced

cement mortar

When PSC (Portland blast-furnace slag cement) was used, the

compressive strength of the PSC specimen was 14.54 MPa at the age of
1 day and 36.51 MPa at the age of 28 days. The compressive strength of
the PSC- α HH10 specimen was measured to be 8.56 MPa—the lowest
observed compressive strength at an early age in this study. These results
indicate that α HH did not have a significant effect as a stimulant for the
hydration of PSC at an early age. However, the compressive strength of
the PSC- α HH10 specimen at the age of days was 27.90 MPa, which is
approximately 68% that of the OPC specimen. Therefore, among the
cement mortars with α HH replacements, the PSC- α HH10 specimen,

10
which used PSC, was confirmed to be most favorable for the
development of the compressive strength.

Overall, replacement with α HH resulted in a decrease in the

compressive strength in cement mortar, which was also reported in a
previous study. Meanwhile, a decrease in compressive strength owing to
the use of only α HH was not observed within the α HH replacement
ratio range used in the current experiment.

Figure 5. Scanning electron microscope micrograph of αHH

3-Relationship between particle size distribution of α-calcium sulfate

hemihydrate and compressive strength of set plaster—Using grey
model

A grey system is defined as the one in which partial information is

known and the remaining is unknown. Grey system theory has been
employed in cement material to analyze the relationship between PSD
and compressive strength.

11
Jiang and Yan evaluated the influence of PSD of fly ash on the
compressive strength of cement using grey correlation analysis and a
grey model.

Zhang and Zhang analyzed the effect of PSD of slag powder on the
compressive strength of cement using grey correlation analysis. The
plaster system can also be regarded as a grey system as this relationship
is concerned. Thus, the grey model, which is successful in the analysis
for a grey system, is expected to help to explore such a relationship in
plaster.

In this study, experiments were carried out to investigate the effect of

PSD on the compressive strength of α-HH based set plaster, focusing On
the establishment and application of a grey model. The hydration rate of
α-HH and the characteristics of pore structure of set plasters with
different PSDs were determined to elucidate the grey model. Such a
study will contribute to a better understanding on the preparation of paste
from α-HH based plaster and other cementitious materials

The plaster system can be regarded as a grey system as the relationship

between the PSD of α-HH and the compressive strength of set plaster is
concerned. The grey model does well in describing such a relationship
The 2 h compressive strength and 1 d compressive strength are derived
from the combined action of each particle fraction.

The fractions can be roughly divided into two groups according to their
contribution to the compressive strength. One works with positive effect
the particle fractions of 0–20 μm, 20–50 μm and 90–140 μm. The other
works with negative effect: the particle fractions of 50–90 μm and 140
μm. The particle fractions of 20–50 μm, 50–90 μm and 90–140 μm are
the relatively dominant factors .The variations of the compressive
strength with the increment of specific particle fractions are in general

12
agreement with the results given by the GM models. The impact of PSD
on the compressive strength indirectly results from its action on the
hydration rate and the characteristics of pore structure. It implies that the
grey model provides a potential method to evaluate the relationship
between the PSD of α-HH and the compressive strength of plaster. But
the availability of the grey model is restricted by the W/H giving
standard consistency of α-H H paste.

Figure 6. Scanning Electron Microscope (SEM) images of α-calcium

sulfate hemihydrate (α-HH) based plasters with different particle size
distributions (PSDs) after 1 d of curing.

4-Particle size distribution of clinker

The compressive strength, particle size and Rosin-Rammler distribution

parameters clearly indicated that grinding time should not be shorter than
two hours for interblending and intergrinding of GA (gasification ash)
and PC clinker.

13
It seems that an optimum grinding time can be established. For both the
GA and the interground blend of GA and PC this optimum seemed to be
in the region of two hours.

The percentage particles in the <3 µm and 3 µm to 30 µm fractions

increased with an increase in grinding time for both interblended GA and
PC clinker ground separately in the ball mill and GA and PC clinker
interground in a ball mill. Compressive strength increased with an
increase in percentage particles in both the <3 µm and the 3 µm to 30
µm fractions in the case of interblended as well as interground of GA
and PC clinker Interblending of GA and PC clinker in the mixer showed
that the percentage particles<3 µm did not increase significantly with an
increase in grinding time of the individual constituents. The compressive
strength for the interground material was slightly more after 28 days for
a higher percentage particles <3 µm.

Fineness has a great effect on 2 days strength. In late ages, strength is

affected more by the amount of coarse particles rather than fines. When
the amount of (32 to 35) µm fraction in the PC 42.5 R sample was
increased by 20%, a 13% improvement in 28 days strength was obtained.
Addition of the 25 µm fraction into PC 42.5 R changed the steepness of
the particle size distributions and reduced the Blaine SSA values.
However, 28 days strength was improved by 5% when compared with
PC 42.5 R. In particular, early strength was affected positively due to
increased homogeneity of size distribution .

The fine and coarse tails of the distribution have different effects on
strength. If both ends are minimized and the distribution is made more
uniform, high strength values can be obtained. Considering water
demand and setting characteristics, some operational parameters in the
separation process can be rearranged to obtain higher strength products

14
As a suggestion; separate marketing of filter product may be more
economic rather than mixing it with separator product, when the
obtained results of this study about the effects offines are considered.

Figure 7.Compressive strengths of PC 42.5 R, -20+5 fraction and

samples including varying amounts of-20+5µm.

5-Effects of size fraction on composition and fundamental properties

of Portland cement

Cement mortars were prepared at cement to sand ratio of 1: 3 by mass

and the flowabilities of obtained mortars were controlled in the range of
220–230 mm by adjusting water addition .The mortars were cast into 40
* 40 * 160 mm moulds. After cured at 20 ± 1C and R.H. 90% for 24 h
the specimens were demoulded and cured in lime-saturated water at 20 ±
1 C. Compressive and flexural strengths were tested at 3 days and 28
days according to EN 196-1.

From Fig( 6) it can be seen that the compressive and flexural strengths
of each cement fraction mainly depend on its mean size Among the eight
tested fractions, the cement fractions falling into the range of 8–24 μm
( = 13.19 μ m and 8.24 μ m) have acceptable 3 days strengths
and highest 28 days strengths. It can be concluded that cement fractions

15
in the range of 8–24 l m contribute most to the properties of Portland
cement.

6-The effect of particle size distribution on the properties of blended

cements incorporating GGBFS and natural pozzolan (NP)

Figure 8.Strengths of cement mortars prepared by different

Portland cement fractions at flowability of 220–230 mm (a)
compressive strength and (b) flexural strength

Products of intergrinding and separately grinding do not have the same

particle size distributions at the same Blaine values. This means that
during intergrinding, different ingredients do not show the same
behaviour as in the case of separate grinding. Therefore, it was
understood that during intergrinding some interactions occur between the

16
particles of different ingredients of blended cements as mentioned by
Erdogdu et al .It was found out that the interactions between the
ingredients in intergrinding is much stronger for coarser particle size
ranges since the difference between the particle size distributions of the
products of different grinding types is higher at those levels GBFS is
harder than clinker and therefore more difficult to grind.

Thus, when clinker and GBFS are interground, the finer portion of the
blended cement is mostly ground clinker whereas the coarser portion is
mostly GGBFS. This can be attributed not only to the action of the
grinding media in the mill but also to the abrasive effect of harder GBFS
particles on clinker particles.

On the other hand, a mineral admixture which is softer than clinker

would result in an opposite interaction. That is, the mineral admixture
will be more in the finer portion and clinker will remain relatively
coarse, for a given fineness, thus improving the durability of the mortar
In the separately ground blended cements, with an increase in the
amount of material above a specific size, the compressive to the different
grindability characteristics of the different materials.

17
Table 1. Compressive strength o f PPC and blended cement specimens
(MPa)

It was observed that specimen C gave slightly better results compared to

others. For the same grinding method and mineral admixture content, the
heat of hydration of the finer specimens are higher than those of the
coarser ones and for the same fineness and grinding method, increasing
the mineral admixture content results in reduced heat of hydration.
Separately ground blended cement had lower heat of hydration than the
interground ones and PPC (Pure Portland cement)

The compressive strength of all mixes studied decreased with an increase

in w/c ratio at all ages. For the two w/c ratios considered ,Use of
GGBFS in the mixes decreased the strength at early ages but showed
increased strength development at 28 days. The 30% GGBFS mix
achieved a higher compressive strength at all ages than both the PC
control and the 70% GGBFS mix. The reason for this may be attributed

18
to the high cement contents associated with the mixes. For 30% GGBFS
mixes, sufficient quantities of alkalies may be liberated leading to a more
rapid hydration of the relatively small quantity of the GGBFS Varying
the PSD of the GGBFS samples by keeping the slope value (n) constant
and increasing the position parameters ( xo ) decreased the compressive
strengths of the mortar mixes.

The reason for this is thought to be caused by the increases of the

position parameter of a GGBFS that are associated with reductions in the
GGBFS fineness. Very little effect was observed on compressive
strength development from varying the size range of PSD (i.e., varying n
at a constant xo) of the GGBFS samples. However, at the 70% level of
replacement, and for both w/c ratios considered the GGBFS mix
containing the sample with the widest range of distribution (i.e., n = 1.2)
showed the highest strength at 28 days of age .The results suggest that
higher-strength concrete or mortar may be attained at 28 days when the
GGBFS amount selected is 30% as opposed to 0 or 70% and when the
PSD of the GGBFS are characterized by R-R parameters of Xo = 15.00
μm and n = 1.2 .

The particle size of the cement clinker and the fly ashes decreased with
increasing grinding time. The median particle size for the cement clinker
after 2 h of grinding was 13.0 μm, and decreased to 4.0 μm after 10 h of
grinding. The median particle size for the Genesee, Lingan and
Sundance fly ashes decreased from 21.2, 14.0, and 12.4 km to 7.7, 6.7,
and 6.5 μm after 2h of grinding, and further decreased to 3.8, 3.8, and
4.1 μm, respectively after 10 h of grinding. For the fly ashes, the particle
size decreases were most significant during the first 2h of grinding. After
2 h of grinding, most of the large particles had been crushed so that all
the particles were less than 65 μm, and more than 60% of the particles

19
were less than 10 μm.. Further increase in the grinding time was less
effective in increasing the particle fineness.

Compressive strength of pastes is presented in Table 2. The compressive

strength of blended cement paste decreased with an increase in the
replacement of fly ash. When fly ash was classified to a reasonably fine
fly ash, the rate of compressive strength gain of the blended cement
pastes was significantly improved and this conformed with other
research studies In fact, the compressive strengths of the CFA(a
classified flyash) paste at 90 days were significantly higher than those of
OFA(an original fly ash ) paste and were only slightly lower than that of
the PC paste at the same age. This was the result of the packing effect of
fine fly ash. The small and spherical fly ash particles filled the voids or
airspaces and increased the density

The smaller particle size of fly ash with a higher surface area and glassy
phase content also improved the pozzolanic reaction Therefore, the CFA
made the blended cement paste more homogeneous and denser as well as
having a higher pozzolanic reaction than the one containing the original
fly ash, and this resulted in an increase in the compressive strength.

Table 2. Compressive strength and percentage of compressive strength

of pastes

20
7- Particle size distribution of limestone
The compressive strengths on days 1 and 28 after casting the mortar with
the cement systems blended with 5% wt. limestone particle size (53 μ m,
25 μ m, or 3μ m) were examined (Fig. 9). The measured compressive
strength of the original cement at 1 d was 18.3 MPa and at 28 d, it was
65.0 MPa. The coefficient variance was less than 1% for all tested
systems. The ratio between the compressive strength of the blended
cement system to the strength of the original cement system (without
added limestone) is presented.
At 1d, a good correlation is clearly observed between the blended
cement‘s compressive strength and the surface area of the blend. The
highest compressive strength was observed for the blended limestone
system with the greatest surface area (CC3 μ m), while the system with
the least amount of surface area had the lowest strength (CC53 μ m).

In addition, the particle system with the greater surface area was 4%
stronger than the original cement system, despite the reduction in the
active component (i.e., clinker) in the mortar. Such improved
compressive strength at 1 day of age can be attributed to the increased
number of nucleation centers created when limestone is added to cement
The porosity of the different systems with and without limestone
replacement was measured by image analysis using TESCAN VEGA3
Control software at 1 d. 15 SEM images of each one particle-size
system, original cement, CC3 l m, CC25 l m, and C53 l m were
analyzed. The estimated porosity values measured by the image analysis
were 7.65%, 11.70%, 13.97%, and 9.16% for the CC3 l m, CC25 l m,
CC53 l m, and the original cement, respectively. Based on these results,
a greater volume of pores was displayed for blended cement with large
size limestone particles of 25 lμ m, and this was even more pronounced

21
for the 53- l m particles compared with the original cement. However,
for the fine particle blended cement (CC3 μ m), the porosity was even
lower than that of the original.

Figure 9. Compressive strengths (days 1 and 28 after casting) of mortars

in which the cement was replaced with 5% limestone powder with mean
particle size of either CC3μ m, CC25 μ m, or CC53 μ m

This finding correlates strongly with the compression strength results at

1 day, exhibiting a reduction in strength for the CC25 μ m and CC53 μm
blended cement systems compared with that of the original cement.
Furthermore, a greater volume of pores was analyzed in the original
cement system compared with the blended limestone cement system with
the 3μ m fine particles, indicating that the fine-particle blended cement
system had a higher hydration rate, which decreased the porosity
by1.51% compared to that of the original cement.

These findings correlate well with the Rietveld quantitative phase

analysis results which revealed greater clinker components for the

22
blended cement with large particle limestone (CC53 μm) compared with
the original cement and fewer clinker components for the fine-particle
blended cement system at the ages of 2.5 h and 1d. Indeed, the reduction
in clinker components indicates a higher degree of hydration, which
results in the greater compressive strength of the fine-limestone blended
system at the age of 1day.

This is in contrast to the increase in clinker components, which indicates

a lower degree of hydration, resulting in the reduced compressive
strength of the large limestone blended system at the age of 1 day.
Compressive strength was also measured 28 days after casting (Fig. 9),
but the relationship between the surface area of the blended cement
powder and compressive strength is not as straightforward as that which
was observed 1 day after casting.

Table 3. Mean particle size and surface area of the tested powders.

At day 28 after casting, the strongest mixture was the cement blend with
the limestone whose surface area was similar to that of the original
cement (CC25 μ m, Table 3). Both of the other limestone particle systems
(CC3 μm and CC53 μ m) exhibited lower strength values that were more
pronounced in the mixture with the fine limestone powder.

It is believed that such reductions in the strength values of the large and
fine limestone systems are due to the opposing mechanisms discussed
before of increased packing density for the larger particle systems with
fewer nucleation centers opposed to the many nucleation centers, but with

23
lower packing density due to agglomeration of the fine particle system. It
can be concluded that the effect of the surface area on the hydration rate
had a more significant effect on the properties of the mortar after 1 day,
as was also shown by Kumar et al. On the other hand, decreasing the
interparticle spacing and increasing the packing density had a higher
effect on the properties of the mortar after 28 days.

Therefore, it is expected that greater compressive strength can be

achieved after 1 day and also after 28 days by partially replacing the
original cement with limestone comprising a combination of several
particle sizes (larger than and smaller than the median cement particle
size) in the same powder.

8- new gap-graded particle size distribution

Fig. 10A shows that the 3 d and 28 d compressive strengths of the
reference cement(prepared by co-grinding)are 11.3 MPa and 29.6 MPa,
respectively. In contrast, both 3 d and 28 d compressive strengths of the
gap-graded (intermediate sizes) blended cements increase significantly
and can be comparable with those of Portland cement.

For instance, although using the same mixture proportions (25% cement
clinker, 36% BFS and 39% fly ash), the 3 d and 28 d compressive
strengths of the BCF cement are 19.3 MPa and 41.8 MPa, respectively,
which are increased by70.8% and 41.2% compared with those of the
reference cement. Fig. 11B demonstrates that there is no obvious
difference in flexural strength between gap-graded blended cements and
Portland cement.

24
Figure 10. Strength of mortar prisms with gap-graded blended cements
(a) Compressive strength. (b) Flexural strength.

9. PSD effect on other properties of cement

1-Packing Density

The variation in packing density with calculated SSA of various binaryand

ternary binders is shown in Fig. 12. Given their higher SSA values, blended
cements were shown to have higher packing densities compared to the
control mixture with 100% OPC. In the case of binder systems with SSA
lower than 1600 /kg, the increase in SSA resulted in an improvement in
the packing density of the granular skeleton. On the other hand, for
SSA>1600 /kg, this tendency was reversed, and the packing density
decreased with further increase in the SSA of the binder.

For example, the increase in SSA from 425 to 1600 /kg led to an
improvement in packing density from 0.58 to 0.73, while a further increase
in SSA to 2200 /kg reduced the packing density to 0.62. The
incorporation of high content of SF can lead to an increase in the inter-
particles distance due to the loosening effect of fine particles .The use of
excessive fine particles can push the larger particles apart thus resulting in a

25
lower packing density and higher water demand to fill the voids between
solid particles. Yu et al. reported that the interparticle forces can become
relatively large when the particle size decreases, which can lead to a
decrease in the packing density.

Therefore, as in the case of water demand, there exists a threshold content of

SF replacement to enhance the packing density. As indicated in Fig. 11,
binder systems with SSA ranging from 1000 to 1600 /kg can exhibit
packing density greater than 0.66 compared to 0.58 for binder with 100%
OPC.

Figure 11.Effect of SSA of blended cements on packing density of

binders made with 0.12% HRWRA.

2- Fluidity of cement

The n value was found by NLSF (explained before) methods. There was
a tendency that the fluidity of cement pastes increased as n value
decreased, i.e., as particle size distribution broadens. However, as there
was an influence due to other factors like the particle shape and the
surface roughness, there was some deviation within a small range.

26
 3- Setting Time
The setting of cement is controlled by the formation of a network of
partially hydrated cement particles connected by hydration products
which can resist a compressive force. In the model, set is determined as
the time or degree of hydration required to frist form a percolated
pathway through the 3-D microstructure consisting of cement particles
connected to one another either by CSH gel or ettringite table 4 reports
the results obtained for the three different/c ratios and the two cement
PSDs. Both hydration time and degree of hydration are reported to
separate the effcts of hydration kinetics from microstructural
considerations. Thus, even though the finer cement requires less time to
achieve set due to its increased hydration rate, it actually requires
more hydration, as more particle-to-particle bridges need to be built to
form a percolated pathway.

Simulation result is consistent with a set of rheological measurements

which indicated that for a C3S cement with the smallest particles
removed, less hydration was needed to achieve set than with the original
C3S cement. For the w/c=0.5 systems, as shown in Table I, executing the
simulation for dispersed cement particles resulted in small increases in
both the time and degree of hydration needed to achieve set, as more
hydration is needed to link the particles when they are initially dispersed
further apart.

This microstructural observation may partially explain the retardation

generally observed when using water-reducing agents or
superplasticizers, in addition to any chemical effects these admixtures
may produce. As the w/c ratio is increased, the difference in setting
times between the 5 μm > and < 30 μ m cements becomes more

27
significant (several hours for w/c=0.5 vs. about 30 min for the two
lower w/c ratios).

Table 4. setting properties of cement paste

4- Heat Release

Naturally, the finer cement hydrates more rapidly, resulting in a higher

initial rate of heat release as shown in Fig. 12. For w/c=0.3 cement
pastes, however, after 5000 cycles of model hydration, the cumulative
degrees of hydration (Table 5) and heat released are nearly equivalent.
For many applications, the avoidance of a rapid initial heat release is
beneficial in limiting the development of thermal stresses and
minimizing early-age cracking problems.

Thus, this is one area where the use of a coarser cement may offer a
performance benefit relative to a finer one For the w/c=0.5 cement
pastes, even after 5000 cycles of model hydration, the degree of
hydration of the coarser cement still lags far behind that of the finer
cement, 0.83 vs. 0.95. This suggests that in conventional concrete the
finer cements denitely offer a performance benefit in terms of an
enhanced degree of hydration.

28
Table 5. Porosity of Cement Pastes after 5000 Cycles of Hydration

Figure 12.Cumulative heat release for hydration under isothermal conditions

for w/c=0.3 cement pastes.

5- Capillary Porosity Percolation

The percolation properties of the phases in cement paste have been

examined previously using computer model. In that initial study, based
on a simple model of C3S hydration only. a percolation threshold of

29
 about 18 % was identified for the capillary porosity phase Using the
most recent version of the NIST microstructural model.

Fig. 13 presents results for the two different cement PSDs at the three
different w/c ratios examined in this study. One can clearly see that the
cement PSD has a significant effect on the capillary porosity at which
depercolation occurs. This topic is being explored further in current
research and will be the topic of an upcoming paper .With a coarser
cement, the average interparticle spacing is larger, so that more
hydration is needed to close of the capillary porosity. Compared to the
effects of PSD, those of w/c ratio are minor. For the w/c=0.5, PSD= <
30 m> system, the model is unable to hydrate the cement sufficiently to
achieve depercolation of the capillary porosity. But, even in this case,
the percolation curve is symptotically approaching those of the two
lower w/c ratios. In a general, the percolation threshold for the < 30 m>
systems is about 18% while that for the < 5 m> systems is about 22 %.
Forthe w/c=0.5 systems, the effects of occulation/dispersion on the
capillary porosity percolation were negligible, as the data sets for the
dispersed systems(not shown) basically overlapped those shown for the
occulated ones in Fig. 13. Previously, this depercolation has been
discussed in terms of the curability" of the concrete .In a cement paste,
once the capillary porosity depercolates, the imbibition of water to
replace that lost due to chemical shrinkage during hydration slows
significantly, as transport shifts from being dominated by the capillary
pores to being controlled by the much smaller gel pores in the CSH.

Thus, the longer it takes for the capillary porosity to disconnect, the
longer one has to continue to add water to the interior of the concrete.
For example, for the w/c=0.3 cement pastes, depercolation occurs after
32 hours and 250 hours of hydration for the < 5 m> and < 30 m>

30
systems, respectively, implying an increased ―curability" for the coarser
cement systems. This change in percolation threshold could also have
major effects on diffusivity and chemical shrinkage in these systems.

Figure 13: Model results for capillary porosity percolation for cement
pastes.

10. Improving Particle Size Distribution in Cement Paste

The existing mathematical models of ideal particle size distribution,

which originated from aggregates for mortar and have been applied to
mortar and concrete production, did not cater for the powder phase and
hence is not directly applicable to cementitious paste mixes where the
powder phase plays an important role while the aggregate phase is
absent. Modifications to the existing equations are necessary. A new
equation of optimal particle size distribution has been developed in this
paper. The proposed equation has been verified experimentally based

31
on cementitious paste mixes produced by blending superfine cement
(SFC) with ordinary Portland cement (OPC). The particle size
distribution of cementitious paste blended with SFC was shown to be
closer to the optimal particle size distribution. The wet packing density,
flowability, rheology and strength performance of the cementitious
paste mixes were measured. Experimental results have demonstrated
improvement in properties by blending with SFC, which rendered the
particle size distribution in cementitious paste closer to the optimal.
Subject to further investigations to confirm its accuracy, the authors
advocate utilization of the proposed equation of optimal particle size
distribution for mix design optimization of cementitious paste,
including cementitious grout and he paste phase in mortar and concrete.
Further research is needed to generalize the proposed equation to aid
the mix design of mortar and concrete.

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