Subhas G. Malghan ~ and Lin-Sien H.

L u m ~

An Analysis of Factors Affecting Particle-Size Distribution of

Hydraulic Cements

REFERENCE: Malghan, S. G. and Lum, L.-S. H., "An Analysis of

Factors Affecting Particle-Size Distribution of Hydraulic Cements,"
Cement, Concrete, and Aggregates, CCAGDP, Vol. 13, No. 2, Winter
1991, pp. 115-120.
ABSTRACT: Particle-size distribution of hydraulic cements plays an
indispensable role in controlling the product quality and maintaining
reliable performance in end applications. Selection of particle-size
measurement methods is becoming increasingly complex due to the
availability of a variety of instruments based on different measurement principles. This paper discusses the primary criteria to be met
by a particle-size distribution analyzer for applications in hydraulic
cement characterization. Among the several methods available for
measuring the particle-size distribution, a light diffraction technique
was utilized to examine the effect of dispersion solvents on the resulting size distribution. Distilled water, distilled water containing a
polyacrylate surfactant, isopropyl alcohol, and a commercially available organic surfactant were used as dispersion solvents. The resulting
data are analyzed with respect to variations due to the dispersion
solvents and factors responsible for the observed variations.
KEY WORDS: particle-size distribution, hydraulic cements, dispersion in solvents, methods of size analysis, light scattering, instrument
selection, sample preparation
More than one property of hydraulic cement is relevant in
defining its characteristics. Many of these properties are related
to some of the more fundamental measurements of particles such
as mean size, size distribution, shape, concentration and form
of impurities, and surface chemical composition. The measurement of particle-size distribution constitutes one of the most
important aspects of hydraulic cement characterization because
particle size affects homogeneity, settling time, and strefigth of
the final product. Therefore, size distribution of the cement particulates can be obtained either for product quality evaluation
or for on-line measurement in process control.
In recent years, the availability of particle-size measurement
systems has increased markedly due to application of different
physical principles. The range of particle-size measurement covered by each instrument has also broadened. Some of the driving
forces for the availability of a large number of systems are: increased recognition of a need for measurement of particle-size
distribution, emphasis on quality control and reliability, and a
need for overall manufacturing cost reduction.
In response to these technical and market-driven forces, numerous particle-size measurement systems have been developed.
This paper discusses steps involved in the particle-size measurement, describes a classification of measurement methods, and

outlines criteria for selection of measurement systems. In addition, results are given for the measurement of particle-size distribution of a typical hydraulic cement in aqueous and nonaqueous liquid environment. A light diffraction technique was
used in these studies since it is not affected by density differences
of the particles.

Steps Involved in Particle-Size Analysis

Some of the requirements of the size analysis are to obtain
data in similar conditions to that existing in the process or to
meet technical specifications of the cement. This necessitates
obtaining a representative sample from a bulk lot. The second
requirement is the dispersion of particles in a chosen solvent so
that true particle size (as determined by scanning electron or
optical microscopy) is determined. Dry techniques do not require
the use of solvents for dispersion. However, as the mean particle
size of the hydraulic cement becomes smaller, dispersion-related
errors increase. For cements of particles sizes in the 1 to 100Ixm range, wet techniques are generally preferred. The third
requirement in the particle-size measurement is the appropriate
use of standard materials and procedures for material and instrument calibration. Each instrument should be checked for
calibration errors using the appropriate standard materials. The
steps involved [1] in the particle-size measurement are shown
schematically in Fig. 1. The overall measurement error is a function of the error associated with the individual steps. For hydraulic cements, errors due to chemical aspects of dispersion and
due to sampling are expected to dominate [].

Selection Criteria and Types of PSD Measurement Techniques

Selection of a particular technique for size distribution measurement is dependent on several criteria [-4]:
1. Accuracy of measurement (systematic error).
2. Reproducibility and repeatability of measurement (random
error).
3. Chemical reaction of particles with liquid.
4. Size range of application.
5. Time required for measurement.
6. Skill level of operator.
7. Cost of instrument.
Accurate measurement of particle-size distribution requires
the development of improved techniques of sample preparation
and associated measurement techniques. Systematic errors can
be minimized by enhanced precision (agreement within a set of
observations obtained as directed in a method) and repeatability

~Group leader, Ceramics Division, and chemical engineer, respectively, National Institute of Standards and Technology, Gaithersburg,
MD.
1991 by the American Society for Testing and Materials
115

This standard is for EDUCATIONAL USE ONLY.

116

CEMENT,CONCRETE, AND AGGREGATES

I Homogenization of Cement
I

I Sampllngfrom a LargeLot I
1

Preparationand

Dispersion ]

[ CalibratlonofInstrument]
l

1.-=-= I
I
Interpretationand

Conversion of Data

FIG. 1--Schematicofstepsinvolved m the measurement Qfpanic~size d~tribution.

(comparison of data obtained in a single laboratory and technique). However, reproducibility is totally dependent on precision involving comparison between laboratories and/or between
different techniques. Accuracy of the technique is enhanced when
the degree of agreement between the true and average of many
observed values increases.
Since hydraulic cements react with aqueous environment, other
solvents, especially organic solvents, can be used. However, for
ease of handling and cost effectiveness, the use of water-based
dispersants is desirable. Dispersion of cement particles in aqueous
environment can be carried out in the presence of low-molecularweight (5000 to 10 000) polyacrylates, which provide steric stabilization [5] at high pH. Examples of organic dispersants are
alcohols and commercially available mineral oil-based solvents.
The cost of the instrument, the time requirement for analysis,
and the skill level of the operator, etc, are some of the external
factors which influence the decision on the selection of instruments. The overall cost of analysis should also include those due
to the instruments, dispersion solvents, and cement samples.
When extensive cleaning between the runs is necessary, the overall cost increases. The time requirement for analysis can range
from 5 rain to several hours depending on the particle-size distribution of a specific material, instrument principle, and dispersion preparation. Instruments based on light scattering offer
high speed of operation. The selection of these instruments is
dependent on the skill level of the operator (e.g., production
environment versus research laboratory), In most cases, a reasonably well-trained operator is required.
Therefore, the question of which technique/instrument to select for a given application leads to the analysis of factors affecting particle-size distribution and specific requirements of the
process. The myriad of analysis techniques, measurement parameters, and the nominal range of application of these techniques are broadly grouped in Table 1.
Wet Versus Dry Methods

The potential for determining the particle-size distribution accurately depends on the ease with which the cement particles

can be dispersed. As the particles become smaller their tendency

to adhere to each other increases due to van der Waals and
coulombic attractive (between chemically dissimilar particles)
forces. Hence, in a dry mode of particle-size measurement, agglomeration or the tendency of fine particles to stick to large
ones cannot be easily controlled. Therefore, accurate and reproducible size distribution measurement may not be obtained
by methods based on dry particulates. In addition, accuracy of
quantitative determination of the finest size fraction is diminished
in the case of dry powders.
Though wet techniques are preferred over dry techniques, they
suffer from interactions between the particles and surrounding
solvent. When the hydraulic cement comes in contact with a
solvent, the silicates and aluminates of lime are expected to
undergo surface dissolution and thereby contributes ionic species
to the adjoining bulk solution. The extent of surface dissolution
depends on a number of characteristics of which the chemical
composition of the cement and that of the solvent are the most
important, Water, being a polar solvent, induces higher surface
dissolution than organic solvents. The resulting electrical double
layer properties of a given cement particle are expected to be
different in water than in organic solvents. The electrical double
layer formation and the resulting dispersion properties are described elsewhere [6].

Size Distribution Measurement in Wet Dispersions

The primary goal of the measurement of particle-size distribution is to determine the absolute size distribution of the particles in the cement sample. Therefore, the formation of agglomerates should be prevented. The major steps involved in the
preparation of highly deagglomerated dispersions in aqueous and
nonaqueous solvents are shown in Fig. 2.
In the case of hydraulic cement, obtaining a representative
sample for size distribution measurement involves the use of a
spinning riffler [2]. Since cement is a highly heterogeneous maTABLE 1--Techniques of particle-size analysis and a typical
measurement parameter 1~-41

Techniques

Measurement
Diameter

Nominal Range,
Ixm

Image
Optical
Electron

Image

Mechanical sieving
Dry
Wet

Sieve/mechnical

Sedimentation
Elutriation
Gravity
Centrifugal

Dynamic/
Stoke's

1-100
0.1-130
0.05-100

Zone sensing
Optical
Resistivity

Geometric

0.01 - 500
0,05-500

Hydrodynamic
chromatography

Geometric

0.0t-1.0

Brownian motion

Geometric
Equivalent
spherical

0.01-I

Other
Gas adsorption
Gas permeability
Mercury intrusion

This standard is for EDUCATIONAL USE ONLY.

0,5-1000
0.01 - 10
>10
>2

0.05-50

O.1-40
O.1- 200

MALGHAN AND LUM ON HYDRAULIC CEMENTS

Dry Sample Preparation ]

[ Wetting and Mixingwlth a Surfaetant ]

!

-r.=-.-oo

I Measurementof Slze Distributlon 1

I

[ ,,Presentationof Data [
FIG. 2--Sequence of steps involved in the measurement of particlesize distribution by wetting the cement.
terial consisting of chemical components of various sizes and
densities, segregation is a serious issue. Therefore, care should
be exercised in the division of a bulk lot of cement sample into
subsamples. Each type of instrument requires a different weight
of the sample. Errors in sampling can be minimized by using the
largest possible subsample for analysis consistent with the sample
requirement. For fine-size cements, wet samples of higher than
the required particle concentration can be prepared, and the final
sample for size determination can be taken from this parent
sample. When dilution of the parent sample is involved, the
surfactant concentration in the final dispersion should be maintained at the same level as in the parent sample.
Wetting and mixing of the powder requires the selection of a
proper combination of the solvent and a surfactant. Organic or
inorganic surfactants [6] can be used; however, organic dispersants provide higher flexibility and more definite dispersion in
complex chemical systems. Water is a preferred solvent, though
it has certain disadvantages, such as surface dissolution, swelling,
and setting. In dilute suspensions (less than 1% by weight), the
effects of these interactions are considered to be minimum.
The selection of an appropriate dispersant requires the knowledge of surface charge and isoelectric point, pH~ep (the pH at
which the particles carry a net zero charge) of the cement particles in a given solvent. Since cement has a highly complex
chemical composition, accurate determination of pHie p by traditional electrokinetic techniques is somewhat tedious and difficult. However, based on relative weight ratios of silicates, aluminates, and other components, the pHiep can be estimated.
Also, experimental determination of the pH~ep is possible by the
application of a relatively new technique in which electrokinetic
sonic amplitude is measured [7] as a function of pH.
Ultrasonication of the slurry containing the cement particles
is an essential step in the preparation of well-dispersed suspensions. During ultrasonication, the particles are subjected to cavitation which dislodges loosely held particles [8]. Two primary
devices of ultrasonication are baths and probes. The probe is a
preferred device because it allows the application of a specific
quantity of ultrasonic power localized to the sample. Ultrasonication by the probe is completed in just a few minutes since the
power intensity is high.
The size distribution of a well-dispersed slurry is determined
by following the recommended procedure of a particular equipment. If the suspension has to be diluted, the solvent chemistry

117

should be the same as that used in the preparation of the parent

suspension. Care should be exercised to avoid settling of coarse
particles during sampling of the parent suspension.
Presentation of the data is dependent on the equipment. Most
often, the data are provided in the form of number or weight/
volume fraction. Direct conversion of data from the number to
weight/volume fraction is not possible without taking into account densities of different chemical components of the hydraulic
cement. Similarly, the size distribution data from gravitational
and centrifugal sedimentation devices is affected by different
densities of the constituting chemical components of the cement.
This is probably one of the main reasons for using the light
diffraction-based device in this study for the size measurement
of cement. Irrespective of the method of size measurement, the
resulting data can be analyzed by using a number of mathematical
models. The parameters of these models can serve the purpose
of comparing the characteristics of various cements.

Application of the Light-Scattering Method

The particle-size distribution of Portland Cement Proficiency
Sample 95 [9], distributed by the Cement and Concrete Reference Laboratory (CCRL), was determined using a light diffraction-based particle-size measurement system (Horiba LA-500)
[10]. CCRL is a research associate program at NIST sponsored
by ASTM [11]. The primary focus of this study was to examine
the influence of solvents in which the cement is dispersed. The
solvents examined were distilled water, distilled water containing
500 ppm polyacrylate (Darvan C-Vanderbilt Chemical Company) as a dispersant, isopropyl alcohol, and Sedisperse A-12 (a
surfactant manufactured by Micromeritics Corporation). 2
Dispersions of the cement were prepared by mixing cement
and the solvent in the weight ratio of 1 to 20, followed by ultrasonication (ultrasonic probe of 19 mm diameter, 30 W, total of
3 rain). The dispersion was ultrasonicated stepwise by applying
power for 1 min followed by 1 rain of cooling. This process was
repeated to give a total uttrasonication time of 3 rain. The dispersed powders were size analyzed using a procedure developed
for ceramic powders. Each measurement is an average of 25
scans, and triplicate data were obtained using three separate
subsamples from the primary dispersion. The data presented are
an average of the three measurements.
The size distribution data of the cement sample are presented
in Fig. 3. In general, all four dispersions show a bimodal size
distribution in which there is a small quantity of submicrometre
fraction and a large quantity of fraction whose ds,, is in the range
of 10 to 20 p.m. The dso is the size in micrometres through which
50% of the particles pass. The following general guideline was
used in the evaluation of the effectiveness of solvents and dispersants: the most suitable solvent-dispersant combination is one
that gives the finest size distribution. Based on this criterion,
isopropyl alcohol (IPA) appears to be the most suitable solvent.
On the other hand, Sedisperse A-12 is the least effective dispersant. Both water and water containing 500 ppm Darvan C
give similar size distributions in the fine-size range and a slightly
2Certain commercial equipment, vendors, instruments, or materials
are identified in this report in order to describe adequately experimental
requirements. In no case does such identification imply recommendation
or endorsement by the National Institute of Standards and Technology,
nor does it imply that the vendor, material, or equipment identified is
necessarily the best available for the purpose.

This standard is for EDUCATIONAL USE ONLY.

118

CEMENT,CONCRETE, AND AGGREGATES

11
10

Cement in H20

- - - Cement in H20 w / 5 0 0 ppm Darvan

9
rItc(3n
,m
0)

>
-)
c

Cement in IPA

-.-

Cement in A - 1 2

6
5

2
1

.'

.,;s"

0 ,-

1.0

0.1

10.0

100.0

Particle Diameter, microns

FIG. 3--Size distribution data of CCRL portland cement proficiency sample by using Horiba LA-500
device. The effect of four solvents is shown: (1) water; (2) water plus 500 ppm Darvan C; (3) 1PA; and
(4) Sedisperse A-12.
Another important feature of these data is that 90% of the
weight is finer than 19 ~m in the case of IPA. When using other
solvents, a coarser size distribution is observed. In addition, in
the case of IPA, more fines are observed at the finer end of size
distribution. A possible reason for IPA's superiority in this particular case is its inertness to surface reactivity with cement particles.

different dgo. The overall differences in the entire size range are
presented in Fig. 4. These data, in terms of cumulative size
fraction, show that IPA is by far a superior solvent. The dg0, ds0,
and d25 data summarized in Table 2 show specific differences in
the size distributions. The size distribution data are presented in
terms of weight fraction by assuming that density variation between the particles is negligible.

tO0
Cement in H20

90
-

Q)

.E

ta_
.Cn
, m

Q)

80
70

"'"

Cement in H20 w / 5 0 0 ppm Darvan

Cement in IPA

." t/~/t

b,'

---- Cement in A - 1 2

." t~,/

60

." .i/1P

50

:;7

>

-.a,.,a

/ ~
/ Y
..' / /

20

- f~
jQ

1"

10

O,
0.1

1
1
1.0
10.0
Porticle Diometer, microns

I
100.0

FIG. 4--Size distribution data of Fig. 3 presented in the form of cumulative weight fraction to highlight
differences in the entire size distribution,

This standard is for EDUCATIONAL USE ONLY.

MALGHAN AND LUM ON HYDRAULIC CEMENTS

TABLE 2--Effect of solvent on the dispersion of a cement sample

(CCRL Portland Cement Proficiency Sample 95) during particle-size
determination by Horiba LA-500.
Size in Micrometres Through
Which the Specific Weight
Percent Passes

IPA

d9o

dso

dz5

19.0

9.0

3.6

Water

26.0

12.0

7.5

Water + Darvan C

30.0

13.0

7.5

A-12

30.0

it.0

5.0

Bimodal distribution obtained for this sample could be the

result of the application of both ultrasonication energy and solvents for dispersion. Fine, submicrometre particles loosely adhered to coarse particles tend to dislodge by the application of
a combination of mechanical (ultrasonication promoting cavitation) and surface chemical (steric in the case of IPA and A12) dispersive forces. During ultrasonication, the particles are
subjected to cavitation which separates loosely held particles.
Once the particles are separated, they are kept dispersed by the
steric forces imparted by the adsorbed hydrocarbon molecules
of IPA. If the size distribution is carried out by dry sieving, the
bimodal distribution may not be observed in such detail.
Repeatability of the size distribution data is shown in Figs. 5
and 6 for IPA and Sedisperse A-12, respectively. These data
show that, irrespective of the solvent used, the repeatability is
excellent in the case of fine-size fraction (<1.0 ~m). However,
there is a slightly larger variation at the coarse-size fraction when
using IPA; whereas, for Sedisperse A-12, the variation is neg-

ligible. Since the final selection of a solvent-dispersant should

include the evaluation of both accuracy and repeatability, a thorough evaluation of those factors is required in a round-robin
characterization program.

Summary and Conclusions

Major steps involved in the measurement of particle-size distribution are sampling and sample preparation (including dispersion). Errors in these steps are often responsible for lack of
repeatability and reproducibility. A large number of systems are
available that provide data over a wide range of size distributions.
The selection of instruments for a given application depends on
a number of criteria. In recent years, systems based on lightscattering principles are widely used for particulate systems.
Dispersion of hydraulic cement particles in a suitable solvent
is an excellent way to ensure the determination of accurate size
distribution. Selection of an appropriate level and type of ultrasonication and dispersion parameters is the key factor in obtaining near-true size distribution data. The selection of solvents and
dispersants for hydraulic cements can be systematized if surface
charge and pHi~p data are available. In the absence of such data,
four solvents were evaluated by using the CCRL portland cement
proficiency sample. The size distribution data from a light-scattering device indicated that the cement sample has a bimodal
size distribution irrespective of the sotvent-dispersant composition. However, the data from isopropyl alcohol showed that the
overall size distribution was finer. Independent verification of
these size distribution data with those from scanning electron
microscopy is required to test their validity. A slight variation
was observed at the peak of the coarse end of the PSD in the
replicate tests using IPA. In the case of Sedisperse A-12, this
type of variation was negligible.

CEMENT IN IPA
1
0

Sample I

9
C
cD
I,
cljn
{D

Sample

--'- S a m p l e 3

6
,5

.//

>
-

0
O.

1.0

119

'ii,
10.0

100.0

Particle Diameter, microns

FIG. 5--Repeatability of size distribution data by using Horiba LA-500 for cement in 1PA.

This standard is for EDUCATIONAL USE ONLY.

120

CEMENT, CONCRETE, AND AGGREGATES

CEMENT IN A - 1 2
11
10

Sample

- Sample

c-

- - . - S a m p l e .3

b..

o~
,!

f.

/Z

3~

"

>
-{3
c"

~
~

O.1

1.0

10.0

100.0

Porticle Diometer, microns

FIG. 6--Repeatability of size distribution data by using Horiba LA-500 for cement in Sedisperse A-12.

References
[1] Allen, T. and Davies, R., "Modern Aspects of Particle Size Analysis," Advances in Ceramics, Vol. 21: Ceramic Powder Science,
G. L. Messing et at., Eds., American Ceramic Society, pp. 721746.
[2] Allen, T., Particle Size Measurement, 3rd ed., Chapman and Hall,
New York, 1981.
[3] Modern Methods of Particle Size Analysis, H. G. Barth, Ed., Wiley
Interscience, New York, 1984.
[4] Pohl, M., "Selecting a Particle Size Analyzer: Factors to Consider,"
Powder and Bulk Engineering, Vol. 4, No. 2, February 1990, pp.
26-29.
[5] Napper, D. H., Polymeric Stabilization of Colloidal Dispersions,
Academic Press, Inc., London, 1983, pp. 18-30.

[6] Parfitt, G. D., Dispersion of Powders in Liquids, Chapters 1 and

2, Applied Science Publishers, 198t.
[7] Malghan, S. G. and Lum, L.-S., "'Factors Affecting Interface Properties of Silicon Nitride Powders in Aqueous Environment," in
Ceramic Powder Science, G. L. Messing, et al., Eds., American
Ceramic Society, September 1990.
[8] Anonymous, "Branson Sonifer," Bulletin 200-214-082, Branson Ultrasonics Corp., Danbury, CT, 1989.
[9] Samples obtained from Pielert, J. H., Cement and Concrete Reference Laboratory, Building Materials Division, NIST, July 1990.
[10] Anonymous, "Horiba LA-500 Laser Diffraction Particle Size Analyzer," Bulletin HRE-3610B, Kyoto, Japan, January 1990.
[11] Pielert, J. H., "Construction Materials Reference Laboratories at
NIST," ASTM Standardization News, December 1989, pp. 40-44.

This standard is for EDUCATIONAL USE ONLY.