Int. J. Miner. Process.

44-45 (1996) 395-404

Grinding technical questions of producing

composite cement
Ludmilla Opoczky
CEMKUT Co. Ltd. Budapest, Hungary

Abstract

A study has been made of the grinding of composite cements produced from clinker and two
additional interground additives such as granulated blast-furnace slag, fly ash, trass and limestone.
The grindabilities of composite cements depend on the grindability of the individual compo-
nents. In case of intergrinding the interaction of the individual components plays a positive role.
It has been stated that the particle size distribution of the ground products consisting of three
components well follow the RRSB-distribution thus enabling this type of distribution to describe
them. The particle size distribution of the “composite ground products” depends on their
grindability and nature: the easier grindable interground additives promote the formation of wider
particle size distribution. For approximately identical composition the fly ash and limestone have
more widen particle size distribution than e.g. the trass.
The presence of easier grindable components leads to wider particle size distribution and
generally to lower mixing water demand. The water demand of composite cements with
pozzolanic components is higher, especially in the presence of trass. In order to achieve standard
strength the composite cements should be ground finer than the non-blended ones.

1. Introduction

In a.ddition to conventional cements with interground additives the draft European

Cements Standard (ENV 197) also covers the so-called composite cements which
contain at least two further components in addition to clinker and gypsum. In cement
manufacturing practice these components are normally pozzolanic materials like trass
and fly ash, latent hydraulic (granulated blast-furnace slag) or limestone. Nowadays
these mterground additives are either added to the grinding process in measured
quantities or interground with the cement clinker. An interground additive like limestone
is designated inert or quasi inert; during the cement hydration it shows little or no
reaction with the cement constituents. The main role of the limestone in the cement is
that of a filler.

0301-7516/96/$15.00 0 1996 Elsevier Science B.V. All rights reserved

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396 I.. Opoczky/Int. .I. Miner. Process. 44-45 (1996) 395-404

Table 1
Test materials and their proportions in composite cements K, to K,
Material/composition (wt.%) Designation

Starting materials
Clinker KL
Blast-furnace slag S
Fly ash F
Trass Tr
Limestone K

“Composite ground malerials”

1.09 S+ 1.25 Tr+ 1.25 F+ 1.75 K I 35 (ENV 197/as at 1989)
68.5% KL + 17.5% S + 14.0% F K,
68.5% KL+ 17.5% S + 14.0% Tr K2
72.5% KL+ 17.5% S + 10.0% K K3
75.1% KL+ 14.5% F+ 10.4% K K4

As composit cements are generally produced by intergrinding, their quality is also

affected by the particle size distributions of the individual components produced during
grinding. The relationships between the grinding properties and the quality of composite
cements made from three components (max. 35 wt.% interground additive content) are
investigated below.

2. Test materials and investigative methods

The experiments were carried out in a laboratory scale ball mill with the starting
materials shown in Table 1 and with three-component cements. The fineness of the
ground material was characterized by the Blaine specific surface area (a,) and by the

5 a S
z
b KL
KL 2
; 100”
1 K2
*
= KI
,’
-Ioolx50 -: 50-- & 3
_)
4
z TC z
z a
K _ _ .
g 0 0 f,
z 0
300 600 0 300 600
SPECIFIC SURFACE AREA as, in m2/kp SPECIFIC SURFACE AREA aJ, in ??
2/ka

Fig. 1. Grindabilities of the starting materials (a) and of the composite cements (b) as a function of specific
surface area a,. KL = clinker; S = blast furnace slag; F = fly ash; Tr = trass; K = limestone. K ,= 68.5%KL
+ 17.5%S + 14.O%F; K, = 72.5%KL + 17.5%S -t lO.O%K; K, = 68.5%KL + 17.5%S + 14.O%Tr; K, =
75.1%KL + 14.5%F+ 10.4%K.
 L. Opoczky/lnt. J. Miner. Process. 44-45 (1996) 395-404 397

particle size distribution determined by laser granulometer. The RRSB ditribution as

well as tlhe position parameter 0 and the coefficient of uniformity (n> were used for
describing the particle size distribution of the ground material. The grindabilities (W,) of
the starting materials and of the composite cements were measured with a Zeisel
apparatus. The mixing water demand (AW) was tested to characterize the quality of the
composite cements. The mixing water demand was taken to be the quantity of water
which must be added to the cement in order to obtain a cement paste of standard
consistency as definied in EN Msz 196:1990 (Hungarian Cement Standard).

10 10
PARTICLE SIZE x, in ,um

FINENES PARAMETERS

Fig. 2. Fineness and particle size distribution of the starting materials.

398 L. Opoczky/lnt. J. Miner. Process. 44-45 (19%) 395-404

3. Results

3.1. Grindability and particle size distribution

The grindabilities of the materials (with the exception of the fly ash) and of the
“composite ground materials” are shown in Fig. 1. The fly ash originaly had a specific
surface area of 453 m’/kg. The grindability of the clinker is also plotted in the two
diagrams a and b for comparison. It is clear that granulated blast-furnace slag is the
hardest to grind and that trass and limestone are easier. The grindabilities of the
composite cements are governed by the grindabilities of the individual components, but
in every case turned out to be better than the individual grindability of the clinker. The
presence of fly ash had a more favourable effect on the grindability of the composite
cement than did the same percentage by weight of trass. The grindabilities of the
composite cements were always favourably influenced by presence of limestone.
Fig. 2 contains the particel size distributions and the fineness parameters of the
starting materials including their grindabilities determined by laboratory grinding over
the same time period of 2 h. The results have confirmed earlier opinions that there is a
relationship between the grindability and the resulting particle size distrubition and
uniformity coefficient n such that the more easily ground materials generate a wider
particle size distribution than those which are harder to grind. From this it follows that
addition of the more easily ground limestone to the clinker widens the particle size
distribution of the ground material, and conversely, the addition of granulated blast-fur-
nace slag narrows the particle size distribution of the ground material @chiller and
Ellerbrock, 1992). These realionships also apply in the assessment of composite cements
although in this case the effects appear in a more complicated form.
Fig. 3 shows not only the curves for the particle size distributions of the “composite
ground materials” but also the associated fineness parameters 6, n) as well as the
correlation coefficient (r). It can be observed that the particle size distributions of the
three-component ground materials follow the RRSB distribution,
Fig. 4 shows the particle size distribution of “composite ground materials” of
different product finenesses. The fineness parameters, i.e. specific surface areas, uni-
formity coefficients and positional parameters and mixing water demand of four
composite cements of different grindabilities are listed in Table 2. It shows that
composite cement K, containing clinker, granulated blast-furnace slag and trass has the
narrowest particle size distribution and the largest uniformity coefficient of n > 0.95. It
should be noted that this composite cement was the hardest to grind. On the other hand,
composite cement K, consisting of clinker, fly ash and limestone has the widest particle
size distribution with a uniformity coefficient of about 0.84. This composite cement was
the easiest to grind. In a composite cement the particel size distribution of the ground
materials is widened more strongly by fly ash than by trass.
The particle size distributions of the clinker, granulated blast-furnace slag and

Fig. 3. Particle size distributions of composite cements with different compositions but approximately the same
specific surface area.
 L. Opoczky/lnt. J. Miner, Process. 44-45 (1996) 395-404 399

1
10

367;
:i
90

99.9
1 10 loo 500

:9
I ’ I

‘“4 Y
75
I.
FINENESSPARMETERS
90
8= in ii in
r
n2/kg /” n
________._____.*_______ _______
392 23 0.9565 0.9982
99.9
1 10 lb0 500

1
-10

2;
kl
75
90

99,9

::
‘“53

90

99,9

PARTICLE SIZE x, in
/um
400 L. Opoczky / ht. J. Miner. Process. 44-45 (1996) 395-404

a.

b.

Fig. 4. Distributions of the “composite ground materials”. (a) Specific surface area (a,) 307 m*/kg, (b)
specific surface area (a,) 356 m*/kg, Cc) specific surface area (a,) 3% m*/kg.

limestone components of the composite cement K, were also studied in detail. The
composite cement with a specific surface area of 402 m’/kg was separated into
different particle size classes with an Alpine zigzag classifier, and the quantities of
limestone, granulated blast-furnace slag and limestone in the individual fractions were
determined by derivatographic and chemical analyses or by calculation. These results
were used to make an approximate calculation of the distributions of the individual
components in the composite cement. Fig. 5a shows that the particle size distributions of
the individual components produced during grinding follow the original distributions,
i.e. the limestone, e.g. always has a wider particle size distribution than clinker or
granulated blast-furnace slag. The blast-furnace slag, which is harder to grind, becomes
 L. Opoczky/Int. J. Miner. Process. 44-45 (1996) 395404 401

Table 2
Fineness, particle size distribution and mixing water demand of the composite cements

Composition Designation Fineness parameter Mixing water

demand in wt.%

u, cm2 /kg) X(pm) n(-1

68S%KL+ 17.5Sf 14.OF K, 309 31 0.8892 25.4
362 28 0.8898 25.6
392 24 0.8896 25.4

68.5%KLi- 17SS+ 14.OTr K, 310 29 0.9617 26.0

357 26 0.9509 26.2
392 23 0.9565 26.5

72.5%Kl-t 17.5S+ lO.OK K, 301 25 0.8650 24.2

355 23 0.8560 24.4
402 20 0.8399 24.4

75.1%KL+ 14.5F+10.4K K, 306 29 0.8150 24.9

347 26 0.8448 25.0
406 22 0.8360 25.6

concentrated in the coarser fractions, the relatively easier to grind clinker tends to
become concentrated in the middle and finer fractions, while the limestone, with is
easiest tlo grind, becomes concentrated in the finest fractions. The largest percentage of
the limestone is concentrated in the finest fraction (< 5 pm), although limestone
particles are also to be found in all the other fractions (> 30 pm, lo-30 pm, 5-10
pm) investigated (Fig. 5b).

3.2. Particle size distribution and quality of the composite cements

A shady was made of the mixing water demands of composite cements with different
finenesses and particle size distributions. It is clear from Table 2 that the mixing water
demand is dependent on the particle size distribution of the composite cement and on the
nature of the interground additives. In general, the composite cements with narrower
particle size distributions had higher mixing water demands than the cements with wider
particle size distributions. The mixing water demands of these latter composite cements
did not increase in spite of the higher fineness. The mixing water demand of the
composite cement made with fly ash is higher than of the composite cement with
approximately the same uniformity coefficient but made without fly ash.
To produce cement in the 350 strength class (Msz 4702 - Hungarian Standard) the
composite cements have to be ground to a fairly high specific surface area, at least 350
m*/kg.. The differences between the composite cements with differing compositions but
with approximately the same specific surface areas appear mainly in the 3- and ‘I-day
strengths. In practice, raising the fineness to specific surface area of 400 m*/kg also
raises the. early strengths of the clinker/slag/fly ash and clinker/slag/limestone
compositions. It should be noted that last-named composition had a good consistency at
low water demand (Opoczky, 1993).
 L. Opoczky /ht. J. Miner. Process. 44-45 (1996) 395-404

1
10
25

365!
75

90

99,9 ___-+.._ _.._ 1,I _,_I . . +. .__._“_~.

._l
1 10 100 500
PARTICLE SIZE x, in ,um

COMPOSIlE CEMENT’

CLUrlXEK BLAST FURNACE SLAG LJMESTONE

 L. Opoczky/lnt. J. Miner. Process. 44-45 (1996) 395-W 403

4. Conclusions

The grindabilities of the three-component composite cements depend on the grind-

abilities Iof the individual components. However, even in the presence of granulated
blast-furnace slag, which is harder to grind, the grindabilities were always below the
grindabil:ity of clinker. The mutual interaction of the individual components therefore
plays a part during the intergrinding, e.g. the influence of the harder-to-grind blast-fur-
nace slag is reduced. This phenomenon is explained by the fact that the essentially
harder granulated blast-furnace slag particles also abrade the clinker particles with leads
to an enrichment of the clinker in the fine fractions and raises the early strength of the
composite cement.
The change of the particle size distribution is jointly influenced by the different
grindabil:ity and fineness of the components. In the early period of grinding (at lower
fineness) the components do not interact each other and the properties of the easier
grindable ones (limestone, trass) are prevailing. In this period the harder grindable
component is still present in an “unground state”. Upon progressed grinding the
breakage of blast-furnace slag particles is starting but simultaneously that of the small
ones (limestone, trass) is slowing down (due to the reduction of defects the resistance to
breaking increases and particle interaction occurs). Consequently the harder breakable
larger particles gradually approach the smaller ones. In this period the positive effect of
the particles upon one another (abrading effect, inhibition of particle interaction) is
already effective and as a consequence of this - as well as of the better fitting-together
of the different morphology particles next to one another - a “more compact”
structure is formed.
The particle size distribution of the “composite ground material” is dependent on its
grindability and nature: the more easily ground additives favour a wider particle size
distribution. For approximately the same composition the particle size distribution is
widened more by fly ash and limestone than, e.g. by trass. In general, the composite
cements with wider particle size distributions have lower mixing water demands. The
water demand of composite cements with pozzolanic components is greater, especially
in the presence of trass.
In order to provide for proper physical-mechanical properties the composite cements
- comp,ared to traditional ones - should be ground to higher fineness. When fixing
the optimal grinding fineness, the composition of the composite cement, the grinding
technical properties of the components (grindability, interaction of particles) should be
taken into account.

Fig. 5. (a) Distributions of the limestone, clinker and blast-furnace slag in the composite cement of
compositiou: 72S%KL+ 17S%S+ lO.O%K particle size distribution in accordance with DIN 66145 and
fmeness pammeter in accordance with RRSB. (b) Distributions of the limestone, clinker and blast-furnace slag
in the composite cement of composition: 72S%KL+ 17.5%S+ lO.O%K composition of the particle size
structure.
404 L. Opoczky/ Int. J. Miner. Process. 44-45 (1996) 395-404

5. Explanation of symbols

Symbol Units Designation

as m*/kg specific surface area (Blaine)
3 kJ/k Zeisel grindability
x pm position parameter
x P-Lm particle size
n - uniformity coefficient
r - correlation coefficient
R wt.% sieve residue
h grinding time
kv wt.% mixing water demand

References

Opoczky, L., 1993. Problems relating to grinding technology and quality when grinding composite cements.
Zement-Kalk-Gips, 5: 141- 144.
Schiller, B. and Ellerbrock, H.G., 1992. Mahhmg und Eigenschaften van Zementen mit mehreren Hauptbe-
standteilen. Zement-Kalk-Gips, 7: 325-334.