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10.

Cement Additive
Technology
C E M E N T T E C H N O L O G Y N O T E S 2 0 0 5 117
1 0 . 1 I NT R ODUC T I ON
1 0 . 2 GR I NDI NG A I D ME C HA NI S MS
1 0 . 2 . 1 I NT R ODU C T I ON
1 0 . 2 . 2 R E HB I NDE R E F F E C T
1 0 . 2 . 3 A GGL OME R AT I ON A ND C OAT I NG
1 0 . 2 . 4 MI L L R E S I DE NC E T I ME
1 0 . 2 . 5 S E P A R AT OR P E R F OR MA NC E
1 0 . 2 . 6 C E ME NT P E R F OR MA NC E
1 0 . 3 I NF L UE NC E ON MI L L P E R F OR MA NC E
1 0 . 3 . 1 I NT R ODU C T I ON
1 0 . 3 . 2 MI L L C OAT I NG
1 0 . 3 . 3 MI L L HOL D- U P
1 0 . 3 . 4 S P E C I F I C C ONS T R A I NT S
1 0 . 4 C US T OME R OB J E C T I V E S
1 0 . 5 P OT E NT I A L B E NE F I T S
1 0 . 5 . 1 I NT R ODU C T I ON
1 0 . 5 . 2 R E DU C E D K WH/ T ONNE
1 0 . 5 . 3 I NC R E A S E D P R ODU C T I ON
1 0 . 5 . 4 R E DU C E D R U N HOU R S
1 0 . 5 . 5 I MP R OV E D MAT E R I A L S HA NDL I NG
1 0 . 5 . 6 I MP R OV E D C E ME NT P E R F OR MA NC E
1 0 . 5 . 7 E C ONOMI C S
1 0 . 6 E NV I R ONME NTA L I S S UE S F OR A DDI T I V E S
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10.1 INTRODUCTION
Cement grinding additives have been used since the early
1930's. One of the first references to the use of grinding aids
was given in a British patent in 1930, where the addition of
small amounts of resins was defended.
The development of "TDA" started in the early 1930's and
achieved U.S. patent coverage in 1935/36.
HEA2 was patented in 1965 and the use of formulated quality
improvers began in the early 1970's.
The objective of today's modern grinding additives is to assist in
minimising manufactured cost, while maximising cement
quality. There has been continued research and development
activity over the last 60 years or so together with analysis of
their influence on the cement grinding process and resultant
quality characteristics. However, reported results, even for
apparently "similar" products in "similar" circumstances, have
been quite wide ranging. As the understanding of their use
continues to improve, so the probability of successful
applications also improves. This requires a continual
improvement in our knowledge of the mechanisms involved as
well as increased awareness of our customers' grinding plant,
cement performance characteristics and their market criteria.
Therefore, to ensure success in the application of cement
grinding additives, we need to assess:-
- the mechanisms of additives
- the influence on mill performance
- the economics involved
- the quality characteristics and customer objectives
- any environmental concerns
These are discussed in the following sections in more detail.
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10.2 GRINDING AID MECHANISMS
10.2.1 INTRODUCTION
The mechanisms by which additives influence grinding
performance have been discussed in the literature for many
years and reference is usually made to the role of:-
- decrease in the resistance to comminution (so-called
Rehbinder Effect)
- the prevention of agglomeration and mills internal
coating
- a decrease in mill residence time
- an improved separator efficiency
In addition, there is reference to various influences on the
cement properties (See Section 10.3).
The Rehbinder effect has increasingly become seen as less
important with the majority of emphasis placed on the de-
agglomeration and coating. The influence on powder flowability
and the reduction in residence time is often discussed but
without sufficient assessment of the quantified effects on
grinding efficiency.
10.2.2 REHBINDER EFFECT
According to Rehbinder's hypothesis, grinding additives are
absorbed on to the surface of particles, including into
microcracks, thereby making crack propagation easier by
reducing their valency forces, i.e. prevention of rejoining of
cracks as they form.
Theoretically a reduction in the surface energy and a consequent
reduction in the critical stress of crack propagation would be
expected in the presence of grinding aids. This would then be
expected to produce an increase in the impact breakage.
However this assumes that the velocity of additive absorption
takes place at a similar rate to that of crack propagation.
Increasingly, it is recognised that the velocities of crack
propagation are very much higher than the velocities of grinding
additive diffusion. Hence it seems unlikely that the absorption
of additives can positively influence the rate of impact breakage.
Indeed, a number of researchers have found this to be the case.
However some workers (e.g. Moothedath and Ahluwalia -
Powder Technology, 71, (1992), 229-237) found that the surface
hardness of materials, and their subsequent resistance to
attrition, changes when grinding additives are present. They
concluded that attrition was increased when additives were used
in low dosages but reduced at higher concentration (probably
because of lubrication).
10.2.3 AGGLOMERATION AND COATING
We have already seen that, according to Rittinger, the area of
new surface produced by grinding is directly proportioned to
the useful energy input. Hence the grinding efficiency in terms
of cm
2
/j (See Section 6) is constant for any level of fineness (See
Figure 111).
However in reality the energy input increases by an amount in
excess of this as a result of the negative influences of
agglomeration and coating. As grinding progresses and grains
become smaller the attractive thermodynamic, mechanical and
chemical forces result in strong adhesions of particles. This
causes agglomeration, which limits the increase in specific
surface area, and coating of the mill internals, which results in a
reduction of the rate of breakage. (See section 6.3).
The grindability curve was discussed in Section 5 (See Figure 56).
If we assume that Eg is the energy for grinding and that Ec is
the energy lost because of coating and agglomeration, then we
can consider 3 regions of the curve (See Figure 110).
Figure 110. Grindability Curves Rittinger.
In region 1, Ec = O (or negligible), and thus the relationship
between Eg and SSA is linear (as Rittinger).
In region 2, Ec becomes increasingly high but remains below Eg.
Hence there is an increasing deviation from the Rittinger linear
relationship. Region 2 typically starts at around a SSA of 200-
250 m
2
/kg.
At the interface of region 2 and region 3 grinding in effect
ceases, Ec = Eg. In other words, the energy lost due to
agglomeration and coating equals that applied. This can happen
at around 500-700 m
2
/kg and can be referred to as the Grind
End-Point.
In region 3, Ec > Eg and no further grinding (increase in SSA) is
seen. And agglomeration is occurring.
All grinding additives contain chemicals, which neutralise the
surface charges on cement grains and shield against the inter-
particle attractive forces. This reduces the tendency for
agglomeration and adhesion to media and linings and thus the
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efficiency of grinding is enhanced. Thus, in effect, Ec is reduced.
This means that region 1 is prolonged, the deviation in region 2
is reduced and region 3 is delayed or virtually eliminated.
However additives are not capable of achieving the linear
relationship of Rittinger (See Figure 111).
Figure 111. Mill Efficiency versus Mill Exit Fineness
From Figure 111, which aims to show a typical influence on the
cm
2
/j versus SSA of an additive, we would expect the following
increases in efficiency, and hence output:-
SSA Increase in Efficiency
(m
2
/kg) %
300 5%
350 10%
400 12%
450 20%
500 30%
Thus, the effectiveness of grinding aids would be expected to
increase with increasing fineness and thus result in increasing
mill efficiency.
10.2.4 MILL RESIDENCE TIME
In Sections 4 and 6 we examined the parameters of mill
residence time, hold-up and void filling. These can be
summarised as (for steady-state):-
- the residence time refers to the mean time that
material remains in the mill
- the hold-up refers to the tonnes of material (not
media) in the mill
- the void filling refers to proportion (fractional or
percentage) of the voidage in the media filled by
material
The simplest way to compare material levels in the mill is to use
the void filling, since the others require some qualification by
other parameters (such as tonnes/hour, circulating load, mill
size, media tonnages).
In Section 6 we saw that there is an optimum filling of 85% of
the media voids occupied by material. At this filling the grinding
efficiency is maximised and both higher and lower levels will
result in a reduction in the grinding efficiency (See Figure 92).
The chemicals contained in grinding additives reduce the
tendency for agglomeration and coating (See Section 10.2.3) and
as a result also reduce the powder cohesion and therefore
increase the flowability.
Many factors influence the material void filling (See 10.3), but
an increase in material flowability will reduce the head of
material required in the mill to discharge from the outlet.
Hence, for other parameters constant, the void filling is reduced
by the addition of a grinding aid. Hence the residence time and
hold-up are also reduced.
This reduction in residence time was considered in detail by
Frank Mardulier with the use of sodium fluorescein tracer to
assess residence time (See Section 4 and 6). Residence time
distribution curves for a mill, with and without the use of a
grinding aid is shown in Figure 112.
Figure 112. Residence Time Distribution
In this case the mean residence time was reduced by 30% (Peak
of 3.5 minutes compared to 5 minutes). This would thus
represent a 30% reduction in the hold-up and a 30% reduction
in the void filling (for constant total mill throughput and
material density).
Since many mills operate with a high filling level (i.e. above the
optimum) the application of an additive therefore moves the
filling level to the optimum (or closer to). Hence there is an
increase in the overall grinding efficiency. (See 10.3).
10.2.4 SEPARATOR EFFICIENCY
As we have already considered, separators operate by exerting a
force balance on individual particles (of which there are many)
(See Section 6). Separator efficiency is reduced for increased
loading of the separator as a result of poor dispersion, particle
agglomeration and fines entrainment. Thus it can be expected
that the improved dispersion resulting from the presence of
grinding additives should assist in the separation efficiency.
Because the Tromp Curve is significantly influenced by the
circulating load, comparisons of separation with and without
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additive should only be made at constant or similar conditions.
Such a comparison is shown in Figure 113.
Figure 113. Separator Performance.
The often lower by-pass and less pronounced fish hook (See
Section 6) means that less fines are returned to the mill and
hence their negative influence on the overall fineness balance
around the mill is reduced. Thus overall grinding efficiency can
be improved.
10.2.5 CEMENT PERFORMANCE
It is not the intention to review in detail the mechanisms of
additives on cement properties. This remains complex and only
partially understood.
We have seen that cement additives are formulated to provide
benefits to the grinding process, but many are also formulated
to additionally provide a benefit to the cement performance
characteristics, with an influence on cement hydration mechanisms.
Cement additives contain various combinations of organic and
inorganic salts. Some components are able to behave as catalysis
for the hydration reactions of C
3
S and water to produce earlier
initial set and strength. Others have retarding properties and
interact with the C
3
A, leading to the formation of stable
complexes in solution that later precipitate coating the C
3
A phase.
Such an ability to form a complex is correlated with improved
flow and set properties of cement. The inorganic and organic salts
as Na/Ca Chlorides and Na Acetate/Formate are known to be
strong accelerators for C
3
S, increasing early strengths of cement.
Other polymers are adsorbed on the surface of the cement
particles, and impart repelling charges to the particles, releasing
the water normally entrapped by the surrounding cement
particles, which can then contribute to the fluidity of the mix.
The properties of CBA additives has been researched in detail
and the role of C
4
AF in limiting overall silicate hydration,
together with the proposed mechanism of facilitated transport
for iron, at least partially explains the enhancement in strength
development. (See Figure 113a).
A comprehensive understanding of the fundamental mechanisms
involved would help in the success of applying and developing
new additives. However this assumes that there is equally a
comprehensive understanding of the influence of the many
natural cement characteristics on cement performance.
Therefore it is likely that any improved knowledge will also
have to include careful statistical analysis of data from the use
of additives in laboratory and plant studies.
The principal parameters that are known to influence cement
performance were discussed in section 1, and it is likely that
many, if not most or all, of these will also influence the
behaviour of cement additives.
If this is considered in combination with the way in which
cement performance can be judged (See Section 7), then there is
a rather complex picture.
However we continue to understand the role of additives, by,
for example, differentiating between certain clinker types and
certain additive types, e.g.
Figure 113a. The Facilitated Iron Transport mechanism of
strength enhancement by CB100.
Cement types:-
- Pure or composite
- High or low fineness
- High or low alkali
- High or low clinker SO
3
(alkali solubilisation)
- High or low D.SO
3
(availability of soluble CaSO
4
)
- High or low Free Lime
- Hard or soft burned
- Fresh or surface conditioned
- High or low C
3
A
- High or low C
4
AF
Additive types:-
- according to active components
- according to dosage
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10.3 INFLUENCE ON MILL PERFORMANCE
10.3.1 INTRODUCTION
If we conclude that grinding efficiency is principally influenced
by cement grinding additives by their influence on:-
- de-agglomeration
- reduction in void filling
then, to assess the likely influence on the performance of any
mill system, we need to assess the characteristics of the mill
system in terms of the above parameters.
In simple terms, we can expect good results of using a cement
additive where milling efficiency is significantly below optimum
as a result of agglomeration and coating, poor separator
efficiency and high void filling.
To ensure the appropriate application of a cement grinding
additive we therefore need to consider:-
- the propensity for agglomeration and coating
(including separator efficiency)
- the mill filling level (void filling)
- any specific constraints of the mill system
- current cement performance
- customer objectives
- economics involved
- environmental concerns
10.3.2 MILL COATING
The higher the degree of agglomeration and coating present, the
greater the deviation will be from Rittingers straight line
relationship for SSA versus kWh/tonne (and the poorer the
separator efficiency will be).
Agglomeration and coating of mill internals is strongly
influenced by temperature, fineness and pre-hydration.
As temperature in the mill rises the degree of agglomeration and
coating increases. Up to around 110C thus may not be a
significant factor, but at higher temperatures the negative
influence on mill output increases.
Milling temperature (See Section 4) can be expected to rise for:-
- hotter clinker
- higher kWh/tonne (either through inefficiency or
higher fineness)
- poor ventilation
- inappropriate, or absence of, water injection
Particle agglomeration and coating can also be expected to
become more severe where surface hydration occurs, e.g.:-
- high moisture input in materials
- excessive water injection
- inadequate ventilation
- nature of stored clinker (weathered)
As we have already discussed, the deviation from Rittingers law
increases with increasing fineness (at the mill exit). This will be
influenced by:-
- Product SSA target
- Mill circuit type and efficiency
- Circulating load
- Separator efficiency
Non-clinker components, such as slag (if not with excessive
moisture), sand, pfa can reduce coating whilst others, such as
limestone and some pozzolans can exacerbate the coating.
If anything, larger ball sizes appear to coat more severely.
However grinding efficiency probably reduces more rapidly
where small media become coated.
Coating often seems to be more severe where the void filling is
high (it maybe also that the filling level becomes higher with
more coating and hence less flowability). Thus, for whatever
reasons, the more severe the agglomeration and coating, the
more likely there will be substantial benefits of a grinding
additive.
It can be possible to make a direct assessment of coating during
a mill inspection (See Section 11).
The influence of these factors on agglomeration and coating will
also influence the performance of the separator in the mill
system circuit.
10.3.3 MILL HOLD-UP
As discussed previously there is an optimum void filling and
grinding additives reduce the mill hold-up and residence time,
perhaps by around as much as 20-40%. Thus the increase in
efficiency will very much depend on the existing filling level
before an additive is used. For a high void filling level of say
120%, a 30% reduction will give a new void filling of 84% (i.e.
close to the optimum level). As a result the grinding efficiency
would increase (From Figure 92) by around 7-8%.
On the other hand for a lower void filling level of say 90%, a
30% reduction would produce a new level of only 63%, which
could reduce the grinding efficiency by around 5%.
The overall influence of the additive on mill efficiency would of
course also depend on the other parameters, such as the positive
influence on the agglomeration and separation. The void filling
in the mill is principally influenced by:-
- the total mill throughput (See Figure 93)
- the media grading (See Figure 97)
- the mill ventilation rate
- diaphragm design and condition
- number of diaphragms/chambers
- separator efficiency
- volume loading
- mill speed
- mill length
- material flowability
The combination of these parameters will result in a
characteristic void filling for any given mill system. It maybe
possible to assess the void filling by careful consideration of the
above parameters or by discussion with plant personnel or by a
mill inspection (See Section 11).
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