Special reprint from Kunststoffe international 12/2006

Holger Müller

Calcium Carbonate -
Benefits of Direct Addition

Volume 96 www.kunststoffe-international.com 12/2006

Kunststoffe
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Joining

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Page 98

SPECIAL
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© Carl Hanser Verlag, München. 2006. All rights including reprinting, photographic reproduction and
translation reserved by the publishers.
■ EXTRUSION

Direct Addition. Usually, PVC and additives are processed in a hot/cool mixer to yield
a dry blend that is then conveyed pneumatically to silos for intermediate storage. In
the course of this operation, the PVC and calcium carbonate can separate when the
loading is high. With the Direct Addition approach, the calcium carbonate is added to
the PVC-U dry blend by a cold mixer immediately prior to entry into the extruder.

Calcium Carbonate –
Benefits of Direct Addition
HOLGER MÜLLER
he use of calcium carbonate when
As a rule, both problems must be taken to unstable extrusion behaviour, varying
into account starting at loading levels of mechanical properties and possibly even
20–30 phr, or already at 10-20 phr in the to visible defects in the extrudate. Ac-

T extruding rigid PVC (PVC-U ) se-

mi-finished products has been a
time-tested procedure for decades [1–6].
case of “double batching” [7] as also en-
countered in industry.
The reason for each of these is that the
cordingly, the amount of calcium car-
bonate added in practice is reduced until
the problems described above no longer
Calcium carbonate is used primarily to calcium carbonate can no longer bind ful- occur.
increase stiffness, improve toughness and
processing characteristics and optimise
formulation costs. The amounts added
for individual applications depend on the
desired property profile, regulatory agen-
cies and processing requirements:
■ The property profile of PVC-U changes
as a function of the amount added in
both positive (e.g. elastic modulus,
toughness) and negative ways (e.g. ten-
sile strength, gloss).
■ In Europe many plastic products are
produced to standards that specify the
materials to be used.
■ Processing is an important aspect. The
formulation of the plastic compound
must be adjusted to ensure problem- Fig. 1. PVC-U dry blend with calcium carbonate (attached and non-attached)
free processing.
ly to the PVC particle during the hot mix- Adding Upstream from
Known Limitations ing process and separates to some extent the Extruder
(Fig. 1). During the mixing process, cal-
If neither properties nor industrial stan- cium carbonate deposits can form on the In order to avoid these problems, trials
dards limit the amount of calcium car- mixer walls and subsequently drop into were conducted where the calcium car-
bonate that can be added, the question the dry blend in an uncontrolled manner bonate was mixed uniformly with the dry
that remains is what limitations exist on and cause irregularities during extrusion. blend immediately prior to entering the
the basis of processability. From actual The segregation that can occur during extruder.
practice, essentially two factors are pneumatic conveying of the dry blend A cold mixer (Fig. 2) was employed for
known: from the mixer to the intermediate stor- this purpose. To date, cold mixers have
■ segregation of PVC and calcium car- age silo because of the density differences been used only to incorporate smaller
bonate particles during pneumatic between PVC (1.4 g/cm3) and calcium amounts into the formulation, e.g. pig-
conveying of the dry blend, carbonate (2.7 g/cm3) must be viewed ments or blowing agent batches or lubri-
■ formation of deposits on the walls of more critically. Depending on the air ve- cants (0.1–2 phr). The idea of using this
the hot mixer. locity, the vertical elevation to be over- technology to add large amounts of ma-
come and the length of the conveying dis- terial of 5 to 50 phr is new.
tance, the unbound calcium carbonate The trials were conducted under near-
Translated from Kunststoffe 12/2006, pp. 62–66 can separate during conveying. This leads production conditions on a T-Rex 90-33

2 © Carl Hanser Verlag, München Kunststoffe international 12/2006


Fig. 2. Cold mixer from the company E.M.F.,
Enschede
extrusion line from the company
Rollepaal, Dedemsvaart/Netherlands us-
ing metering equipment and a patented
cold mixer (Fig. 3) from Enschedese
Maschinefabriek, Enschede/Netherlands.
Solid-wall pipe with dimensions of 160 ×
5 mm was produced at a rate of 161 m/h.
Depending on the mineral content, the
throughput ranged from 600 to 670 kg/h
to compensate for the increasing density
of the compound with increasing calci-
um carbonate content (constant-volume
extrusion).
The dry blend used was produced con-
ventionally on a hot/cold mixer and al-
ready contained 10 phr of coated calcium
carbonate (grade: OMYALITE® 50H, sup-
plier: Omya). Using the cold mixer, an ad-
ditional 21/27 phr of this calcium car-
bonate were added to the dry blend im-
mediately upstream from the extruder.
Three trials were conducted:
■ A1: 10 phr calcium carbonate (dry
blend produced in a hot/cold mixer)
■ A2: 31 phr calcium carbonate
(dry blend A1 (10 phr) and 21 phr
via cold mixer)
■ A3: 37 phr calcium carbonate
(dry blend A1 (10 phr) and 27 phr
via cold mixer)
Results
Extrusion proceeded without problems
with no further modifications to the for-
mulation or the screw design up to and
including 37 phr (A3). The quality of the
Kunststoffe international 12/2006
dry blend/calcium carbonate mixture was
investigated in the extruded pipe by
means of a visual evaluation, scanning
electron microscope images and testing
of the mechanical properties:
Visually, the pipe appeared perfect; no
agglomerates or defects could be detect-
ed on the visible surfaces (inside and out-
side).
With the aid of scanning electron mi-
croscope images of pipe cross-sections
obtained from trials A1–A3, the perfect
dispersion of the calcium carbonate was
confirmed (Figs. 4–6). The calcium car-
bonate particles can be recognised in the
images as light-coloured points. All visi-
ble particles are clearly smaller than
10 µm (see scale). Considering that the
calcium carbonate used has a top cut
(d98%) of 10 µm, i.e. 98 wt.% of all cal-
cium carbonate particles are smaller than
10 µm, this is an indication that no ag-
glomerates are present.
The mechanical properties tested from
trials A1–A3 confirm the results obtained
from the microscopic images. To better
understand the change in properties with
increasing calcium carbonate content in
the formulation, a typical empirical val-
ue for unfilled PVC-U was added under
the designation A0. Conclusions regard-
ing the quality of the dispersion can be
drawn largely from the toughness values,
since this property depends on not only
the amount added, but also strongly on
the fineness and dispersion of the miner-
als.Agglomerates would act as coarse par-
Fig. 3. Metering equipment with cold mixer on the extruder
EXTRUSION ■
ticles and have a negative impact on the
toughness. In contrast, the elastic modu-
lus is affected primarily by the amount
added, but only slightly by the fineness of
the additives. Experience shows that the
elastic modulus increases in a mostly lin-
ear manner with increasing percentage of
calcium carbonate (Fig. 7).
As the percentage of calcium carbon-
ate increases, the notched impact strength
also increases noticeably at first and then
decreases again at higher loading levels
(Fig. 8). Prerequisites for this clear in-
crease are optimal dispersion of the cal-
cium carbonate particles in the PVC ma-
trix and an appropriate fineness. Expla-
nations for this phenomenon include the
formation of microcracks (craze forma-
tion) in the PVC matrix in the immedi-
ate vicinity of the calcium carbonate par-
ticles as well as site exchange processes in-
volving the polymer molecules on the
surface of the mineral particles. The fin-
er the particles are, the greater the amount
of (impact) energy that can be absorbed
by microscopic site exchange processes
involving the polymer molecules as well
as by craze formation without macro-
scopic failure of the test specimen being
the result [8]. Even at 37 phr of calcium
carbonate, the measured notched impact
strength exhibits values at the same level
found in an unmodified material (A0).
(Note: The different gelation conditions
in trials A1–A3 and the associated change
in the degree of gelation in the extrudate
were not investigated).
3

Fig. 4. Scanning electron microscope images of
a pipe cross-section (Trial A1)
Termination of Trials at 37 phr
Calcium Carbonate
Addition of more than 37 phr calcium
carbonate was not possible, as the trials
were conducted with neither a change in
formulation nor a modification of the
screw design. It is known that calcium
carbonate changes the rheology of the
polymer melt and that gelation in the ex-
truder at high loading levels is delayed.
When adding more than 37 phr, it was
not possible to achieve adequate gelation
of the dry blend by the time the vacuum
degassing zone was reached in the ex-
truder, which lead to termination of the
trials. Gelation can, however, be varied
over a wide range by adjusting the
lubricant content (reduction of exter-
nal lubricants), by adding processing
aids such as acrylate or by changing the
screw geometry. Use of special metering
equipment can also influence the gela-
tion behaviour in the desired manner
[9].
The conclusion can be drawn that the
performance limit of the cold mixer had
not yet been reached when adding 27 phr
calcium carbonate in addition to the 10
phr already contained in the dry blend
(trial A3). The actual limit, which must
still be determined, could lie considerably
higher.
Summary
The additional installation of a cold mix-
er for highly filled systems brings a num-
ber of benefits: One of the greatest bene-
fits is that the limitation on the addition
of minerals due to segregation processes
during pneumatic conveying of the dry
blend is precluded. The possible poten-
tial for savings through use of calcium
carbonate can thus be better exploited.
Increasing the calcium carbonate per-
centage leads to a significant increase in
stiffness and can thus be utilised to reduce
the wall thickness, but even if the wall
Kunststoffe international 12/2006
Fig. 5. Scanning electron microscope images of
a pipe cross-section (Trial A2)
thickness is maintained, the addition of
calcium carbonate contributes to a no-
ticeable optimisation of material costs.
Limits on the use of calcium carbonate
are ultimately still determined by the re-
quired appearance and physical proper-
ties of the extrudate.
There is likewise a noticeable energy
and time savings when producing the dry
blend in the classical hot/cold mixing
process. The energy savings results from
the fact that the calcium carbonate need
not be heated from room temperature to
about 120°C and then cooled again. The
space that becomes available in the mix-
er (due to the absence of calcium car-
bonate) can be used to increase other
components (primarily PVC). This trans-
lates into increased mixing capacity.
A further benefit lies in the increased
flexibility of the extrusion line. Often, the
formulation is adjusted to run on the
weakest (oldest) extruder or to the most
difficult application. Here, use of a cold
mixer offers the benefit of a system-spe-
cific modification. Calcium carbonate as
well as lubricants and pigments can be
added directly at the extruder and dis-
persed homogeneously in the dry blend.
Direct Addition of the calcium car-
bonate at the extruder also generally elim-
Determination of the quality of mixing
(elastic modulus)
EXTRUSION ■
Fig. 6. Scanning electron microscope images of
a pipe cross-section (Trial A3)
inates the problem of deposits caking on-
to the walls of the hot mixer.
Economic Considerations
It is difficult to estimate the overall costs
associated with installation of a cold
mixer and all the necessary compo-
nents. These will differ from plant to
plant.
Assuming that gravimetric metering is
already present on the extruder, the in-
vestment is limited to procurement of a
cold mixer and a volumetric metering and
conveying system for the calcium car-
bonate (use a twin screw!). The costs for
both pieces of equipment come to about
25 000 EUR.
The most difficult challenge then is to
get the calcium carbonate to the meter-
ing and conveying equipment in a dust-
free condition. Before installing a costly
piping system to connect the (usually al-
ready existing) calcium carbonate silo to
the cold mixer, it is recommended that the
potential savings be examined concrete-
ly on an individual basis. This is possible
by first starting with “big bag”stations op-
erated directly at the extruder. The man-
ufacturers of such systems advertise dust-
free operation.
Fig. 7. Elastic modu-
lus as a function of
calcium carbonate
content
© Kunststoffe
4
■ EXTRUSION
The savings potential is considerable,
if one assumes that the calcium carbon-
ate content could be increased in certain
applications from the current value of 25
phr (limitation based on segregation dur-
ing pneumatic conveying) to 45 phr in the
future (e.g. technical profiles, special pipe
etc.).
For an extrusion line with an output of
600 kg/h and a production availability of
5000 h/a, the payback time for the in-
vestment is considerably less than one
year.
Determination of the quality of mixing
(notched impact strength)
Outlook
In addition to the benefits already dis-
cussed, further interesting possibilities are
conceivable, however these require more
in-depth investigations.
When building new extrusion facilities,
the dry blend is often prepared at the par-
ent plant initially and then transported to
the new facility by lorry in order to delay
making the high investment for new mix-
ing equipment.
5 © Carl Hanser Verlag, München
It is conceivable that at the parent plant
a “dry blend masterbatch” be prepared,
which is then mixed homogeneously with
the locally available PVC and calcium car-
bonate in a cold mixer. This would reduce
the transport costs dramatically.
To improve the economics further, it is
also conceivable that two or more ex-
truders be supplied with the same dry
blend simultaneously from a (larger) cold
mixer. The dry blend is then conveyed to
the individual extruders by using a twin
screw metering unit.
Fig. 8. Notched im-
pact strength as a
function of calcium
carbonate content
© Kunststoffe
Elimination of the mixing unit entire-
ly also appears possible. The cold mixer
used could be operated with four meter-
ing stations (e.g. for PVC, calcium car-
bonate, lubricant, stabiliser). An expan-
sion to permit addition of even more ad-
ditives is conceivable.
Ultimately, it is necessary to investigate
the specific applications and quality re-
quirements for which cold mixing alone
suffices. ■
ACKNOWLEDGEMENT
Special thanks go to Mr. Jan Visscher of the company
Rollepaal for organising and conducting the trials
under near-production conditions and to Mr. Hette
Zuidema of the company E.M.F. for providing free use
of the metering, mixing and conveying equipment as
well as his readiness to cooperate when making mod-
ifications.
I also wish to acknowledge all of the colleagues
from the Research and Technology Services depart-
ment in the company Omya who participated in the
trials and the evaluation of the results.
REFERENCES
1 Murphy, J.: Additives for Plastics Handbook, 2nd
Edition. Elsevier Science Ltd., Oxford 2001
2 Katz, H. S., Milewski, J. V.: Handbook of Fillers for
Plastics. Van Nostrand Reinhold Company, New
York 1987
3 Gächter, R., Müller, H.: Taschenbuch der Kunst-
stoff-Additive, 3. Ausgabe. Carl Hanser Verlag,
München 1990
4 Wypych, G.: Handbook of Fillers, 2nd Edition.
Chem Tec Publishing, Toronto 1999
5 Oberbach, K. et al: Saechtling Kunststoff Taschen-
buch, 29. Ausgabe. Hanser Verlag, München 2004
6 Zweifel, H.: Plastics Additives Handbook, 5th Edi-
tion. Hanser Verlag, München 2001
7 Große-Aschoff, M.: Double-Batching in der Fen-
sterprofil-Herstellung. Shaker Verlag, Aachen
1998, M. H. Pahl (Eds.)
8 Müller, H.: Beitrag zur Erhöhung des Kreidege-
haltes in PVC-H-Extrudaten. Dissertation TU
Chemnitz 1987
9 Reisenhofer, D.: Präcision for Highly Filled Formu-
lations, Kunststoffe international 95 (2005) 10,
Document Number PE103363
THE AUTHOR
DR.-ING. HOLGER MÜLLER, born in 1958, joined
Omya GmbH, Cologne, in 1990 and is “Head of Ap-
plied Technology Services Rigid Plastics Applications”
within the company; Holger.Mueller@omya.com
Kunststoffe international 12/2006