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Editor: Omya AG
Marketing Segment Plastics
Responsible for the content:
Gil Morieras

Calcium Carbonate in Blown HDPE Film

New Developments to Increase Productivity and Profitability

by
Gil Morieras - Marketing Manager Polyolefines (Omya)
and
Dr. Gerard Schaeffer (GS Technology)

Many interesting developments have taken place in the film industry over the past few years
due to new improved resins and the increased capability of extrusion lines. Technical
progress must however be subject to the cost factor and the use of mineral modifiers,
especially calcium carbonate can play an important role. Most polymers are ductile but may
become brittle under certain circumstances.

Introduction

It is now well established that the introduction of both elastomeric and hard mineral particles
can increase the impact toughness of semi-crystalline polymers.
W and P.Bartczak showed that the critical inter-particle distance, which is a fundamental
property of the matrix material, is affected by the presence and characteristics of the particles
dispersed in the matrix. Compared to elastomeric particles, CaCO3 increases the stiffness
but does not affect the Tg of the final compound.
 Calcium Carbonate in Blown HDPE Film / page 2

A.S. Argon from the MIT claimed that by introducing hard fillers (CaCO3), interfaces around
those inclusions will be generated. Interfaces consist of preferentially oriented crystalline
lamellae, having a lower plastic shear resistance in the crystal planes parallel to the filler
particle surface. If CaCO3 particles are well enough dispersed in the matrix, the oriented
lamellae form bridges between particles lowering the shear resistance throughout the
structure and so enhance the toughness of the matrix .

In this investigation, the impact toughness of HDPE modified with fine particles of CaCO3
was determined to study the influence on the processing and productivity of polyethylene film
manufacturing.

Materials and Methods

The calcium carbonate used in this work was surface-coated and had a top cut (d98%) of 7
and a mean particle size (d50%) of 1.7 microns (µm).
This fine CaCO3 was first compounded in LLDPE (MFI = 1g/10’, under 2.16 kg at 190°C) to
give a 65% master batch
The reference film had the following composition:

HDPE GM 9450F (MFI = 0.2g/10’ under 5 kg at 190°C) from Basell 80%

LLDPE from Sabic (MFI = 1 under 2.16 kg at 190°C) 15%
White master batch 5%
The test extruder was an HDPE Kieffel line with a 25 L/D 80 mm screw. The extruder was
equipped with a 200 mm IBC die and the AERO-COOL system.

The initial parameters for the production of the reference sample were :-

• Lay flat width : 1440 mm

• Thickness : 14 µm
• Weight per metre : 39.13 g/m
• Blow-up ratio : 4.584
• Constant line speed: 111 m/min
• Constant output: 261 kg/hr
• Screw speed: 102 rpm
• Specific screw output : 2.56 kg/rpm/hr
 Calcium Carbonate in Blown HDPE Film / page 3

Different mineral loadings (10, 17.5 and 25 %) by weight in the film were studied. During the
different trials, the film thickness was down-gauged to ensure a constant weight per running
metre.

Results

A Productivity Improvement

Output Extrusion Line Increase

By introducing the 65 % concentrate in a ratio of 15.3, 26.8 and 38.3 % corresponding to a

CaCO3 content in the film of 10, 17.5 and 25 %, the melt pressure decreased by 16.73 % or
from 550 down to 458 bar. This reduction of pressure is shown in figure 1.

F IG U R E 1 - V A R IA T IO N M E L T P R E S S U R E
575 bar

0 ,0 0 %
550 bar 0 ,0 %
550 bar

525 bar -4 ,5 %

-8 ,1 8 %
500 bar -9 ,1 %
505 bar

-1 3 ,4 5 %

475 bar -1 3 ,6 %
476 bar

-1 6 ,7 3 %

450 bar -1 8 ,2 %
458 bar

425 bar -2 2 ,7 %

400 bar -2 7 ,3 %
0 ,0 0 % 5 ,0 0 % 1 0 ,0 0 % 1 5 ,0 0 % 2 0 ,0 0 % 2 5 ,0 0 % 3 0 ,0 0 %

C a C O 3 C o n te n t

This beneficial behaviour could be explained thanks to the following 5 factors :

1. The internal volume of the screw will be reduced due to the non-dilation (expansion) of
CaCO3 particles replacing polymers.
2. The viscosity of the blend will be reduced compared to that of the reference blend. The
increased internal friction from CaCO3 particles in the polymer mix raises the shear,
reducing the melt viscosity .
3. Due to the good thermal conductivity of the CaCO3 particles, exchange of heat is
improved providing a higher melt homogeneity.
4. Increase of the blend density HD + LL + White + CaCO3
5. The efficiency of the grooved feed section of the extruder is improved by the compound
pellets.
 Calcium Carbonate in Blown HDPE Film / page 4

Due to this fall of pressure, the increase of the specific screw output and the faster cooling of
the bubble, the output of the blown film line can be increased.

During the trials, we achieved without any problem, an output of 310 kg/hr at 132 m/min line
speed means an increase of 18.8% with a blend containing 20 % CaCO3 compound (or
13.05 % CaCO3).

As a general rule, the use of 1% CaCO3 will increase the output by at least 1%. Depending
upon the machine specification, the production programme and the polymer blend
composition of the film, this output increase could reach up to 1.5 % for each percent of
CaCO3 .

FIGURE 2 - VARIATION SPECIFIC OUTPUT

3,50 kg/tr/hr

32,5%

27,5%
3,25 kg/tr/hr 25,19%

3,211 kg/tr/hr
22,5%
16,88%
2,869 kg/tr/hr

3,00 kg/tr/hr 17,5%

2,998 kg/tr/hr

11,85% 12,5%
2,565 kg/tr/hr

2,75 kg/tr/hr 7,5%

2,5%

0,00%
2,50 kg/tr/hr -2,5%
0,0% 2,5% 5,0% 7,5% 10,0% 12,5% 15,0% 17,5% 20,0% 22,5% 25,0%
CaCO3 Content

Bubble stability

Besides this tremendous increase of productivity, CaCO3 will also improve the quality of the
polyethylene bubble by increasing its stability. This is again due to the excellent heat
conductivity which is 5 times higher than the polymers’. The better melt strength and the
excellent cooling give the bubble a remarkable stability even at higher outputs and line
speeds.

The neck height of the HDPE bubble can now be increased from the usual 8 x die diameter
to 12 x die diameter.
 Calcium Carbonate in Blown HDPE Film / page 5

FIGURE 3 – THERMAL CONDUCTIVITY (W/ M°K)

3,00

2,50

2,00

1,50

1,00

0,50

PP LDPE HDPE CaCO3

This higher stability improves the process, resulting in a better film quality with :

(a) Closer thickness tolerances (less deviation)

(b) Excellent micro and macro film flatness, thus good film appearance
(c) A slight decrease of width variation and pleats in the film
(d) An increased output thanks to higher neck.

Dart Drop Increase

By achieving an extremely good dispersion of the very fine CaCO3 particles in the PO matrix
and by reaching the critical and necessary ratio to create the appropriate network as
described in the different studies mentioned in the introduction, the toughness will be
dramatically increased. In figure 4 we give the evolution of this value. The maximum of 17.25
g/µ or + 36.7 % of the original dart value is achieved with a 20 % CaCO3 content.

FIGURE 4 - VARIATION DART DROP TEST

18 g/µ
38,5%
36,70%
17 g/µ 33,93%
32,6%
17,250 g/µ

16,900 g/µ

27,59%
16 g/µ 26,7%
16,100 g/µ

20,8%
15 g/µ
14,8%
14 g/µ
12,619 g/µ

8,9%

13 g/µ 3,0%
0,00% -3,0%
12 g/µ
-8,9%
11 g/µ
-14,8%

10 g/µ -20,8%
0,0% 2,5% 5,0% 7,5% 10,0% 12,5% 15,0% 17,5% 20,0% 22,5% 25,0%

CaCO3 Content
 Calcium Carbonate in Blown HDPE Film / page 6

The dart impact is of great interest in some applications, specially for all types of bags. Thus,
if the final requirements for some applications only specify the dart value, the film thickness
can be reduced whilst still attaining the value of the original reference film.

Elmendorf Tear Resistance

Here again, CaCO3 dispersed in the film improved the tear resistance. Figure 5 shows an
increase up to 11.254 mN/µ or + 45.87 % of this value in the machine direction.

FIGURE 5 - VARIATION ELMENDORF MD

12 mN/µ

45,87% 46,5%

11,254 mN/µ
11 mN/µ
39,73% 37,2%

10,780 mN/µ
32,86%
10,250 mN/µ

10 mN/µ 27,9%

18,6%
7,715 mN/µ

9 mN/µ
9,3%
8 mN/µ
0,0%
0,00%
7 mN/µ -9,3%
0,0% 2,5% 5,0% 7,5% 10,0% 12,5% 15,0% 17,5% 20,0% 22,5% 25,0%

CaCO3 Content

These results are impressive and are the result of the creation of a stable 3-dimensional
polymer matrix.
Thus the same benefits are to be found when the tear resistance is measured in the TD.
However, these values are much higher and so are not so critical to the properties of the final
film.
Figure 6 shows an increase up to 130,116 mN/µ or nearly 70 %.

FIGURE 6 - VARIATION ELMENDORF TD

140 mN/µ
78% 69,71%
130 mN/µ 72,52%
70%
61%
130,116 mN/µ

128,000 mN/µ

120 mN/µ
53%
110 mN/µ 46,00% 45%
110,120 mN/µ

37%
100 mN/µ
29%
75,423 mN/µ

90 mN/µ 20%
12%
80 mN/µ 4%
-4%
70 mN/µ 0,00%
-12%
60 mN/µ -20%
0,0% 2,5% 5,0% 7,5% 10,0% 12,5% 15,0% 17,5% 20,0% 22,5% 25,0%

CaCO3 Content
 Calcium Carbonate in Blown HDPE Film / page 7

The improvement of these mechanical properties results from the better and controlled
orientation of the polymer chains. Calcium carbonate is both binding the polymer chains and
inhibiting their orientation in the film.

Tensile Strength/Elongation at Break

By using resins with low MFIs, corresponding to those of the polymers used to blow the film,
the expected decrease of the tensile strength is minimised and reduced to a maximal loss of
10 % at a mineral loading of 25 %. Moreover this slight loss could be assigned to the
reduction of thickness when CaCO3 is introduced.

Tensile Strength @ Break MD Tensile Strength @ Break CD

60,00 N/mm2
50,00 N/mm2

50,00 N/mm2
40,00 N/mm2

40,00 N/mm2
30,00 N/mm2
30,00 N/mm2

20,00 N/mm2
20,00 N/mm2

10,00 N/mm2 10,00 N/mm2

0,00 N/mm2 0,00 N/mm2

0% 10% 17,5% 25% 0% 10% 17,5% 25%

CaCO3 Content CaCO3 Content

Elongation @ Break CD Elongation @ Break MD

600,00 % 500,00%

500,00 % 400,00%

400,00 %
300,00%

300,00 %
200,00%
200,00 %

100,00%
100,00 %

0,00 % 0,00%
0% 10% 17,5% 25% 0% 10% 17,5% 25%
CaCO3 Content CaCO3 Content

Orientation / Isotropy

The optimum mechanical properties of high molecular weight HDPE films are obtained if the
molecular chains are orientated equally in the MD and TD directions. In this case the film has
a good isotropy. This is all the time achieved with optimum adjustments of the processing
parameters. With the use of CaCO3 compounds, the balance of the orientations and the film
isotropy are improved.
 Calcium Carbonate in Blown HDPE Film / page 8

The MD and TD orientations depends from the “actual draw down” or from following ratio :

ACTUAL DRAW DOWN = LINE SPEED / MELT SPEED AT BUBBLE NECK-IN POSITION

The best mechanical film properties are obtained when the value of this actual draw-down is
between 1.5 and 2, or when the polymer speed at the bubble neck-in position is high and the
neck height is very high.

With 15 to 35 % compound, the increased bubble stability allows much higher neck heights -
up to 12 x die diameter. The bubble neck-in melt speed is then over 50 % of the line speed
and the optimum film orientation can now be achieved. The dart and Elmendorf values are
maximised and the TD/MD ratio is low.

C Improvement during Converting

Secant Modulus

Eg (secant modulus) is determined by the shape of the line connecting the origin and a given
point on the strain-stress curve.

This characteristic is particularly important during the film converting operations, for example
during the stacking of the bags at the end of the bag maker. By increasing the secant
modulus, the converting machines are able to run at much higher speeds without any
disruption during the bag stacking. The scrap rate of the converting machines is reduced.

Stress

Eg

secant modulus

Strain , ε
 Calcium Carbonate in Blown HDPE Film / page 9

Printability

It is generally agreed that the presence of CaCO3 in polyolefines enhances printability.

This assumption has been once again verified during bag production.
CaCO3 creates micro-roughness of the surface, allowing better adhesion of the ink to the
substrate.
But due to the permanent presence of CaCO3, the corona treatment is enhanced and the
effect will be prolonged. Due to higher treatment level, the printing speed can be increased
and the scrap rate due to poor ink adhesion is reduced.

Improved Heat Sealing

Heat sealing is improved. The main reason is the high thermal conductivity of CaCO3. The
sealing bar temperature can be reduced and less polymer degradation occurs. Once again
the processability and productivity of the bag maker are significantly improved.

C Better Profitability

Higher Throughput & Lower Extrusion Costs

Depending on the parameters of each production unit, the costs incurred in the production of
HDPE films could be different. In the table below, we have taken into consideration the costs
obtaining on the trials dates (fixed costs, variable costs, polymer costs).
It was shown that due to lower melt pressure and the excellent cooling, productivity could be
increased depending on the mineral loading, together with down-gauging to compensate for
the extra weight of the CaCO3. By improving the mechanical properties, we came to the firm
conclusion that substantial cost savings could be achieved in this trial.

TiO2 Reduction

It is well known that CaCO3 particles help to disperse fine particle pigments such as TiO2 or
carbon black, increasing their efficacy. When CaCO3 particles are added into the film they
will contribute to the light diffraction and so increase the opacity. These 2 effects allow the
reduction of the TiO2 content by 20 to 30 %, depending on final opacity required.
 Calcium Carbonate in Blown HDPE Film / page 10

The use of CaCO3 in waste bags, could also bring comparative advantages by reducing
pigment content in colour master batches.

Down-Gauging / Raw Material Savings

It has been demonstrated that the mechanical properties are improved by the addition of
CaCO3. Depending upon the final requirements, the thickness of the film could be adjusted to
fulfil the specifications of end users. In this experiment, the dart drop increased by up to 37 %
and the Elmendorf tear strength by up to 46 % in the machine direction.

The optimum CaCO3 concentration always depends on the production programme, on the
polymers used and on the extrusion line. As results are related directly to the real thickness
of the film, which is decreased with CaCO3 loading, we do recommend choosing the final
content of CaCO3 in the film in accordance with the optimum mechanical characteristics. For
this trial, the optimum CaCO3 loading is 15 % corresponding to 23 % of compound.

Film producers, and specially bags manufacturers, where dart drop and tear strength are of
major importance, could then decide to produce thinner films with equal mechanical
properties or the same thickness with much improved mechanical properties. CaCO3 could
then help to upgrade standard resins, allowing them to compete with higher performance
resins.

Consequently down-gauging will lead to raw material savings. Less energy is then required.
The ecological aspects are without any doubt in favour of CaCO3. Moreover CaCO3 is a
sustainable raw material.

Higher Throughput and Lower Extrusion Costs

Depending on the parameters of the extrusion line, the production costs of HDPE films could
be different. Figure 7 shows the calculation of the extrusion costs with and without CaCO3.
We take in consideration , the following costs:
• FIXED COSTS for depreciation of building and machinery and the interest for the capital.
• VARIABLE COSTS for labour, scrap production, spare parts and electrical power. The
production with CaCO3 needs slightly more spare parts, but the scrap rate is reduced
from 2.5 to 1.25 %.
• OVERHEAD COSTS are evaluated at 50 000 €.
 Calcium Carbonate in Blown HDPE Film / page 11

Figure 7 – Table with Cost Structures

0 % CaCO3 10% CaCO3 17.5 % CaCO3 25 % CaCO3

Production 2.660 2.926 3.126 3.325
(mT/Year)

Total Fixed 236.875 € 236.875 € 236.875 € 236.875 €

Costs

Variable Costs 228.359 € 234.147 € 237.660 € 240.878 €

Polymer Costs 2.056.111 € 2.246.466 € 2.361.295 € 2.471.805 €
Total Costs 2.521.345 € 2.717.488 € 2.835.830 € 2.949.558 €
Price/Kg of Good 0,95 € 0,93 € 0,91 € 0,89 €
Film

Total Saving 0,00% - 3,88% - 5,71% - 7,51%

Money
0€ - 91.472 € - 165.130 € - 242.442 €

With the polymer prices listed in figure 8 and a compound price of 750 €/kg, the costs of the
polymers are 1.79 €cent/kg less and the extrusion costs are lowered by 4.91 €cent/kg. The
total saving is 6.7 €cent/kg or 5.9 % of total costs. Over the year, when 20 % CaCO3 master
batch is used, this Kiefel line will produce 395 tons more film and the total saving is 150 000
€. (see annexe 1)
 Calcium Carbonate in Blown HDPE Film / page 12

References
J.A.W van Dommelen, W.A.M Brekelmans and F.P.T Baaijens : Micromechanical
Modelling Of Particle-Modified Semi-Crystalline Materials

Bernard A.G. Schrauwen, Leon E.Govaert and E.H. Meijer : Structure And Properties Of
Flown Induced Orientation In Semi-Crystalline Polymers

B.A.G. Schrauwen, G.M. Kim, S. Rastogi, L.E. Govaert and E.H. Meijer : Crystal
Orientation On A Substrate : A New Route Towards Toughness

Bernard A.G. Schrauwen, Leon E.Govaert and E.H. Meijer : Toughness Of High –Density
Polyethylene With Hard Filler Particles

Z. Bartzack, A.S Argon, R.E. Cohen, M. Weinberg : Toughness Mechanism In Semi-

Crystalline Polymer Blends: II. High-Density Polyethylene Toughened With Calcium
Carbonate Filler Particles.

A.S. Argon : Mechanisms Of Inelastic Deformation And Fracture Of Solids

J.L.H Batiste, L.G. Shaw, R. Ballard : Benefits And Performance Mechanism Of Fine,
Treated Calcium Carbonate In Blown Polyethylene Films

Omya Group
Gil Morieras
Marketing Manager Polyolefines
Baslerstrasse 42, CH-4665 Oftringen (Switzerland)

Telephone: +41 62 789 29 29

Telefax: +41 62 789 20 77
e-mail: info.ch@omya.com
Internet: www.omya.com

The information contained in this Technical Documentation relates only to the specific material designated herein
and does not relate to use in combination with any other material or in any process. The information provided
herein is based on technical data that Omya believes to be reliable, however Omya makes no representation or
warranty as to the completeness or accuracy thereof and Omya assumes no liability resulting from its use or for
any claims, losses, or damages of any third party. Recipients receiving this information must exercise their own
judgement as to the appropriateness of its use, and it is the user’s responsibility to assess the material’s suitability
(including safety) for a particular purpose prior to such use. (October 2002)
 Calcium Carbonate in Blown HDPE Film / page 13

Annexe 1

CaCO3 MB Price per kg 750 €/MT

WITHOUT CaCO3 WITH 20% CaCO3 MB
Number of production 11,00 or 13% CaCO3 particles
months per year: Months
Extruder efficiency: 93.14%
Number of production hours 7,500 hr Increa
per year: se
Average production output: 260 kg/hr New 310 kg/hr 19.23
output %
Annual production per year: 1,950 mT 2,325,000
kg
Scrap rate: 2,50% 48.75 mT 1.25% 29,063 (less
kg/hr scrap)
Net production per year: 1,901 mT 2,295,938
kg

FIX COSTS CALCULATION

Investment for the extrusion 100,000 € (Pro-rata for this extruder)
building:
Investment for the extrusion 650,000 €
building:
Investment for ancillaries 75,000 € (Tower, silos, etc)
equipment:
Working capital for 1,5 356,850 € (1.25€ per kg film)
months production:
Building depreciation over 10,000 €
10 years:
Extruder and accessories 145,000 €
depreciation over 5years:
Total deprecations per year: 155,000 € 8.15 32.11 6.75 32.97
€cent/kg % €cent/kg %
Total interest: 5.00% 59,093 € 3.11 12.24 2.57 12.57
€cent/kg % €cent/kg %
TOTAL FIX COSTS 214,093 € 11.26 44.35 9.32 45.53
€cent/kg % €cent/kg %

VARIABLE COSTS CALCULATION

0.75 operators for 8052 hr. (15 € / hr / 120,80 € 6.5 €cent/kg 25.02 5.26 25.69
operator) % €cent/kg %
Costs for scrap production: 1.1400 55,575 € 2.92 11.51 1.29 6.29%
€/kg €cent/kg % €cent/kg
Scrap rest value. -0.2700 -13,163 € -0.69 - -0.34 -1.67%
€/kg €cent/kg 2.73% €cent/kg
Costs for spare parts: 2.00% 14,500 € 0.76 3.00% 3.00% 0.95 4.63%
€cent/kg €cent/kg
Cost for electrical power at 350 40,950 € 2.15 8.48% 300 1.82 8.90%
0,06€/kw: Wh/kg €cent/kg Wh/kg €cent/kg
TOTAL VARIABLE COSTS 218,643 € 11.50 45.29 8.98 43.83
€cent/kg % €cent/kg %

OVERHEAD COSTS 50,000 € 2.63 10.36 2.18 10.63

€cent/kg % €cent/kg %
 Calcium Carbonate in Blown HDPE Film / page 14

TOTAL EXTRUSION COSTS 482,735 € 25.39 100.0 20.48 100.00

€cent/kg 0% €cent/kg %

PRICE DENSITY COSTS -

REDUCTION= 19,34
%
OR 4,91
€cent/kg
HDPE: 850 €/MT 0,950 % HDPE= 84.00 % 69.17%
g/cm3 % HDPE
=
LLDPE: 800 €/MT 0.918 % LLDPE= 12.00 % 11.08%
g/cm3 % LLDPE
=
WHITE MB: 1,800 1.710 % WHITE= 4.00% % 3.75%
€/MT g/cm3 WHITE
=
CaCo3 MB: 750 €/MT 1.608 % CaCO3= 0.00% % 16.00%
g/cm3 CaCO3
=
TOTAL= 100,0 TOTAL 100.00%
0% =
AVERAGE DENSITY: 0.963 1.031
g/cm3 g/cm3
POLYMER PRICE FOR FILM: 0.882 €/kg 0.864 €/kg
COSTS -2.03%
REDUCTION=
OR 1.79
€cent/kg
FILM PRODUCTION COSTS= 1.1359 1.0689
€/kg €/kg

TOTAL EXTRUSION COSTS REDUCTION= - 5.901%

6.7029
€/kg