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Calcium Carbonate in Blown HDPE Film

New Developments to increase Productivity and Profitability


Version 2.1 - October 2003
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CaCO3 in Polyolefines : Oriented Lamellae


Oriented Layer

CaCO3 Particles

Polyolefines Matrix Bridge


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(oriention of lamellea)

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Estimation of Matrix Ligament Thickness

= d x[ ( / 6 )1/3 - 1] x exp[(ln )2]


d = number average geom.. mean diam. of particles

= geom.. constant depending on assumed packing :


1.0 for cubic lattice, 1.09 for body-centered cubic, 1.12 for face-centered cubic

= volume fraction of particles

= geom.. std dev. of particle size distribution


Ref : Bartczak et al. Polymer 40 (1999) 2331

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Brittle Behavior

When ligament thickness is larger than 2 times the thickness of the oriented crystallization layer around the particles.

Ref : Bartczak et al. Polymer 40 (1999) 2331

Filler / Rubber Particle

Bulk Matrix

Oriented Layer

Ductile Behavior
When ligament thickness is less than 2 times the thickness of the oriented crystallization layer around the particles and material with reduced plastic resistance percolates through the blend.
* Connecting lines show orientation of lamellae in inter-particle ligaments

Objective

To introduce CaCO3 in PE Blown Film in order to improve profitability by enhancement of productivity and mechanical properties.

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New Concept - Methods Description


1- To produce a concentrate of a fine coated CaCO3 To use the base resin from film producer as the carrier for a 65% to 75% Masterbatch 2- To introduce this Masterbatch till 25 % CaCO3 in the film extrusion line
No additional changes are required

Increase the screw rpm to maximise the benefits of CaCO3

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Trials & Process Conditions

Film Extrusion Line Basic Polymer Blend Masterbatches

KIEFEL EXTRUDER COMPEX 80 SA Screw Size : 80 mm X 25 D Die Diam : 200 mm X 1.4 IBC System with Aero-Cool Output without CaCO3 : 260 kg/hr. Specific Screw Output : 2,56 Kg/rpm/hr

80% Unimodal HDPE + 15% butene LLDPE + 5% White

65 % Omyafilm + LLDPE

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Process Conditions

Layflat Width 1440 mm

Production Programme

Initial Thickness (without CaCO3) : 14 then downgauged Film to work at identical Weight by adding 10 %,17,5 % and 25 % of CaCO3

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Production Enhancement
Melt Pressure By introducing CaCO3 in the screw, melt pressure drops allowing an increase of screw speed. Lower manufacturing cost per unit (bag)

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Variation Melt Pressure


575 bar 550 bar 525 bar 500 bar 475 bar
476 bar -16,73% 458 bar 0,00% 550 bar

0,0% -4,5%
-8,18% 505 bar -13,45%

-9,1% -13,6% -18,2% -22,7% -27,3% 30%

450 bar 425 bar 400 bar 0% 5% 10% 15%

20%

25%

CaCO3 Pigments

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Production Enhancement
Higher Spec. Output internal volume of the screw will be reduced viscosity of the blend will be reduced higher melt homogeneity Increase of the blend density higher efficiency of the grooved feed section of the extruder

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Variation Specific Output


3,5
+ 25,2%

3,0

3,21 2,87 3,00

Mixture Density / Spec Output

2,5 2,0 1,5

2,57

+19,5%

1,0
0,97 1,038

1,095

1,159

0,5 0,0 0%

Spec. Output [kg/h/rpm]


Mixture Density [kg/dm3]

5%

10 %

15 %

20 %

25 %

CaCO3 Pigments

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Production Enhancement

Bubble stability improved Faster cooling of blown bubble thanks to higher thermal conductivity of CaCO3 Neck Height could be increased from 8 X Die Diam to 13 X.

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Thermal Conductivity
[W/ MK]
3.00 2.50 2.00 1.50 1.00 0.50 -

PP
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LLDPE

HDPE

CaCO3
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Mechanical Properties Enhancement


Increased Dart Drop Impact Strength Toughening of PE matrix thanks to addition of CaCO3. Possibility of down-gauging

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Variation Dart Drop Test


18 g/
17,250 g/ 36,70% 16,900 g/ 33,93%

38,5% 32,6% 26,7% 20,8% 14,8% 8,9% 3,0%

17 g/ 16 g/ 15 g/
12,619 g/ 27,59% 16,100 g/ 0,00%

14 g/ 13 g/ 12 g/ 11 g/ 10 g/

-3,0% -8,9% -14,8% -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 Pigments

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Mechanical Properties Enhancement


Increased Dart Drop Impact Strength Toughening of PE matrix thanks to addition of CaCO3. Possibility of down-gauging Higher Elmendorf Tear Strength

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Variation Elmendorf MD
12 mN/ 45,87% 11 mN/
11,254 mN/

39,73% 46,5%
37,2%

32,86%
7,715 mN/ 10,250 mN/

10 mN/ 9 mN/ 8 mN/

10,780 mN/

27,9% 18,6% 9,3% 0,0% -9,3%

0,00% 7 mN/ 0,0% 2,5% 5,0% 7,5%

10,0% 12,5% 15,0% 17,5% 20,0% 22,5% 25,0%

CaCO3 Pigments

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Variation Elmendorf TD

140 mN/ 130 mN/ 120 mN/


110,120 mN/

72,52%
130,116 mN/

69,71%
128,000 mN/

110 mN/
75,423 mN/

46,00%

100 mN/ 90 mN/ 80 mN/ 70 mN/

0,00%

60 mN/ 0,0%

2,5%

5,0%

7,5%

10,0%

12,5%

15,0%

17,5%

20,0%

22,5%

78% 70% 61% 53% 45% 37% 29% 20% 12% 4% -4% -12% -20% 25,0%

CaCO3 Pigments

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Mechanical Properties Enhancement


Increased Dart Drop Impact Strength Toughening of PE matrix thanks to addition of CaCO3. Possibility of down-gauging Higher Elmendorf Tear Strength Higher secant modulus Helps in bag production Better folding and winding on bag lines

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Tensile Strength at Break MD


60 N/mm2

50 N/mm2

40 N/mm2

30 N/mm2

20 N/mm2

10 N/mm2

0 N/mm2 0% 10% CaCO3 Pigments 17,5% 25%

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Tensile Strength at Break TD


60 N/mm2

50 N/mm2

40 N/mm2

30 N/mm2

20 N/mm2

10 N/mm2

0 N/mm2 0% 10% CaCO3 Pigments 17,5% 25%

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Elongation at Break MD
600 %

500 %

400 %

300 %

200 %

100 %

0% 0% 10% CaCO3 Pigments 17,5% 25%

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Elongation at Break TD
600 %

500 %

400 %

300 %

200 %

100 %

0% 0% 10% CaCO3 Pigments 17,5% 25%

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Isotropy : CaCO3 Balances Polymers Orientation


TD TD

.
MD
Neck Height 8X Die

.
Neck Height 12X Die

MD

Without CaCO3
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With CaCO3
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Isotropy : Elmendorf TD/MD


CaCO3 0%

10% 25,433

17,50% 16,501

25% 13,672
Rate TD/MD
Aver. Decrease Rate

40 30 20 10 0 31,849 -10 -20 -30 -40 -50 -60


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-20,15

-48,19 -57,07
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Sealing
Sealing Strength with Omyalene 2021 P
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Sealing Strength [N/15mm]

15m monolayer
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82% HDPE 13% LLDPE 5% White MB change HDPE for CaCO3 keep LLDPE const.

Sealing Strength 160 [N/15mm]] Sealing Strength 150 [N/15mm]] Sealing Strength 140 [N/15mm]] Sealing Strength 130 [N/15mm]] Sealing Strength 120 [N/15mm]]

0 0 5 10 15 CaCO3 Pigm ents [%] 20 25 30

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Mechanical Properties Enhancement Summary


CaCO3 will bring a homogeneous and isotropic film with upgraded characteristics.
Decreased orientation and equalisation of MD and TD properties Better bubble stability Neck length can be increased up to 13 X die diameter BUR can be reduced by 10% and a bigger die can be used, increasing output Improved film flatness and thickness tolerances Better roll quality Better Printability Faster welding
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Mechanical Properties Enhancement Summary

Dart drop increased by up to 45% Elmendorf MD tear increased by up to 150% Elmendorf TD tear increased by up to 140% Thinner film with equal mechanical properties OR Same thickness with much improved mechanical properties

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Process Enhancement Summary

 Lower melt pressures  Higher specific screw output  Better bubble stability  Faster cooling due to higher thermal conductivity of CaCO3  Better melt homogeneity

Higher Extruder Output by up to 1% per percent CaCO3

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Productivity Enhancement Summary

 Potential raw material cost savings  Potential to compete with higher performance resins  Reduction of TiO2 Masterbatch  Elimination of blocking problems  Lower extrusion costs

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Final Costs Calculation

0 % CaCO3

10% CaCO3 2.926 236.875 234.147 2.246.466 2.717.488 0,93 -3,88% 0 - 91.472

17.5 % CaCO3 3.126 236.875 237.660 2.361.295 2.835.830 0,91 -5,71% - 165.130

25 % CaCO3 3.325 236.875 240.878 2.471.805 2.949.558 0,89 -7,51% - 242.442

Production (mT/Year) Total Fixed Costs Variable Costs Polymer Costs Total Costs Price/Kg of Good Film Total Saving Money

2.660 236.875 228.359 2.056.111 2.521.345 0,95 0,00%

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Additional Benefits

CaCO3 cleans the die and extruder Shorter changeover times CaCO3 is an ecological product Replacing polymer Neutralising flue gases so preventing acid rain

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Additional Benefits

Incineration of bags containing CaCO3 decreases CO2 emission 1 Kg of PE gives 2.917 Kg CO2 1 Kg of bags containing 20 % CaCO3 gives 2,602 Kg CO2 - 17,2 % CO2

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Summary
Improve physical properties Competitive with higher performance resins Potential for down-gauging film Potential raw material cost savings Higher output rates Lower manufacturing costs
Contribute to a cleaner environment
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