Struktol Company of America

201 E. Steels Corners Road · P.O. Box 1649

Stow, OH 44224-0649
(330) 928-5188 Fax (330) 928-8726

Improved Processing of Highly Filled

Calcium Carbonate Compounds

EK Koss, Dr. John vander Kooi, Michael S. Fulmer*

*Presenter

Presented at the SPE ANTEC 2000

Orlando, FL

Wednesday, May 10, 2000 stp0198

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ABSTRACT

Calcium carbonate treated with an interfacial agent such as stearic acid or a

stearate is often used in place of untreated calcium carbonate to take advantage of
improved lubricity and wetting characteristics. These characteristics typically lead
to lower mixing viscosity, improved filler dispersion and better flow properties. In
this paper, the effect of fatty acid derivatives on polypropylene compounds highly
filled with calcium carbonate, both treated and untreated, will be discussed. The
use of fatty acid derivatives can be effective for lowering extrusion pressure
leading to throughput increases. The overall effect on filler addition, viscosity,
mixing and processing properties will be shown for one class of fatty acid
derivatives.

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EFFECT MECHANISMS OF THE ADDITIVES:

u Tribological
˜ Adhesives

˜ Lubricants

˜ Surfactants

u Molecular

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EFFECT MECHANISMS OF THE ADDITIVES:

u Tribological
l Adhesives

– Increased interfacial forces created by surface attachment

– Increase energy required to break adhesive bonds causing increased
shear
l Lubricants

– Function to minimize the frictional forces between moving surfaces

– Can be divided into internal and external
– Internal is polymer:polymer, polymer:filler interaction
– External is polymer:hot metal, filler:hot metal interaction
l Surfactants

– Create a surface active film via polar and non-polar ends

– Polar end absorbs/bonds to a surface
– Wetting of the filler allows for improved low energy dispersion
– Similar to lubricants effect

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EFFECT MECHANISMS OF THE ADDITIVES:

u Molecular
l Chemical alteration of molecular weight average and number

l In polypropylene, addition of peroxide results in chain scission

l Lower molecular weight results in increased flow rates/low viscosity

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TYPICAL PROPERTIES OF HIGHLY FILLED COMPOUNDS:

u Increased:
3 Viscosity (-Negative)
3 Flexural modulus (+Positive)
3 Heat deflection temperature (HDT) (+Positive)
3 Dimensional stability (+Positive)

u Decreased:
3 Izod Impact (-Negative)
3 Mold shrinkage (+Positive)
3 Thermal expansion (+Positive)
3 Part cost (+Positive)

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MATERIALS USED IN THIS PROGRAM:

u Montell Homopolymer Polypropylene ProFax 6323 (12 MFI)

u Amoco Polypropylene 1016 (5 MFI)
u Calcium Carbonate
l Omyacarb F (Untreated)

l Omyacarb FT (Treated)

u Struktol ZB30A
l Fatty acid derivative

u Struktol ZB30B
l Fatty acid derivative

u Struktol ZB31/1
l Fatty acid derivative

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FORMULATIONS:

Material Treated Untreated A B C D E F

PP Resin 100 60 59.6 59.4 59.2 59.6 59.4 59.2
CaCO3 (F or FT) 40 40 40 40 40 40 40
ZB30A 0.4 0.6 0.8
ZB30B 0.4 0.6 0.8
ZB31/1
TOTAL 100 100 100 100 100 100 100 100

Material G H I
PP Resin 59.6 59.4 59.2
CaCO3 (F or FT) 40 40 40
ZB30A
ZB30B
ZB31/1 0.4 0.6 0.8
TOTAL 100 100 100

NOTE: All formulations with additives use untreated CaCO3

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LABORATORY EXPERIMENT:

Data generated is based on compounding on a Brabender PL2000 torque rheometer

using the bowl mixer equipped with cam blades at 180°C and 70 rpm. The total time
of the mixing cycle was 800 seconds.

Capillary rheometer testing was performed on a Shimadzu CFT-500C equipped with

a 10 mm by 1 mm diameter die and set at 200°C. A variety of shear rates were used
to give a complete viscosity picture.

Physical property data was generated using injection molded test specimens
prepared on a Cincinnati Milacron 33 ton lab molding machine:

Color measurements were taken on injection molded specimens using a Minolta

Spectrophotometer.

Thermal stability measurements were made on a Mettler Toledo DSC at 10°C/min.

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 MIXING CURVES FOR 40% CaCO3 FILLED COMPOUNDS
ProFax 6323
10

Untreated
8
Torque, Nm

4
Treated
ZB30A-1%
2
ZB30B-1%
ZB31/1-1%
0
0 100 200 300 400 500 600 700 800
Time, sec
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 MIXING CURVES FOR 40% CaCO3 FILLED COMPOUNDS
Amoco 1016
10

Untreated
8
Torque, Nm

4
Treated
ZB30A-2%
2 ZB30B-2%
ZB31/1-2%
0
0 100 200 300 400 500 600 700
Time, sec
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MIXING PROPERTY RESULTS:

u Untreated CaCO 3 with no additives showed higher torques throughout the

mixing cycle and the resulting compound displayed poor dispersion with residue
CaCO3 left in the bowl.

u The treated CaCO 3 showed improved wetting characteristics resulting in lower

torques throughout the mixing cycle. The resulting compound displayed good
dispersion and color.

u The untreated CaCO 3 with fatty acid derivatives added showed wetting and
mixing characteristics typical of treated CaCO 3. The resulting compound
displayed good dispersion and color.

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 VISCOSITY AND SHEAR STRESS AT 200°C
ProFax 6323 Compounds
10000

Untreated
Treated
ZB30A-1%
Apparent Viscosity, Pa.s

1000
ZB30B-1%
ZB31/1-1%

100

10
1E+4 1E+5 1E+6

Shear Stress, Pa
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 VISCOSITY AND SHEAR STRESS AT 200°C
Amoco 1016 Compounds
1000
Apparent Viscosity, Pa.s

100 Untreated
Treated
ZB30A-2%
ZB30B-2%
ZB31/1-2%

10
1E+4 1E+5 1E+6

Shear Stress, Pa
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VISCOSITY TESTING RESULTS:

u Untreated CaCO 3 with no additives had higher melt viscosities across the
shear range when compared to treated CaCO 3.

u The untreated CaCO 3 with fatty acid derivatives added had melt viscosities
comparable to treated CaCO 3 across the shear range.

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SPECTROPHOTOMETER DATA, D65/10°

Description L* a* b* C* h
ProFax 6323
Untreated 85.2 0.6 4.5 4.6 82.4
Treated 87.2 -0.3 3.5 3.5 94.3
ZB30A - 1% 88.1 -0.3 3.5 3.5 95.0
ZB30B - 1% 87.8 -0.3 3.6 3.6 94.0
ZB31/1 - 1% 88.3 -0.3 3.3 3.3 95.0
ZB30A - 1.5% 88.2 -0.3 3.3 3.3 95.6
ZB30B - 1.5% 88.1 -0.3 3.4 3.4 95.0
ZB31/1 - 1.5% 88.2 -0.3 3.4 3.4 95.1
Amoco 1016
Untreated 84.2 0.7 6.5 6.5 84.2
Treated 86.4 -0.5 5.2 5.2 96.0
ZB30A - 1.5% 87.6 -0.6 5.5 5.5 96.5
ZB30B - 1.5% 88.0 -0.4 5.0 5.0 95.1
ZB31/1 - 1.5% 87.7 -0.5 4.7 4.7 96.1

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 REFLECTANCE BY SPECTROPHOTOMETER FOR ProFax 6323 COMPOUNDS,
D65/10 degree

75

70

65
Reflectance, %

60
Untreated
55 Treated
ZB30A-1%

50 ZB30B-1%
ZB31/1-1%

45
300 400 500 600 700 800

Wavelength, nm

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 REFLECTANCE BY SPECTROPHOTOMETER FOR AMOCO 1016 COMPOUNDS
D65/10 degree

75

70
Reflectance, %

65
Untreated
Treated
60
ZB30A-2%
ZB30B-2%
55 ZB31/1-2%

50
300 400 500 600 700 800

Wavelength, nm
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COLOR TESTING RESULTS:

u Untreated CaCO 3 with no additives gives a more yellow/grey compound when

compared to treated CaCO 3.

u The untreated CaCO 3 with fatty acid derivatives gives a much whiter
compound comparable with and in some cases better than the treated CaCO 3.

u In the 5 MFI PP compound, reflectance data shows a much whiter compound

in the untreated CaCO 3 with fatty acid derivatives.

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FLEXURAL PROPERTIES AND IZOD IMPACT STRENGTH:

Flex Flex Notched Unnotched

Strength, Modulus, Impact, Impact,
MPa MPa J/m J/m
ProFax 6323
Untreated CaCO3 44.1 2191 75 641
Treated CaCO3 48.6 2795 150 No Break
ZB30A - 1% 45.7 2274 171 No Break
ZB30B - 1% 49.0 2640 171 No Break
ZB31/1 - 1% 45.9 2265 176 No Break

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MELT TEMPERATURE AND DEGRADATION BY DSC:

Tm, °C Tdeg, °C
Unfilled ProFax 6323 166 246
Untreated CaCO3 168 237
Treated CaCO3 166 231
ZB30A - 1% 167 248
ZB30B - 1% 167 248
ZB31/1 - 1% 168 247

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OVEN AGING DEGRADATION (158 hrs. AT 150°C:

ProFax 6323 ProFax 6323 ProFax 6323

+ Untreated CaCO3 (40%) + Treated CaCO 3 (40%) + Untreated CaCO3 (40%)
+ Fatty Acid Derivative (0.4%)

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ECONOMICS:

u Price estimations used:

− Untreated, F Grade CaCO 3 = $0.093/lb.
− Treated, F Grade CaCO 3 = $0.122/lb.
− Untreated, UF Grade CaCO 3 = $0.134/lb.
− Treated, UF Grade CaCO 3 = $0.180/lb.
− Polypropylene, generic = $0.400/lb.
− Fatty Acid Additive analyzed at $1.25, 1.00 and 0.80/lb.

u Compound costs based on the formulations used in this study

u No change in output rates or other production costs

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 COST SAVINGS REALIZED USING FATTY ACID DERIVATIVES
VS. TREATED CONTROL
1 MM LB. PRODUCTION RUN
20000
Estimated Annual Cost Savings Based on F Grade CaCO3
18000 Estimated Annual Cost Savings based on UF Grade CaCO3

16000

14000
TOTAL $ SAVED PER ANNUM

12000

10000

8000

6000

4000

2000

0
Untreated Control 0.4% FA 0.6% FA 0.8% FA 0.4% FA 0.6% FA 0.8% FA 0.4% FA 0.6% FA 0.8% FA
FA = $1.25/lb. FA = $1.00/lb. FA = $0.75/lb.

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 COST SAVINGS REALIZED USING FATTY ACID DERIVATIVES
VS. TREATED CONTROL
10 MM LB. PRODUCTION RUN
200000

Estimated Annual Cost Savings Based on F Grade CaCO3

180000 Estimated Annual Cost Savings based on UF Grade CaCO3

160000

140000
TOTAL $ SAVED PER ANNUM

120000

100000

80000

60000

40000

20000

0
Untreated Control 0.4% FA 0.6% FA 0.8% FA 0.4% FA 0.6% FA 0.8% FA 0.4% FA 0.6% FA 0.8% FA
FA = $1.25/lb. FA = $1.00/lb. FA = $0.75/lb.

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