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IMPROVING MOLDING PRODUCTIVITY AND ENHANCING
MECHANICAL PROPERTIES OF POLYPROPYLENE WITH
NUCLEATING AGENTS
James H. Botkin, Neil Dunski*, and Dietmar Maeder+
Ciba Specialty Chemicals Corporation, Tarrytown, New York
*Ciba Specialty Chemicals Corporation, St. Louis, Missouri
+
Ciba Specialty Chemicals Inc., Basel, Switzerland
Introduction
Polypropylene-based materials are widely used in automotive applications due to their excellent
balance of properties and low cost. Further improvements in properties can be achieved through
the use of nucleating agents. These additives function by promoting the crystallization of
polypropylene during molding, providing a wide range of benefits including improved molding
productivity, increased modulus without sacrificing impact strength, enhanced thermal properties,
and improved clarity for special visual effects. This paper presents an overview of the various
types of nucleating agents and compares the effects they provide.
Overview of Nucleating Agents
The first scientific studies on the nucleation of polypropylene were conducted by Beck
1
and
Binsbergen
2-5
. Based on this work it can be concluded that nucleating agents act by introducing a
heterogeneous surface to the supercooled polymer melt, making crystallization more
thermodynamically favorable. As a result of the nucleating effect, the temperature at which the
polymer begins to crystallize is increased, as are the rate of nucleation and overall rate of
crystallization. Nucleating agents also promote the formation of smaller and more numerous
spherulites, resulting in enhanced properties.
A variety of nucleating agents have been used in polypropylene
6
. Talc and carboxylate salts (e.g.
sodium benzoate, NaOBz) were among the first additives used for this purpose and are still
widely used today. In the 1980’s, sorbitol acetals came into use. These additives can produce
spherulites smaller than the wavelength of visible light, providing transparent polypropylene.
Nucleating agents that provide this effect are commonly referred to as clarifiers. More recently
phosphate ester salts have been introduced as high performance nucleating agents. Pigments
(organic & inorganic) used as colorants in polymers can also produce nucleating effects.
Structures of representative nucleating agents are given in the Appendix.
The efficacy of nucleating agents is typically evaluated by determining the peak crystallization
temperature (Tc) on cooling the polymer melt using differential scanning calorimetry. Tc is defined
as the temperature at the peak of the crystallization exotherm. An example of the effect of
nucleation on the crystallization exotherm of polypropylene is shown in Figure 1. Alternatively,
the crystallization half-time can be determined upon rapid cooling of the polymer melt to the
temperature of interest.
Nucleation Effects
Crystallization Effects and Implications for Molding Productivity
Nucleating agents increase the temperature at which the supercooled polymer melt begins to
crystallize on cooling (Figure 2). They also serve to increase the overall rate of crystallization
(Figure 3). As a result, shorter cooling cycles can often be used in injection molding, enabling
shorter molding cycles and a significant improvement in molding productivity. The high
performance phosphate ester salt NA-P is notable in that it shows a significant effect even at low
concentrations.
Figure 1. Effect of Nucleation on the Crystallization of PP Homopolymer on
Cooling (10
o
C/min) from the Melt.
0.0
0.5
1.0
1.5
2.0
2.5
3.0
80 100 120 140 160
Temperature (
o
C)
HeatFlow(mW/mg)
Nucleated
Control
Figure 2. Effect of Nucleating Agents on the Crystallization Temperature (Tc)
of PP Homopolymer.
105
110
115
120
125
130
0 250 500 750 1000
ppm nucleating agent
Tc(
o
C)
NA-P
NaOBz
NA-S
Figure 3. Effect on Crystallization Half Time (140
o
C) in PP Homopolymer.
0
10
20
30
40
50
60
0 250 500 750 1000
ppm nucleating agent
time(sec)
NA-P
NaOBz
Mechanical & Thermal Properties
The formation of a larger number of small spherulites in the molding of nucleated polypropylene
results in increased modulus (Figure 4) without sacrificing impact strength, leading to a superior
stiffness/impact balance (Figure 5). The phosphate ester salt NA-P was most effective at
increasing modulus. A similar increase in modulus has been observed in polypropylene
copolymer
7
. This effect can help to enable the thinwalling of automotive parts such as bumper
fascia.
Figure 4. Effect of Nucleating Agents on Modulus in PP Homopolymer.
1100
1200
1300
1400
1500
1600
1700
0 250 500 750 1000
ppm nucleating agent
FlexuralModulus(MPa)
NA-P
NaOBz
Figure 5. Effect of Nucleating Agents on Stiffness/Impact Balance in PP
Homopolymer.
350
400
450
500
550
600
1100 1200 1300 1400 1500 1600 1700
Flexural Modulus (MPa)
TensileImpact@23o
C(kJ/m2
)
Control
250 ppm NA-P
500 ppm NA-P
1000 ppm NA-P
500 ppm NaOBz
1000 ppm NaOBz
Nucleated polypropylene also exhibits improved thermal properties, such as heat deflection
temperature (Figure 6) and Vicat softening temperature (Figure 7). The phosphate ester NA-P
provided superior performance vs. sodium benzoate. Improving thermal properties is important
for under-the-hood applications as well as for interior applications with high thermal demands,
such as instrument panel structures.
Figure 6. Effect of Nucleating Agents on Heat Deflection Temperature in PP
Homopolymer.
49
50
51
52
53
54
55
56
57
58
59
0 250 500 750 1000
ppm nucleating agent
HDT(o
C)
NA-P
NaOBz
Figure 7. Effect of Nucleating Agents on Vicat Softening Temperature in PP
Homopolymer.
86
87
88
89
90
91
92
93
94
95
0 250 500 750 1000
ppm nucleating agent
VicatTemperature(o
C)
NA-P
NaOBz
Clarity
Another consequence of reducing the size of spherulites in polypropylene is an improvement in
transparency. Haze is decreased (Figure 8) and clarity is increased (Figure 9) by the addition of
Figure 8. Effect of Nucleating Agents on Haze in PP Homopolymer.
20
30
40
50
60
70
80
90
100
0 500 1000 1500 2000
ppm nucleating agent
Haze(%)
NA-P
NaOBz
NA-S
nucleating agents. At higher concentrations (~0.2%), sorbitol-based nucleating agents such as
NA-S give the best results and are commonly used to produce transparent polypropylene for
applications such as food packaging. In automotive applications, increasing the clarity of
polypropylene-based materials may be valuable to provide enhanced colorability or special visual
effects.
Figure 9. Effect of Nucleating Agents on Clarity in PP Homopolymer.
0
10
20
30
40
50
60
70
80
90
100
0 500 1000 1500 2000
ppm nucleating agent
Clarity(%)
NA-P
NaOBz
NA-S
Other Considerations
As heterogeneous additives, the particle size and dispersion of nucleating agents in the polymer
are crucial. Nucleating agents are available in a variety of particle sizes. In general, provided
they are properly dispersed, finer particles give better results. The benefit of using finer
nucleating agents must be weighed vs. potential disadvantages, such as handling characteristics.
Even sorbitol-based clarifiers which are soluble in polypropylene must be properly dispersed for
optimal results. However, additive packages containing nucleating/clarifying agents are available
in feedable forms which alleviate handling, conveying and feeding difficulties while achieving
appropriate dispersion in the resin.
Sodium benzoate is a highly reactive nucleating agent capable of reacting with other formulation
components, including calcium stearate (Table 1). This coadditive is widely used as an acid
scavenger and lubricant in polyolefins. This problem can be avoided by substituting a
hydrotalcite-based acid scavenger. Interaction with calcium stearate is not an issue with higher
performance sorbitol acetal and phosphate ester salt nucleating agents.
Table 1. Effect of Coadditives on the Crystallization of PP Homopolymer
Nucleated with Sodium Benzoate.
Formulation Tc (
o
C)
1000 ppm NaOBz
1000 ppm Calcium stearate
117
1000 ppm NaOBz
500 ppm Mg/Al hydrotalcite
129
Conclusions
Nucleating agents provide many benefits for polypropylene-based materials in automotive
applications, including:
· Improved molding productivity through increased crystallization temperature and
crystallization rate of the supercooled polymer melt,
· Enhanced stiffness/impact balance to enable thinwalling of parts,
· Improved thermal properties for high temperature applications, and
· Improved clarity for enhanced colorability and special visual effects.
Common nucleating agents include carboxylate salts (sodium benzoate, NaOBz), sorbitol acetals
(NA-S), and phosphate ester salts (NA-P). The use of the phosphate ester salt NA-P is
particularly recommended to improve physical properties and molding productivity, while the
sorbitol acetal NA-S is recommended as a clarifier.
Experimental
Substrate
Polypropylene homopolymer, nominal MFR 4 dg/min.
Additives
Except where noted, all formulations contained 0.05% AO-1 + 0.10% AO-2 + 0.10% calcium
stearate as base stabilization. The sodium benzoate used had a maximum particle size of 20 mm
and mean particle size of <3 mm; NA-P had a mean particle size of 6-8 mm.
Compounding
Polymer and additives were blended using a high speed mixer (Henschel). The powder blends
were compounded using a twin screw extruder (Berstorff) at a maximum temperature of 250°C.
Injection Molding
Injection-molded test specimens were prepared on an Arburg 320 S (maximum temperature
240°C, mold temperature 45°C).
Differential Scanning Calorimetry
A TA instruments DSC 2920 was used. Crystallization temperature (Tc) was determined using a
heating/cooling rate of 10
o
C/min under nitrogen. Crystallization half-time (T1/2) was determined
isothermally at 140
o
C after rapid cooling from the melt under nitrogen. Sample size: 10 mg.
Measurement of Polymer Properties
Property Test Method Notes
Tensile Modulus ISO 178 Zwick tensile tester
Tensile Impact Strength ISO 8256
Heat Deflection Temperature ISO 75 Method A (1.80 MPa stress)
Vicat Softening Temperature ISO 306
Haze ASTM D1003-61 BYK Gardner Haze Guard Plus
Clarity ASTM D1003-61
References
1. Beck, H. N. J. Appl. Pol. Sci., 1967, 11, 673.
2. Binsbergen, F. L. Polymer, 1970, 11, 253.
3. Binsbergen, F. L. and DeLange, B. G. M. Polymer, 1970, 11, 309.
4. Binsbergen, F. L. J. Poly. Sci., 1973, 11, 117.
5. Binsbergen, F. L. J. Poly. Sci., Poly. Symp., 1977, 59, 11.
6. Kurja, J. and Mehl, N. A. in “Plastics Additives Handbook”, 5
th
ed.; H. Zweifel, Ed.; Hanser
Gardner Publications, Inc.: Cincinnati, 2001; Ch. 18.
7. Pukanszky, B.; Mudra, I.; Staniek, P. J. Vinyl Add. Tech., 1997, 3, 53.
Appendix
Nucleating Agents
Name Class Composition Tradename
NaOBz Carboxylate
salt
O
ONa
IRGASTABâ NA 02
IRGASTABâ NA 04
NA-S Sorbitol
acetal
O
O
O
O
CH3
CH3
OHOH
IRGACLEARâ DM
NA-P Phosphate
ester salt
O O
P
O ONa IRGASTABâ NA 11 UH
Other Additives
Name Class Composition Tradename
AO-1 Hindered
phenol
OH
O
O C
4
IRGANOXâ 1010
AO-2 Phosphite
O
P
3
IRGAFOSâ 168
IRGACLEARâ, IRGAFOSâ, IRGANOXâ, and IRGASTABâ are registered trademarks of Ciba
Specialty Chemicals Corporation.

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Nucleating Agents for Polypropylene

  • 1. IMPROVING MOLDING PRODUCTIVITY AND ENHANCING MECHANICAL PROPERTIES OF POLYPROPYLENE WITH NUCLEATING AGENTS James H. Botkin, Neil Dunski*, and Dietmar Maeder+ Ciba Specialty Chemicals Corporation, Tarrytown, New York *Ciba Specialty Chemicals Corporation, St. Louis, Missouri + Ciba Specialty Chemicals Inc., Basel, Switzerland Introduction Polypropylene-based materials are widely used in automotive applications due to their excellent balance of properties and low cost. Further improvements in properties can be achieved through the use of nucleating agents. These additives function by promoting the crystallization of polypropylene during molding, providing a wide range of benefits including improved molding productivity, increased modulus without sacrificing impact strength, enhanced thermal properties, and improved clarity for special visual effects. This paper presents an overview of the various types of nucleating agents and compares the effects they provide. Overview of Nucleating Agents The first scientific studies on the nucleation of polypropylene were conducted by Beck 1 and Binsbergen 2-5 . Based on this work it can be concluded that nucleating agents act by introducing a heterogeneous surface to the supercooled polymer melt, making crystallization more thermodynamically favorable. As a result of the nucleating effect, the temperature at which the polymer begins to crystallize is increased, as are the rate of nucleation and overall rate of crystallization. Nucleating agents also promote the formation of smaller and more numerous spherulites, resulting in enhanced properties. A variety of nucleating agents have been used in polypropylene 6 . Talc and carboxylate salts (e.g. sodium benzoate, NaOBz) were among the first additives used for this purpose and are still widely used today. In the 1980’s, sorbitol acetals came into use. These additives can produce spherulites smaller than the wavelength of visible light, providing transparent polypropylene. Nucleating agents that provide this effect are commonly referred to as clarifiers. More recently phosphate ester salts have been introduced as high performance nucleating agents. Pigments (organic & inorganic) used as colorants in polymers can also produce nucleating effects. Structures of representative nucleating agents are given in the Appendix. The efficacy of nucleating agents is typically evaluated by determining the peak crystallization temperature (Tc) on cooling the polymer melt using differential scanning calorimetry. Tc is defined as the temperature at the peak of the crystallization exotherm. An example of the effect of nucleation on the crystallization exotherm of polypropylene is shown in Figure 1. Alternatively, the crystallization half-time can be determined upon rapid cooling of the polymer melt to the temperature of interest. Nucleation Effects Crystallization Effects and Implications for Molding Productivity Nucleating agents increase the temperature at which the supercooled polymer melt begins to crystallize on cooling (Figure 2). They also serve to increase the overall rate of crystallization (Figure 3). As a result, shorter cooling cycles can often be used in injection molding, enabling shorter molding cycles and a significant improvement in molding productivity. The high
  • 2. performance phosphate ester salt NA-P is notable in that it shows a significant effect even at low concentrations. Figure 1. Effect of Nucleation on the Crystallization of PP Homopolymer on Cooling (10 o C/min) from the Melt. 0.0 0.5 1.0 1.5 2.0 2.5 3.0 80 100 120 140 160 Temperature ( o C) HeatFlow(mW/mg) Nucleated Control Figure 2. Effect of Nucleating Agents on the Crystallization Temperature (Tc) of PP Homopolymer. 105 110 115 120 125 130 0 250 500 750 1000 ppm nucleating agent Tc( o C) NA-P NaOBz NA-S Figure 3. Effect on Crystallization Half Time (140 o C) in PP Homopolymer. 0 10 20 30 40 50 60 0 250 500 750 1000 ppm nucleating agent time(sec) NA-P NaOBz
  • 3. Mechanical & Thermal Properties The formation of a larger number of small spherulites in the molding of nucleated polypropylene results in increased modulus (Figure 4) without sacrificing impact strength, leading to a superior stiffness/impact balance (Figure 5). The phosphate ester salt NA-P was most effective at increasing modulus. A similar increase in modulus has been observed in polypropylene copolymer 7 . This effect can help to enable the thinwalling of automotive parts such as bumper fascia. Figure 4. Effect of Nucleating Agents on Modulus in PP Homopolymer. 1100 1200 1300 1400 1500 1600 1700 0 250 500 750 1000 ppm nucleating agent FlexuralModulus(MPa) NA-P NaOBz Figure 5. Effect of Nucleating Agents on Stiffness/Impact Balance in PP Homopolymer. 350 400 450 500 550 600 1100 1200 1300 1400 1500 1600 1700 Flexural Modulus (MPa) TensileImpact@23o C(kJ/m2 ) Control 250 ppm NA-P 500 ppm NA-P 1000 ppm NA-P 500 ppm NaOBz 1000 ppm NaOBz Nucleated polypropylene also exhibits improved thermal properties, such as heat deflection temperature (Figure 6) and Vicat softening temperature (Figure 7). The phosphate ester NA-P provided superior performance vs. sodium benzoate. Improving thermal properties is important for under-the-hood applications as well as for interior applications with high thermal demands, such as instrument panel structures.
  • 4. Figure 6. Effect of Nucleating Agents on Heat Deflection Temperature in PP Homopolymer. 49 50 51 52 53 54 55 56 57 58 59 0 250 500 750 1000 ppm nucleating agent HDT(o C) NA-P NaOBz Figure 7. Effect of Nucleating Agents on Vicat Softening Temperature in PP Homopolymer. 86 87 88 89 90 91 92 93 94 95 0 250 500 750 1000 ppm nucleating agent VicatTemperature(o C) NA-P NaOBz Clarity Another consequence of reducing the size of spherulites in polypropylene is an improvement in transparency. Haze is decreased (Figure 8) and clarity is increased (Figure 9) by the addition of Figure 8. Effect of Nucleating Agents on Haze in PP Homopolymer. 20 30 40 50 60 70 80 90 100 0 500 1000 1500 2000 ppm nucleating agent Haze(%) NA-P NaOBz NA-S
  • 5. nucleating agents. At higher concentrations (~0.2%), sorbitol-based nucleating agents such as NA-S give the best results and are commonly used to produce transparent polypropylene for applications such as food packaging. In automotive applications, increasing the clarity of polypropylene-based materials may be valuable to provide enhanced colorability or special visual effects. Figure 9. Effect of Nucleating Agents on Clarity in PP Homopolymer. 0 10 20 30 40 50 60 70 80 90 100 0 500 1000 1500 2000 ppm nucleating agent Clarity(%) NA-P NaOBz NA-S Other Considerations As heterogeneous additives, the particle size and dispersion of nucleating agents in the polymer are crucial. Nucleating agents are available in a variety of particle sizes. In general, provided they are properly dispersed, finer particles give better results. The benefit of using finer nucleating agents must be weighed vs. potential disadvantages, such as handling characteristics. Even sorbitol-based clarifiers which are soluble in polypropylene must be properly dispersed for optimal results. However, additive packages containing nucleating/clarifying agents are available in feedable forms which alleviate handling, conveying and feeding difficulties while achieving appropriate dispersion in the resin. Sodium benzoate is a highly reactive nucleating agent capable of reacting with other formulation components, including calcium stearate (Table 1). This coadditive is widely used as an acid scavenger and lubricant in polyolefins. This problem can be avoided by substituting a hydrotalcite-based acid scavenger. Interaction with calcium stearate is not an issue with higher performance sorbitol acetal and phosphate ester salt nucleating agents. Table 1. Effect of Coadditives on the Crystallization of PP Homopolymer Nucleated with Sodium Benzoate. Formulation Tc ( o C) 1000 ppm NaOBz 1000 ppm Calcium stearate 117 1000 ppm NaOBz 500 ppm Mg/Al hydrotalcite 129
  • 6. Conclusions Nucleating agents provide many benefits for polypropylene-based materials in automotive applications, including: · Improved molding productivity through increased crystallization temperature and crystallization rate of the supercooled polymer melt, · Enhanced stiffness/impact balance to enable thinwalling of parts, · Improved thermal properties for high temperature applications, and · Improved clarity for enhanced colorability and special visual effects. Common nucleating agents include carboxylate salts (sodium benzoate, NaOBz), sorbitol acetals (NA-S), and phosphate ester salts (NA-P). The use of the phosphate ester salt NA-P is particularly recommended to improve physical properties and molding productivity, while the sorbitol acetal NA-S is recommended as a clarifier. Experimental Substrate Polypropylene homopolymer, nominal MFR 4 dg/min. Additives Except where noted, all formulations contained 0.05% AO-1 + 0.10% AO-2 + 0.10% calcium stearate as base stabilization. The sodium benzoate used had a maximum particle size of 20 mm and mean particle size of <3 mm; NA-P had a mean particle size of 6-8 mm. Compounding Polymer and additives were blended using a high speed mixer (Henschel). The powder blends were compounded using a twin screw extruder (Berstorff) at a maximum temperature of 250°C. Injection Molding Injection-molded test specimens were prepared on an Arburg 320 S (maximum temperature 240°C, mold temperature 45°C). Differential Scanning Calorimetry A TA instruments DSC 2920 was used. Crystallization temperature (Tc) was determined using a heating/cooling rate of 10 o C/min under nitrogen. Crystallization half-time (T1/2) was determined isothermally at 140 o C after rapid cooling from the melt under nitrogen. Sample size: 10 mg. Measurement of Polymer Properties Property Test Method Notes Tensile Modulus ISO 178 Zwick tensile tester Tensile Impact Strength ISO 8256 Heat Deflection Temperature ISO 75 Method A (1.80 MPa stress) Vicat Softening Temperature ISO 306 Haze ASTM D1003-61 BYK Gardner Haze Guard Plus Clarity ASTM D1003-61
  • 7. References 1. Beck, H. N. J. Appl. Pol. Sci., 1967, 11, 673. 2. Binsbergen, F. L. Polymer, 1970, 11, 253. 3. Binsbergen, F. L. and DeLange, B. G. M. Polymer, 1970, 11, 309. 4. Binsbergen, F. L. J. Poly. Sci., 1973, 11, 117. 5. Binsbergen, F. L. J. Poly. Sci., Poly. Symp., 1977, 59, 11. 6. Kurja, J. and Mehl, N. A. in “Plastics Additives Handbook”, 5 th ed.; H. Zweifel, Ed.; Hanser Gardner Publications, Inc.: Cincinnati, 2001; Ch. 18. 7. Pukanszky, B.; Mudra, I.; Staniek, P. J. Vinyl Add. Tech., 1997, 3, 53.
  • 8. Appendix Nucleating Agents Name Class Composition Tradename NaOBz Carboxylate salt O ONa IRGASTABâ NA 02 IRGASTABâ NA 04 NA-S Sorbitol acetal O O O O CH3 CH3 OHOH IRGACLEARâ DM NA-P Phosphate ester salt O O P O ONa IRGASTABâ NA 11 UH Other Additives Name Class Composition Tradename AO-1 Hindered phenol OH O O C 4 IRGANOXâ 1010 AO-2 Phosphite O P 3 IRGAFOSâ 168 IRGACLEARâ, IRGAFOSâ, IRGANOXâ, and IRGASTABâ are registered trademarks of Ciba Specialty Chemicals Corporation.