A NEW LOOK AT NUCLEATING AGENTS FOR USE IN

POLYPROPYLENE COLOR CONCENTRATES

Angela Halstead, Milliken & Co.

Jeff Jones, Milliken & Co.

Abstract
Molders of polypropylene are constantly trying to improve productivity and part quality. Variations in
resin performance due to pigment nucleation are often a major obstacle. Many organic pigments act as
nucleating agents, which increase the crystallization temperature and crystallization rate of
polypropylene. These changes have a direct impact on the cycle time of a molding process. Since
pigments nucleate polypropylene to different degrees, the changes in cycle time will be different
depending on the pigment used. Pigments that act as nucleating agents also influence the shrinkage of a
molded part. Differences in overall shrinkage make it difficult to make parts with identical dimensions
using various pigments. Certain pigments also promote anisotropic shrinkage, where the shrinkage in
the direction perpendicular to the flow of polymer is significantly different than the parallel shrinkage.
This often leads to warpage problems and in molded parts. This paper will explore the use of
commercial nucleating agents to reduce or eliminate the problems caused by pigments that nucleate
polypropylene. Two case studies in commercial parts will be used to correlate test data to actual
production trials.

Background
Pigments nucleate polypropylene to different degrees, giving a range of crystallization temperatures and
shrinkages. These differences can lead to the following problems for molders:

• Cycle time variation

• Dimensional inconsistency
• Warpage

Non-warping pigments are available, but they are offered in a more limited color palette and may be
prohibitively expensive. In addition, these specialty pigments do not address the problems of cycle time
variation and dimensional inconsistency. An effective solution to these real-world problems is needed.

This paper will explain:

• The mechanism of polypropylene nucleation

• The classes of commercial nucleating agents and their performance in polypropylene
• The nucleation performance of some commercial pigments in polypropylene
• The use of nucleating agents to over-ride pigment nucleation and reduce or eliminate cycle time
variations, dimensional inconsistencies and warpage problems in molded parts.
 The Mechanism of Polypropylene Nucleation

All known nucleating additives are “heterogeneous” nucleators; that is, they present a heterogeneous
surface to the PP melt during cooling that promotes polymer crystallization through epitaxial effects.
During the cooling phase, a well-dispersed nucleating agent in molten PP, through this epitaxial or
template-like effect, causes the formation of many more polymer crystals at a higher temperature as
compared to the same resin without a nucleating agent. This process is shown pictorially in Figure 1.

Polymer Partially Fully

Melt No Crystallization Crystallized Crystallized

Non-
Nucleated

. .
. .
Nucleated . .
. . .

Nucleating Agent Crystallization Partially Fully

Begins Crystallized Crystallized

Cooling

Figure 1. Schematic of the heterogeneous nucleation process

.
Heterogeneous nucleation has been studied extensively and is reasonably well understood from a
theoretical standpoint. A treatment of this topic is beyond the scope of this paper. Interested readers are
referred to the references for this theoretical background [1]-[10].

Classes of Nucleating Agents

Commercial nucleating agents can be divided into three classes. In this paper, one representative from
each class will be evaluated to compare crystallization and shrinkage performance in polypropylene.
For the purposes of this discussion, these will be identified as follows:

• Nucleator 1: from the class of “conventional nucleating agents” – examples include minerals
such as talc and calcium carbonate and aromatic carboxylic acid salts such as sodium and lithium
benzoate. Sodium benzoate was used as the example from this class for the studies presented in
this paper.
• Nucleator 2: from the class of “advanced nucleating agents” – examples include phosphate
ester salts. Advanced nucleating agents generally give higher crystallization temperatures and
improved stiffness in polypropylene vs. conventional nucleating agents. Irgastab® NA-11 from
Ciba Specialty Chemicals was used as the example from this class for the studies presented in
this paper.
 • Nucleator 3: from the class of “hyper nucleating agents” – examples include organic carboxylic
acid salts. Hyper nucleating agents give higher crystallization temperatures and more isotropic
shrinkage vs conventional and advanced nucleating agents. Hyperform® HPN-68L from
Milliken & Company was used as the example from this class for the studies presented in this
paper.

Nucleating agents increase the temperature at which polypropylene begins to crystallize upon cooling
and increase the overall rate of crystallization. These effects result in shorter part cooling times in
injection molding processes, which translate into shorter molding times and increased productivity. The
polymer crystallization temperature (polymer Tc) can be measured by differential scanning calorimetry
(DSC) following ASTM D-794-85. In the following evaluation, each nucleating agent was compounded
into a medium impact copolymer at 600 ppm, and compared to an unnucleated control. As shown in
Figure 2, each nucleating agent increased the polymer Tc of the polypropylene. Nucleator 3 gave the
highest polymer Tc with a 16 oC increase over the control followed by Nucleator 2 with a 14 oC increase
and Nucleator 1 with an 11 oC increase. Since it gives the largest increase in crystallization temperature,
Nucleator 3 should deliver the fastest cycle times in molding processes. Two case studies will be
presented in this paper that show that even small differences in crystallization temperature can be
significant in terms of nucleation performance.

130 126
124
125
121

120
Polymer Tc (oC)

115
110

110

105

100
Unnucleated Nucleator 1 Nucleator 2 Nucleator 3

Figure 2. Polymer peak crystallization temperatures for commercial nucleating agents.

All formulations were run in medium ICP (MFR = 20). The polymer
crystallization temperatures were determined at a cooling rate of 20oC/min.

Nucleating agents also affect polypropylene shrinkage and thus, part dimensions and warpage. As
described in the Injection Molding Handbook: “warpage is caused by variations in shrinkage throughout
the part. These variations may appear from region to region through the thickness, and as different
shrinkages in the directions parallel and perpendicular to the plastic orientation” [11]. The shrinkage
behavior of the same three commercial nucleating agents was evaluated using an ISO 294 Type D2
shrinkage test plaque, shown below in Figure 3. After the plaques were injection molded and allowed to
cool for 48 hours, the percent shrinkage in the machine direction (MD) and the transverse direction (TD)
were measured. The shrinkage isotropy ratio was then determined by dividing the percent shrinkage in
the machine direction by the percent shrinkage in the transverse direction. A ratio of 1 is the desired
value – indicating uniform shrinkage. The farther away from 1, the more likely a part made from this
polypropylene formulation is to warp. The shrinkage isotropy ratio of the three commercial nucleating
agents is shown in Figure 4. Since Nucleator 3 has a ratio closest to 1, parts made from this formulation
should be less likely to warp. In addition to anisotropic shrinkage, warpage can also be caused by part
design and processing conditions. Nucleator 3 only addresses the problem of anisotropic shrinkage.

ISO 294 Type D2 Shrinkage Test Plaque

Polymer Flow Transverse Direction (TD)

59.980 mm (2.361 in)

Machine Direction (MD)

59.997 mm (2.362 in)

Depth
1.956 mm (0.077 in)

Figure 3. Shrinkage test plaque design

1.1

Target Isotropy Ratio = 1

1.0
Shrinkage Isotropy (MD/TD)

0.91

0.9
0.85

0.83

0.8

0.7
Nucleator 1 Nucleator 2 Nucleator 3

Figure 4. Isotropic shrinkage data for commercial nucleating agents. All formulations were run
in a medium ICP (20MFR) and aged for 48 hours.

One theory that may explain the different shrinkage behaviors of nucleating agents is their particle
morphology. This concept is shown pictorially in Figure 5. Microscopy revealed that the particle shape
of each nucleating agent is different. Nucleator 1 is ruler-shaped and Nucleator 2 is needle-shaped.
Both of these particle shapes should orient in the flow direction of the polymer. In contrast, Nucleator 3
has a particle shape that is plate-like and shows no preferential orientation.
 Nucleator 1 Morphology = rulers
Nucleator 2 Morphology = needles

Flow Direction

Orientation of the nucleating agent particles leads to anisotropic shrinkage

Nucleator 3 Morphology = plates

Flow Direction

Lack of particle orientation leads to more isotropic shrinkage

Figure 5. Particle morphology of nucleating agents and the effect of particle orientation on
shrinkage behavior.

Nucleation Performance of Commercial Pigments

Many organic pigments are also effective nucleating agents. When added to polypropylene, these
pigments give different crystallization temperatures, shrinkages, and shrinkage isotropy ratios. Each
pigment nucleates polypropylene to a different degree, creating variation in molding processes that is
difficult to control. To demonstrate this effect, four commercial pigment concentrates (identified in
Table 1) were evaluated for crystallization and shrinkage behavior.

# CI Name Loading Chemistry

1 Pigment Yellow 139 2% Isoindoline (Aminoketone)

2 Pigment Red 48:3 2% Laked Azo (BON Red 2B, SR Lake)

3 Pigment Blue 15:1 2% Phthalocyanine – Stabilized

4 Pigment Green 7 2% Chlorinated Cu Phthalocyanine

Table 1. Commercial pigments used in the studies presented in this paper.

The variation in both crystallization temperature and machine direction (MD) shrinkage is illustrated in
Figure 6. Each pigment gives a different crystallization temperature, which suggests that the optimal
cycle time for each color will be different. In this case, the formulation containing the blue pigment
would be predicted to run at the fastest cycle time, since it gives the highest crystallization temperature.
The processing speed may have to be decreased in order to make quality parts with the other pigments.
This data also indicates that differences in shrinkage behavior between the pigments may make it
difficult to produce parts with identical dimensions in each color. The variation in directional shrinkage
cause by the pigment formulations is captured as the range in machine direction shrinkage for these
samples. The difference between 1.17% shrinkage for the phthalo blue and 1.53% shrinkage for the azo
red predicts that dimensional consistency will be difficult to achieve.

1.75

Red
1.5
MD Shrinkage (%)

Yellow
Green
1.25
Blue

No Pigment
1

0.75
100 105 110 115 120 125
Polymer Tc (C)
Figure 6. Machine direction (MD) shrinkage vs. polymer Tc for four commercial
pigments in a medium ICP (20 MFR).

Figure 7 shows the variation in crystallization temperature and shrinkage isotropy ratios for the four
pigment formulations. Since the isotropy ratios of the blue and green pigments are further away from
the target value of 1 than the other pigments, parts containing these pigments may be more likely to
warp. This effect is further demonstrated when comparing the seemingly small differences in shrinkage
isotropy between the azo red and phthalo green. The 0.96 isotropy ratio of the red pigment indicates that
it will not warp vs. the 0.89 ratio of the green pigment which is known to cause warpage. In a
production scenario, the processing conditions may have to be adjusted to make the same quality parts
using these different pigments.
 1.1

Target isotropy ratio = 1

Shrinkage Isotropy (MD/TD)

1

Yellow Red
No Pigment The phthalo
0.9
pigments are
Green
more likely
to cause
warpage.
0.8

Blue

0.7
100 105 110 115 120 125
Polymer Tc (C)

Figure 7. Shrinkage isotropy vs. polymer Tc for four commercial pigments in a medium ICP
(20 MFR)

Using Nucleating Agents to Solve Molding Problems Associated with Pigments

Commercial nucleating agents can be added to pigmented polypropylene to make the crystallization
temperatures and directional shrinkages of these formulations more uniform. Certain nucleating agents
can also move the shrinkage isotropy ratio of a pigmented formulation closer to the target value of 1,
reducing the likelihood of part warpage.

The four commercial pigments discussed previously were evaluated in conjunction with the three
nucleating agents. The effect of the nucleating agents on crystallization temperature, MD shrinkage and
shrinkage isotropy of the pigment formulations are shown in the three charts in Figure 8. As shown in
Part A, each of the commercial nucleating agents reduces the variation in crystallization temperatures
seen with the different pigments. Nucleator 3 does this while providing the largest increase in polymer
Tc, indicating that these formulations should give the fastest cycle times in molding processes.

All three nucleating agents also reduce the variation in dimensions of the parts. This is shown in the plot
of MD shrinkage vs. formulation. As illustrated in the Part B of Figure 8, Nucleator 3 gives the least
amount of variation between pigment formulations. Using Nucleator 3 should make it possible to
produce parts with identical dimensions with each pigment using the same processing conditions. This
may not be possible with Nucleator 1 or Nucleator 2.

Part C in Figure 8 shows the effect of the three nucleating agents on the shrinkage isotropy ratio of the
pigment formulations. Both Nucleator 2 and Nucleator 3 reduce the variation in shrinkage isotropy for
each formulation. However, the isotropy ratio of the Nucleator 2 was approximately 0.8 for all colors,
indicating that parts made from these formulations may warp. Conversely, the isotropic ratios of the
samples containing Nucleator 3 were very close to 1, indicating a low tendency to cause part warpage.
 (A) Polymer Tc (B) MD Shrinkage
1.8
135.0

130.0
1.6

% MD Shrinkage
125.0

120.0 1.4

115.0
1.2
110.0
U nnucleat ed N ucl eat o r 1 N ucleat o r 2 N ucl eat o r 3
1.0
2% Yellow 2% Red 2% Blue 2% Green Unnucleated Nucleator 1 Nucleator 2 Nucleator 3

2% Yellow 2% Red 2% Blue 2% Green

(C) Shrinkage Isotropy

1.1

1.0

0.9

0.8

0.7
U nnucl eat ed N ucl eat o r 1 N ucl eat o r 2 N ucl eat o r 3

2% Yellow 2% Red 2% Blue 2% Green

Figure 8. Polymer Tc, MD Shrinkage and Shrinkage Isotropy results for commercial
pigment samples with and without nucleating agents added to the formulations.

The data from these studies was plotted in the same format as Figure 6 to show that the addition of a
nucleating agent (Nucleator 3) can “level” the crystallization temperatures and directional shrinkages of
the pigment formulations. Figure 9 predicts that with the addition of Nucleator 3 to these formulations,
it should be possible to mold parts with identical dimensions at the same fast processing speeds.

1.75

Red
1.5
MD Shrinkage (%)

Yellow
Green
1.25
Blue
Formulations
Containing
No Pigment Nucleator 3
1

0.75
100 110 120 130
Polymer Tc (C)

Figure 9. Machine direction (MD) shrinkage vs. polymer Tc for four commercial pigments
formulated with and without Nucleator 3 in a medium ICP (20 MFR).
In the same manner, the shrinkage isotropy vs polymer Tc was plotted for the pigments with and without
Nucleator 3. Figure 10 predicts that pigment samples formulated with Nucleator 3 will likely process at
the same fast speeds and warpage will be eliminated or reduced, especially for the phthalo pigments.

1.1
Shrinkage Isotropy (MD/TD)

1
No Pigment
Yellow Red
Formulations
Containing
0.9
Green Nucleator 3

0.8

Blue

0.7
100 110 120 130

Polymer Tc (C)

Figure 10. Shrinkage Isotropy vs. polymer Tc for four commercial pigments formulated with
and without Nucleator 3 in a medium ICP (20 MFR).

Therefore, when choosing a nucleating agent to incorporate into pigment formulations, Nucleator 3 is
the only commercial nucleating agent that can reduce cycle time, by providing the highest crystallization
temperature; eliminate variation in crystallization properties and shrinkage behavior across different
pigment colors; and reduce the anisotropic shrinkage effect of pigments. This effect is sometimes
referred to as “pigment leveling,” and will be further demonstrated in the case studies that follow.
 Case Study 1: Warpage Improvement
A color concentrate manufacturer interested in evaluating Nucleator 3 provided three common
commercial pigments known to cause warpage (red, blue, and green). Samples were formulated with
and without Nucleator 3 at a loading of 1000 ppm. All formulations were tested in the laboratory using
the ISO test plaque and molded in ICP (26 MFR) resin. The results are shown in Figure 11. In the test
plaque, the pigment leveling results were similar to those seen in the previous pigment / nucleator
evaluations.

1.1
logo
Shrinkage Isotropy (MD/TD)

1.0

PG
7
0.9 PR
53:10 Formulations
containing
0.8 Nucleator 3
PB 15

0.7
110 120 130
Warpage of side wall
Polymer Tc (C)

Figure 11. Pigment leveling effect of pigment Figure 12. Diagram of warpage
formulations containing Nucleator 3. measurement for houseware base

The same formulations were then injection molded into a houseware container base which had
demonstrated warpage in the side walls. Warpage was measured on each part as shown is in Figure 12
above. The increased quality of the parts made with Nucleator 3 can be observed in Photograph 1. In
this example, Nucleator 3 increased the crystallization temperature of the polymer and improved the
shrinkage isotropy so that all three pigments could be processed the same and overall cycle time
reduced. When the amount of warpage in the side wall was measured, it was observed that Nucleator 3
reduced the amount of warpage for all three pigments, as shown in Figure 13.

4.5
4
Sidewall warpage (mm)

3.5
3
2.5
2
1.5
1
0.5
0 PG 7 PG 7 PB 15 PB 15 PR 53:10 PR 53:10
Nucleator 3 Control with N-3 with N-3 with N-3

Photograph 1. Houseware base showing Figure 13. Warpage measurements for pigment
pigment induced warpage on the left formulations with and without Nucleator 3
vs. the same formulation with (N-3).
Nucleator 3 incorporated.
 Case Study 2: Cycle Time Variation
A closure manufacturer was dealing with significant cycle time variation when running three different
pigments (white, red, and blue) in their ECM (extrusion compression molding) process. As a result,
productivity for each color varied: White = 520 caps/min, Red = 540 caps/min, Blue = 580 caps/min.
Manufacturing had a target production rate of 580 caps/min, which was the current rate of the blue
pigment. Production trials were run on a 28mm CSD closure comparing the standard formulations
(containing Nucleator 1) to formulations containing Nulceator 3.

130

125
Polymer Tc (C)

120

115

110

105
White / Red / Blue / White / Red / Blue /
Nucleator 1 Nucleator 1 Nucleator 1 Nucleator 3 Nucleator 3 Nucleator 3

Figure 14. Comparison of polymer Tc for standard pigment formulations (containing Nucleator 1) vs.
formulations containing Nucleator 3 (at 500 ppm).

Output % Defects As shown in Figure 14, Nucleator 3 significantly

Formulations
(caps/min) (Sink marks) increased the polymer Tc for all three colors and
White / Nucleator 1 520 0
eliminated the variation in crystallization
temperatures caused by the pigments. This result
White / Nucleator 1 580 24.0 indicates that pigment leveling has occurred and all
Red / Nucleator 1 540 0 three colors will process the same and at faster speeds
Red / Nucleator 1 580 26.0 than what was previously achievable.
Blue/ Nucleator 1 580 0
The production trial results, shown in Table 2,
Blue / Nucleator 1 610 1.0 confirm what the Tc data predicted. The addition of
White / Nucleator 3 580 0 Nucleator 3 not only allowed all colors to be
processed similarly, but productivity for all three
White / Nucleator 3 600 0
colors increased above the target rate of 580
Red / Nucleator 3 580 0 caps/min, to 600 caps/min and higher in the case of
Red / Nucleator 3 600 0 the blue.
Blue / Nucleator 3 600 0

Blue / Nucleator 3 610 0

Blue / Nucleator 3 630 0

Table 1. ECM Production trial results

 Conclusions
In situations where pigment induced nucleation results in molding problems such as cycle time
variation, dimensional inconsistency and warpage, a hyper nucleator, such as Nucleator 3, can be
incorporated into a color concentrate formulation to improve part quality and productivity. Other
classes of nucleators, i.e. conventional and advanced, are not effective at controlling shrinkage and
warpage problems; and in some cases actually cause additional warpage. Laboratory data quantifying
crystallization and shrinkage behavior of pigments and commercial nucleating agents has been shown to
correlate very well to actual production trials, providing color concentrate manufactures with a method
for screening nucleating agents for use as problem solving additives in polypropylene.

References
1. Kurja, J.; Mehl, N. A., in “Plastics Additive Handbook”, Chapter 18, Ed. H. Zweifel, 2001.
2. Binsbergen, F. L. Polymer 1970, 11, 253.
3. Van Krevelen, D. W. “Properties of Polymers”, 3rd Ed. 1990.
4. Hieber, C. A. Polymer 1995, 36, 1455.
5. Eder, G.; Janeschnitz-Kriegel, H. Mat. Sci. & Tech. 1997, 18, 269.
6. Lotz, B.; Wittmann, J. C. J. Poly. Sci., Phys. Ed. 1981, 19, 1837.
7. Lotz, B.; Wittmann, J. C. Makromol. Chem. 1984, 185, 2043.
8. Hoffmann, J. D. J. Chem. Phys. 1958, 28, 1192.
9. Avrami, M. J. J. Chem. Phys. 1939, 7, 1103; 1940, 8, 212; 1941, 9, 177.
10. Wunderlich, B. “Macromolecular Physics”, Academic Press, New York, 1976.
11. Rosata, D.; Rosata, D. “Injection Molding Handbook”. Chapman & Hall, New York, 1995.