Equistar

Technical
Tip

tech.topic
Additives: Nucleating and Clarifying Agents
As polypropylene (PP) cools from the molten
state, individual chains begin to form crystalline
structures around nucleation sites. These
nucleation sites can either be imperfections or
inconsistencies in a polymer chain or foreign
particles in the melt. As the polymer continues
to cool, more chains crystallize around the
nucleation site, forming spherulites.

Heat Flow (W/g)

3

102.7C
2

When PP cools completely, it is made up of

approximately 60% crystalline and 40%
amorphous, or non-crystalline, areas. The
crystallization rate of PP is increased by the
presence of foreign particles in the melt around
which the polypropylene chains can crystallize.
While it is cooling, PP also undergoes
supercooling. Supercooling refers to the
difference between the melting temperature and
the temperature at which crystallization of the
polymer begins. This temperature is called the
"onset of crystallization temperature." For
example, PP random copolymers (without a
nucleating agent) melt at about 145C (293F) but
begin to crystallize at about 112C (234F). This
temperature difference means that molded parts
must be cooled well below the melting point of
PP before the resin begins to crystallize (see
Figure 1).
Nucleating agents (nucleators) and clarifying
agents (clarifiers) work by altering the way the
PP chains crystallize and agglomerate in the
molten state. Nucleators and clarifiers also
reduce the degree of supercooling in the resins
by increasing the onset of crystallization
temperature (see Figure 2). These agents
provide numerous nucleating sites around which
the PP chains can crystallize. The numerous
nucleating sites also increase the amount of
crystallinity in the resin and decrease the
average size and narrow the size range of the
spherulites (Figures 3 and 4). Nucleators and
clarifiers also increase the stiffness of the end
product and slightly reduce the impact strength.

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108.3C
88.8 J/g

-1

COOLING CURVE

-2
20

70

120

170

Temperature (C)

Figure 1: Differential Scanning Calorimetry (DSC)

cooling curve for a non-nucleated random
copolymer PP. Note the degree of super cooling
from a melt temperature of 147C to the onset of
crystallization at 108.3C
Heat Flow (W/g)
3

116.9C
2

120.6C
84.7 J/g

-1

COOLING CURVE
-2
40

90

140

190

Temperature (C)

Figure 2: DSC cooling curve for a nucleated

random copolymer PP showing the increase in
onset of cooling temperature (120.6C) and
therefore a decrease in the degree of
supercooling
(Continued on Page 2)

Equistar
Technical
Tip

tech.topic
Additives: Nucleating and Clarifying Agents
(continued)
The most effective nucleating agents are
chemical derivatives of benzoic acid. Because of
its strong nucleating ability and low cost, the
most widely used nucleating agent is sodium
benzoate, a synthetic, white, opaque powder.
Other nucleating agents include naturally
occurring minerals such as kaolin and talc.

Figure 3: Optical microscopy slide showing the

crystal structure of a PP resin without a
nucleating agent.
(Photo Courtesy of Milliken Chemicals)
NUCLEATING AGENTS
Nucleating agents are generally inorganic
materials with a small average particle size and a
high melting point. When a nucleated resin is
melted in an extruder, the nucleating agent
remains solid and provides a site around which
the PP spherulites can form.

Adding a nucleating agent to PP increases crystal

growth, and this growth occurs faster and at a
higher temperature (15 to 20C) than without the
additive. Because the degree of supercooling is
reduced, parts made from nucleated PP resins
can be removed from the mold at higher
temperatures and as a result, cycle times are
decreased and output raised.
However, in multi-cavity and thin-wall injection
molds, nucleating agents may cause the resin to
solidify before the mold cavity is completely
filled, resulting in short shots. Another potential
downside is that sodium benzoate is known to
interfere with red pigments, causing them to turn
orange. Nucleating agents are also not typically
used to stiffen random copolymer PP resins
because clarity decreases.
CLARIFYING AGENTS
Clarifying agents (or clarifiers) are usually
organic, non-polymeric molecules. All clarifying
agents also act as nucleating agents, but
nucleating agents are not necessarily clarifying
agents. Most clarifiers on the market today are
chemical derivatives of dibenzylidene sorbitol
(DBS) and have melting temperatures within the
processing window of PP resins.

Clarifying agents melt during processing and

disperse in the polymer matrix. When the molten
polymer cools, the clarifier solidifies at the same
temperature at which it melted.

Figure 4: Optical microscopy slide showing the

crystal structure of a PP resin with a nucleating
agent. Note the smaller and more uniform
spherulite structure as compared to Figure 3.
(Photo Courtesy of Milliken Chemicals)

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At this point, PP crystallization starts at a

higher temperature than it would have without
the clarifier. So, as with nucleating agents, parts
can be removed from the mold sooner and cycle
times go down.

(Continued on Page 3)

Equistar
Technical
Tip

tech.topic
Additives: Nucleating and Clarifying Agents
(continued)
Clarifiers also increase the clarity of PP by
reducing the size of the spherulites. Smaller
spherulites allow more light through the
polymer, which decreases the haze of the part.
Unlike nucleating agents, clarifiers are
transparent, which also helps decrease haze
values.
Care must be taken in processing clarified
random copolymer PP resins because if too high
of a melt temperature is used, the clarifier
degrades, and haze values go up. Parts molded
from clarified resins may have a slight, cherry or
almond-like odor, but a very strong smell near
the molding machine can be a sign of clarifier
degradation.
Too little mixing (low back pressure) or a low
melt temperature may keep the clarifying agent
from properly dispersing. White specks in the
molded part are usually an indication of poor
clarifier melting and dispersion. The
recommended melt temperature processing
range for clarified PP is between 193 and 232C
(380 and 450F).
To maximize the clarity of the pad, the melt
temperature should be the lowest possible
temperature at which the clarifier disperses
properly. A high gloss mold is also necessary to

achieve the best clarity. In injection molding,

reduce the packing pressure, since high
pressures can cause the polymer chains to
"pack," resulting in higher haze values. To
achieve the best possible clarity in blow molding,
use an injection stretch blow molding machine.
Injection blow molding machines produce parts
with lower clarity and parts from extrusion blow
molding machines are even less clear,
comparatively.
Two problems may arise from the use of a
clarified resin. First, clarifiers perform best
when processed within the normal processing
window for PP. If the resin is processed at too
high a temperature, unwanted odor and taste
characteristics (organoleptics) occur in the end
product. The clarity of the part also decreases if
the processing temperatures are too high. If the
resin is processed at too low a temperature, poor
dispersion and a decrease in clarity may result.
Second, because the clarifying agent causes the
part to set up at a higher temperature, ejecting
the part from the mold may be difficult. Poor
ejection can usually be prevented by increasing
the mold temperature or decreasing the cooling
cycle so that parts eject at a higher temperature.
Anti-static agents are usually added to the
clarified resins to enhance mold release and to
aid in clarifier dispersion.

The information on this document is, to our knowledge, true and accurate. However, since the particular uses and the actual
conditions of use of our products are beyond our control, establishing satisfactory performance of our products for the intended
application is the customer's sole responsibility. All uses of Equistar products and any written or oral information, suggestions or
technical advice from Equistar are without warranty, express or implied, and are not an inducement to use any process or product in
conflict with any patent.
Equistar materials are not designed or manufactured for use in implantation in the human body or in contact with internal body fluids
or tissues. Equistar makes no representation, promise, express warranty or implied warranty concerning the suitability of these
materials for use in implantation in the human body or in contact with internal body tissues or fluids.
More detailed safety and disposal information on our products is contained in the Material Safety Data Sheet (MSDS). All users of our
products are urged to retain and use the MSDS. A MSDS is automatically distributed upon purchase/order execution. You may
request an advance or replacement copy by calling our MSDS Hotline at (800) 700-0946.
Lyondell Chemical Company
1221 McKinney, Suite 700
P.O. Box 2583
Houston, Texas 77252-2583
(800) 615-8999
http://www.Lyondell.com
7972E/0501

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