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Polystyrene and BASF Plastics

key to your success


Styrolux®
General-purpose polystyrene (GPPS)
High-impact polystyrene (HIPS)
Styrene / butadien-block copolymer (S/B/S)
4 Polystyrene and Styrolux® – at a glance

Polystyrene and its characteristic properties

5 Mechanical properties
8 Thermal properties
9 Rheological properties
10 Electrical properties
Optical properties
11 Permeability to gas and water vapor
Water absorption
12 Resistance to chemicals
Environmental stress cracking behavior
13 Aging behavior
Resistance to high-energy radiation
Resistance to microorganisms

Special Polystyrene grades and their particular properties

14 High-gloss Polystyrene – PS 454 C


15 Polystyrene grade with increased environmental stress cracking resistance – PS ESCRimoTM

Styrolux® and its characteristic properties

16 Mechanical properties
20 Optical properties
21 Thermal properties
Electrical properties
22 Rheology
Chemical resistance
Stress cracking
23 Permeability
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Organoleptic characteristics
Aging
Sterilizability
Copyright 2007


Processing of Polystyrene and Styrolux®

24 General information
25 Injection unit
Injection molding tools
26 Injection molding / Polystyrene
29 Injection molding / Styrolux®
31 Extrusion / Polystyrene
38 Blow molding
Thermoforming
39 Machining
40 Extrusion / Styrolux®

Safety information; Safety precautions during processing

43 Safety precautions during processing


Food Contact Applications
Medical Devices and Pharmaceutical Applications
44 Recycling
45 Nomenclature
Colors
Forms supplied and storage
46 Overview of products

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Polystyrene and Styrolux® – at a glance

Polystyrene and Styrolux® – at a glance


Polystyrene is BASF’s trade name for its line of general-purpose and Product line
high-impact polystyrenes for injection molding, extrusion, thermoform- BASF’s Polystyrene range constitutes a highly developed materials
ing, blow molding and injection blow molding. line, including both general-purpose and high-impact Polystyrene
grades. The basic grades differ primarily in their combination of tough-
General-purpose Polystyrene is formed by polymerization of styrene. ness, rigidity, heat distortion resistance and flow behavior.
High-impact Polystyrene is produced by polymerization of styrene
in the presence of butadiene rubber; the elastomer component is Details of the products available are given below:
dispersed in the form of spherical particles in the normal polystyrene
matrix (Fig. 1). General-purpose Polystyrene
High molecular weight grades having high strength and gradated
Styrolux® is the trade name for BASF’s thermoplastic materials con- heat distortion resistance and flow for injection molding and extru-
sisting of styrene-butadiene block copolymers. They can be used uni- sion.
versally for injection molding, extrusion and thermoforming. Product with high heat distortion resistance and intermediate
strength and flow for injection molding, extrusion and expanded
Styrolux® is produced by copolymerization of styrene and butadiene film production.
in the form of connected blocks, The polystyrene and polybutadiene A grade which flows easily and has good strength for general
phases which separately come together form a lamellar structure. injection molding and extrusion applications.

These phases have such vanishingly small dimensions and at the High-impact Polystyrene
same time are arranged so systematically that light can pass through High-impact to super-high-impact grades with normal flow for
virtually unhindered without appreciable scattering. extrusion and injection molding.
Products with increased environmental stress cracking resistance
The electron micrograph in Fig.  2 clearly shows the lamellar structural for extrusion and injection molding.
arrangement and the coherent distribution of the rubber phase (dark Polystyrene with high surface gloss.
zones). These features result in the glass-like transparency and the
high toughness. Styrolux®
The Styrolux® line encompasses grades which differ in toughness,
heat distortion resistance and flow.
A grade which flows very easily for producing injection-molded,
tough-and-rigid parts.
Tough universal grades for injection molding and extrusion.
A high-toughness product for extrusion of flat film in admixture
with general-purpose Polystyrene for deep-drawn parts.
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5 µm 1 µm
Copyright 2007

Fig. 1: Electron micrograph of an ultra-thin section of high-impact Fig.  2: Electron micrograph of an ultra-thin section of Styrolux ®.
Polystyrene: the number, size, size distribution and internal structure
of the rubber particles determine the property profile of high-impact
Polystyrene. 
Mechanical properties of Polystyrene

Polystyrene and its characteristic properties


Mechanical properties The shape of this curve shows general-purpose Polystyrene to be a
rigid and dimensionally stable but relatively non-ductile material hav-
The typical property values determined on standard test specimens ing a high tensile strength and low elongation at break.
and shown in the overview of the product line give the processor
as well as the design engineer the guide values necessary to select High-impact Polystyrene displays a less steep initial rise in the curve
the most suitable grade for a specific application. Of course, the and, after reaching the yield point, pronounced deformation until rup-
mechanical quality of a finished part depends not only on the material: ture. This behavior is characteristic of tough materials.
structural design matched to the material and processing and also
processing conditions appropriate to the product are also of consider- The toughness of high-impact Polystyrene increases with increasing
able importance. rubber content.

Stress-strain characteristics The stress-strain behavior of Polystyrene is dependent on the tempera­


The behavior of Polystyrene under short-term uniaxial tensile stress at ture and on the deformation rate. As can be seen from Figs. 4 and 5,
a low deformation rate is depicted in the stress-strain graph shown in the elongation at break of high-impact Polystyrene decreases as the
Fig. 3 which was obtained in a tensile test in accordance with ISO 527. temperature drops and as the deformation rate increases while the
tensile strength displays the opposite relationship. The temperature
General-purpose Polystyrene is typified by a steep, almost linear curve effect is significantly greater than the influence of the deformation rate.
and rupture after very low deformation.
Tensile stress [MPa]

Tensile stress [MPa]

Test temperature
50 -40°C
-20°C
60 ±0°C

General-purpose Polystyrene 40
+20°C
High-impact
40 30
Polystyrene +40°C

20 +60°C
20
10
+80°C
εR
0 20
0 10 20 30 40 50 60 0 10 20 30 40 50 60 70 80 90 100
Strain [%] Strain [%]

Fig. 3: Stress-strain curves of general-purpose and high-impact Poly- Fig. 4: Stress-strain curves of high-impact Polystyrene at various test
styrene in a tensile test in accordance with ISO 527. temperatures; strain rate = 2 mm / min, determined on injection-
BASF Aktiengesellschaft

molded test specimens.


Copyright 2007


Mechanical properties of Polystyrene

Polystyrene and its characteristic properties


Modulus of elasticity [MPa]
Tensile stress [MPa]

4000 Polystyrene
50 168 N

40 3000

30
2000 Polystyrene
Strain rate 486 M
20
500 mm/min
200 mm/min
100 mm/min 1000
10 10 mm/min
1 mm/min
0.1 mm/min
0 0
0 5 10 15 20 25 30 35 40 45 50 -40 -20 0 20 40 60 80
Strain [%] Temperature [°C]

Fig. 5: Stress-strain curves of high-impact Polystyrene at different Fig. 6: Modulus of elasticity of Polystyrene in accordance with ISO 527
strain rates. Determined on injection-molded test specimens. as a function of the temperature. Determined on injection-molded test
specimens.

Modulus of elasticity (Young’s modulus)


Shear modulus [MPa]

Λ
An important parameter for describing the rigidity is the modulus of
elasticity determined in a tensile test; this is likewise dependent on the
temperature (Fig. 6). 103

Polystyrene
Shear modulus and logarithmic decrement of the mechanical
10 2 168 N 10
damping
486 M
In place of the modulus of elasticity, the shear modulus determined
in the ISO 6721-2 torsional pendulum test is often employed as a
measure of rigidity. Fig. 7 shows the temperature dependence of the 101 1.0
Mechanical damping
shear modulus. The shear modulus of general-purpose Polystyrene is
virtually constant over a wide temperature range. Only in the soften-
ing range of Polystyrene does it drop sharply by several powers of 100 0.10
ten. The logarithmic decrement of the mechanical damping displays a
maximum at this juncture.
10-1 0.01
10 10
High-impact Polystyrene displays an additional slight drop in the shear -150 -100 -50 0 50 100
modulus or a secondary damping maximum at about -80 °C. This is Temperature [°C]
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explained by the glass transition temperature of the rubber component


which lies in this region. Fig. 7: Shear modulus and mechanical damping of Polystyrene as a
function of temperature.
Copyright 2007


Mechanical properties of Polystyrene

Polystyrene and its characteristic properties


Impact toughness In the flexural impact test, the stress direction in injection-molded
In contrast to the relatively low deformation rate in the tensile test and specimens is the same as the preferred orientation direction. This
the creep test, the high deformation rate in the impact test leads to a increases the measured impact toughness and the flexural impact test
significantly higher dynamic load on the test specimens. therefore serves primarily for comparing the toughness of different
products.
Most high-impact Polystyrenes fail in the ISO 179 flexural impact test
only if the test specimens have been notched beforehand. In practice, however, multiaxial stress without a preferred direction has
to be expected. This is addressed by the instrumented puncture test of
The ISO 179 /1e A test of the notched impact toughness is carried out ISO 6603-2, in which a blow is struck centrally on a flat surface (e.g.
on specimens provided with a V-notch. a circular disk).
Charpy ak (kJ/m2)

20
Notched impact strength at 23°C

15

10

0
F

10
I
5
5

27
6

48
49

45
48

Polystyrene

Fig. 8: BASF Aktiengesellschaft


Copyright 2007


Thermal properties of Polystyrene

Polystyrene and its characteristic properties


Thermal properties Linear thermal expansion; specific heat
The temperature dependence of the linear thermal expansion and the
Heat distortion resistance specific heat of Polystyrene can be seen in Figs.   9 and 10.
The heat distortion resistance of finished Polystyrene parts is depen-
dent on their shape, the production conditions, the type of heat source
and the duration of heating and also on the Polystyrene grade in ques-
tion. Parts produced without application of an external load and having
low internal stresses can be heated for a short time to about 15 °C
below the Vicat softening temperature without undergoing distortion.

Specific heat [J/g·K]


Linear thermal expansion [%]

1.5 2.5

Polystyrene 495 F
1.0 2.1

Polystyrene 495 F
0.5 1.7
Polystyrene 168 N
Polystyrene 168 N
0 1.3

-0.5 0.9

-1.0
0 -20 0 20 40 60 80 100 120 -50 0 50 100 150 200 250
Temperature [°C] Temperature [°C]

Fig.  9: Linear thermal expansion of Polystyrene as a function of Fig. 10: Specific heat of Polystyrene as a function of temperature.
temperature.

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Copyright 2007


Rheological properties of Polystyrene

Polystyrene and its characteristic properties


Rheological properties
Output Q [ml/s]

102 Like all thermoplastics, Polystyrene is a non-Newtonian fluid. This


Polystyrene 143 E
means that the viscosity depends not only on the temperature but also
on the shear rate. As a result, the melt output increases overpropor-
101
tionally with increasing pressure. In Fig. 11, the temperature is also
shown as a parameter.
100
The shear rate D in a circular nozzle is proportional to the throughput
Q and inversely proportional to the cube of the radius r as given by the
10-1 formula
280 °C 4Q
260 °C D=
10-2
240 °C π ⋅ r3
220 °C Fig. 12 shows the relationship between viscosity and shear rate for
200 °C 180 °C three different Polystyrene grades.
10-3
0 1 10 100
Extrusion pressure P [bar]

Fig. 11: Melt output of Polystyrene 143 E as a function of the extrusion


pressure (flow curves), measured at from 180 to 280 °C.
True viscosities [Pa ∙ s]

Temperature 230 °C
104
Polystyrene 158
Polystyrene 486
103 Polystyrene 143

102

101

100
10-2 10-1 100 101 102 103 104 105
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True shear rate [1/s]

Fig. 12: Viscosity of Polystyrene as a function of the shear rate


(measured in accordance with ISO 11443).
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Electrical and optical properties of Polystyrene

Polystyrene and its characteristic properties


Light transmittance [%]
εR

2.5 100
Moist
Polystyrene 168 Dry Polystyrene
2
90
10-2
tan δ

10-3 80
10-4 70
10-5
0 1 2 3 4 5 6 7 8 9 60
εR

50
2.5
Polystyrene 495 40
2
10-2
30
tan δ

10-3
20
10-4
10
10-5
0 1 2 3 4 5 6 7 8 9 200 300 400 500 600 700 800 900
logf Wavelength [nm]

Fig. 13: Dielectric constant εR and dissipation factor tan δ of Polysty- Fig. 14: Light transmittance of Polystyrene (thickness = 2 mm).
rene as a function of frequency (measured at 23 °C on both dry speci-
mens and on specimens conditioned to equilibrium moisture content
in a standard 23 / 50 atmosphere – ISO 291).

Electrical properties Optical properties

Polystyrene is a very good electrical insulator. The crystal-clear general-purpose Polystyrene grades have a light
transmission of about 90 % in the visible region (400-800 nm). The
The dependence of the dielectric constant and dissipation factor on absorption increases sharply in the UV region (Fig. 14).
the frequency can be seen from Fig. 13.
Further optical property data for general-purpose Polystyrene are
shown in Table 1.

The high-impact Polystyrenes are more or less opaque depending on


rubber content.

Table 1 Index of refraction and Abbe number of general-purpose


Polystyrene
Index of refraction Abbe number
BASF Aktiengesellschaft

nD – 1
nD* v=
nF – nC

1.59 31

*) Index of refraction and Abbe number measured in accordance with ISO 489 at 20 °C
Copyright 2007

10
Permeability to gas and water vapor,
Water absorption of Polystyrene

Polystyrene and its characteristic properties


Permeability to gas and water vapor The risk of changes caused by gases permeating in is particularly
great in the case of atmospheric oxygen which can lead to oxidative
Like all plastics, polystyrene has a certain permeability to gases and degradation of constituents or give rise to microbiological processes.
vapors which increases with rising temperature. Typical values for
Polystyrene are shown in Table 2.
Water absorption
The gas permeability of Polystyrene is a particularly important fac-
tor in designing packaging for goods which have a pronounced taste Owing to its nonpolar character, Polystyrene displays only a slight ten-
or odor since it is possible for aromas to escape and also for gases dency to absorb water.
and vapors to permeate in from the outside. The outward diffusion of
aromas leads to a change in taste especially when the individual taste
components diffuse at different rates.

 Table 2 T ypical values for the permeability to water vapor and gases of Polystyrene, Styroblend WS and
Styrolux at 23 °C (measured on 100 µm thick films)
Water vapor1) Oxygen Nitrogen Carbon dioxide
g · m -2 · d -1 cm 3 · m -2 · d -1 · bar -1
General-purpose 12 1000 250 5200
Polystyrene
Impact-resistant 13 1600 400 10000
Polystyrene
Styrolux ® * 14 2600 700 15000

1)
DIN 53 122; moisture gradient from 85 % to 0 % relative atmospheric humidity.
* More about water vapor permeability of various plastics also see page 23.

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Copyright 2007

11
Resistance to chemicals and
Environmental stress cracking behavior
of Polystyrene

Polystyrene and its characteristic properties


Resistance to chemicals For example, aliphatic hydrocarbons such as heptane have a very
strong effect in triggering environmental stress cracking in both gen-
Polystyrene is resistant to water, alkalis and dilute mineral acids, as eral-purpose Polystyrene and the high-impact grades.
well as to aqueous solutions of most salts.
A medium is said to initiate environ­men­tal stress cracking if its pres-
However, it is swollen by some organic solvents and dissolved by oth- ence reduces the time-dependent loadability compared to the behavior
ers. This is true of aromatic and chlorinated hydrocarbons, ethers, in a neutral environment.
esters and ketones. Polystyrene is also attacked by concentrated sul-
furic acid and strong oxidizing agents, e.g. nitric acid, chlorine water, The tensile creep test is an example of a method which can be
bromine water and sodium hypochlorite solution. employed for such an evaluation.

Detailed information on the resistance to chemicals is given in the Fig. 15 shows the behavior of high-impact Polystyrene specimens
Technical Information Bulletin “Polystyrene – resistance to chemicals”. produced under identical process conditions but exposed to different
media during the test.

Environmental stress cracking behavior The converse can be seen in Fig. 16, where the medium is the same
in all cases and the differences in the environmental stress cracking
Certain media may initiate cracking in Polystyrene moldings subjected behavior result from the different process conditions.
to external or internal mechanical stresses. Cracking may be induced
even by the agents that normally do not attack or hardly attack The environmental stress cracking resistance depends not only on
unstressed moldings. the type of product in question but also on its condition after process-
ing. If damage by environmental stress cracking is to be avoided, it is
therefore not sufficient to know the product properties but it is just as
important to monitor the quality of the moldings rigorously.
Tensile stress [MPa]
Tensile stress [MPa]

20
30
18
16 6 Higher orientation
5
14
4
20
12 Melt temperature °C
10 169
187
8 205
224
6 10 244
3 262
4 280
Low orientation
2
2
1
0 0
0.1 1.0 10 100 1000
BASF Aktiengesellschaft

1 day 1 week 1 month 10 102 103 104 105


Time [h] 1 day 1 month time [h]
1 week 1-2-3 years

Fig. 15: Stress cracking test on high-impact Polystyrene at 20 °C in Fig. 16: Creep rupture curves of high-impact Polystyrene in olive
various media. Creep rupture curves for oil / oleic acid, 1:1. Determined on test specimens with different de-
Copyright 2007

1. n-heptane 4. Battery acid grees of orientation. The higher the melt temperature, the lower the
2. Olive oil / oleic acid, 1:1 5. Distilled water degree of orientation.
3. Methanol 6. Air

12
Aging behavior of Polystyrene,
Resistance to high-energy radiation and
Microorganisms

Polystyrene and its characteristic properties


Aging behavior Resistance to microorganisms

Polystyrene is stabilized against the aging which can be brought about Polystyrene is immune to termites and is not a nutrient for micro-
by exposure to atmospheric oxygen at elevated temperatures. Indoors organisms. For this reason, any signs of attack can be attributed to
under normal light and temperature conditions, parts made of Poly- foreign substances which have collected on the surface.
styrene retain their appearance and their functionality for years.

Outdoors, the UV rays in direct sunlight are primarily responsible for


damage. This aging shows up both as a gradual change in appear-

Radiation dose [Mrad]


ance, i.e. yellowing and loss of surface gloss, and also as a decrease 104
a
in the mechanical strength. Dark colors have better resistance than a b
c
pale or transparent product. d
e

103
For the above reasons, Polystyrene is not recommended for articles εR
which are used outdoors for a prolonged period. 1
c b

d
102 b a
a 2
Resistance to high-energy radiation a
b
f d d
1 e
The effect of high-energy radiation (fast electrons, protons, α particles, 10 e
neutrons, X- and γ-rays) on polystyrene depends on the radiation f
e
σR 2
dose, the dose rate, the irradiation temperature, the geometry of the
f
irradiated specimen and the surrounding medium. f
1
When atmospheric oxygen is excluded, general-purpose Polystyrene is
one of the most radiation-resistant plastics known. On irradiation in air,
the radiation dose which causes damage is substantially lower.
Fig. 17: Radiation dose at which the tensile strength σR or the elonga-
The radiation resistance of high-impact Polystyrene is significantly tion at break εR of polymers is reduced by 25 % under the radiation
below that of general-purpose Polystyrene. conditions indicated. (method of H. Fischer, K.-H. Hellwege and W.
Langbein)
The good radiation resistance of Polystyrene compared to other ther-
moplastics is demonstrated in Fig. 17. a) Styrene-acrylonitrile copolymer
b) General-purpose Polystyrene
c) Rigid PVC
d) Plasticized PVC
e) Branched polyethylene
f) Polypropylene
1) = Irradiation in vacuo at 500 Mrad / h
2) = Irradiation in air at 1 Mrad / h.
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Copyright 2007

13
High-gloss Polystyrene

Special Polystyrene grades and their particular properties


High-gloss Polystyrene Areas of application:
refrigerator interiors
Polystyrene 454 C toilet water tanks
PS 454 C is a high-impact Polystyrene with a good combination of TV front frames and back panels
impact resistance, high flowability, heat resistance and high gloss. front covers for electronic entertainment
office and household articles
Processing: air conditioning units
In injection molding, PS 454 C can be processed at melt tempera- toys
tures of up to 260 °C. When appropriately processed, parts made of
PS 454 C display a high level of gloss. In this context, it is advanta-
geous to employ molds with a high-gloss polish. PS 454 C is suitable
for the internal gas pressure method. The melt temperature during
extrusion should not exceed 240 °C.

PS 454 C 14

classic
100 high-gloss 4-7
Gloss

HIPS
90 classic high-gloss HIPS
0 2 4 6 8 10 12 14
80
MVI cm3/10
70

60 Fig. 19: Flowability
PS 454 C
50 (mold temperature
= 60 °C)
40

30 PS 454 C 15

20 PS 454 C classic
high-gloss 7-18
10
PS 495 F HIPS
0
200 210 220 0 2 4 6 8 10 12 14 16 18
230 240 250 260
Melt temperature (°C) kJ/m2

Fig. 18: Surface gloss Fig.  20: Impact strength


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Copyright 2007

14
Polystyrene grade with increased environmental
stress cracking resistance

Special Polystyrene grades and their particular properties


Polystyrene grade with increased environmental stress
cracking resistance

Polystyrene ESCRimoTM
Polystyrene generally has only moderate resistance to certain
media which trigger environmental stress cracking. However,
Polystyrene ESCRimoTM has significantly better environmental stress
cracking resistance, as is shown very clearly in Fig.  21. For example,
refrigerator compartments and door linings made from this grade can
be backfoamed directly with polyurethane foam without the protec-
tion against foam blowing agents, e.g. cyclopentane, which is usually
required for high-impact polystyrene.

Partially halogenated hydrocarbons (HCFC) generally behave more


aggressively and need to be looked at on a case-by-case basis.

Polystyrene ESCRimoTM is also significantly more resistant to environ-


mental stress cracking in the presence of fats and oils than is conven-
tional high-impact polystyrene.

PS ESCRimo TM
versus 100
Cyclopentan

PS ESCRimo TM
versus HCFC 80
141b

0 20 40 60 80 100
[%]

Fig.  21: Stress cracking resistance

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Copyright 2007

15
Mechanical properties of Styrolux®

Styrolux® and its characteristic properties


Mechanical properties Stress-strain performance
The stress-strain graph (Fig. 22) to ISO 527 illustrates the perfor-
Important criteria for characterizing Styrolux® grades include mechani- mance of Styrolux® compared with GPPS for shortterm single-axis
cal properties that describe toughness and stiffness, together with the tensile stress and low deformation rate.
level of transparency. Another significant property of Styrolux® is easy
blending with a wide variety of polymers. The blend most frequently Alongside stiffness and toughness, the stress-strain curve here also
encountered uses general-purpose polystyrene (GPPS), permitting gives the yield stress and fracture energy, which is the area under the
highly cost-efficient production of transparent sheet and finished prod- stress-strain curve. GPPS typically has a steep, almost straight-line
ucts with tailored combinations of properties. curve and fractures after very slight deformation. This characterizes
GPPS as a stiff and dimensionally stable, low-extensibility material
Styrolux® compared with general-purpose polystyrene with high tensile strength and low tensile strain at break.
The Styrolux® line includes grades with various combinations of stiff-
ness and toughness (Tab. 3). Stiffness of the products reduces as In contrast, the Styrolux® curve has a flatter gradient, meaning lower
toughness increases. Values for modulus of elasticity (stiffness) and stiffness. Once the yield point has been reached there is no rise in
tensile strain at break (toughness) – determined from the tensile stress as tensile strain continues to increase. This very distinct defor-
test – are important parameters for these properties. Stiffer products mation behavior leads to fracture as tensile strain increases further.
with higher modulus such as Styrolux® 656 C are mainly suitable for This type of curve is characteristic of very tough materials. Because
injection-molding applications. The amounts of GPPS blended with Styrolux® 3G 55 has lower stiffness than Styrolux® 656 C, the stress
these grades are generally very small or zero. Tough to very tough values on the curve are lower.
grades such as Styrolux® 3G 46, Styrolux® 684 D or Styrolux® 3G
55 are mainly used in extrusion to give films or thermoforming sheet,
since this is where extremely easy blending with GPPS is a prime
requirement.

Styrolux ® Stiffness Toughness  50


Tensile Stress [MPa]

Modulus of elasticity Tensile strain at break


GPPS
[MPa] [%]
656 C 1800 20
40
3G 46 1550 >100
684 D 1500 160
693 D 1300 260
30
3G 55 900 >300
Styrolux® 656 C
GPPS 3300 2-3
20
Tab. 3: Guideline values for stiffness and toughness of Styrolux ® pro­
ducts compared with GPPS; measured by the ISO 527 tensile test. Styrolux® 3G 55
10
BASF Aktiengesellschaft

0
0 10 20
Tensile strain [%]

Fig.  22: Stress-strain curves for Styrolux ® 656 C,


Copyright 2007

Styrolux ® 3G 55, and GPPS measured by the ISO 527 tensile test.

16
Mechanical properties of Styrolux®

Styrolux® and its characteristic properties


Stiffness in blends with GPPS Toughness in blends with GPPS
Styrolux® is very often blended with GPPS for practical applications. As In contrast to stiffness, the toughness of Styrolux® / GPPS blends
GPPS content increases, the effect on stiffness (Fig.  23) is an almost reduces when GPPS is added. The sequence of toughness reduction in
linear rise in modulus of elasticity or yield stress. This is particularly blends is the same as that for pure Styrolux® products:
desirable for extrusion applications.
Styrolux® 3G 55 > 693 D > 684 D > 3G 46

This reduction in toughness can also be described using the tensile


strain at break obtained from the tensile test (Fig.  24).
Modulus of elasticity [MPa]

3300
The sharp reduction in tensile strain at break when GPPS content in
the blend is more than 40 % can be clearly seen. Blends with less
2800 than 20 % of Styrolux® show hardly any improvement in tensile strain
at break.
2300
684 D Tensile strain at break in the extrusion direction is generally relatively
low – a consequence of orientation of the rubber phase in Styrolux®.
1800 Lamellar morphology of Styrolux® in blends with GPPS parallel to the
3G 55 direction of extrusion reduces the amount of additional strain avail-
able on stretching in that direction. Depending on the Styrolux® grade,
1300 blends of from 30 to 70 % of Styrolux® with GPPS have proven suc-
cessful in most extrusion applications.

800
Impact strength of Styrolux® products
0 20 40 60 80 100
In circumstances contrasting with the relatively low deformation rate
GPPS content in Styrolux® [%]
in the tensile test high deformation rates subject the test specimens to
Fig.  23: Stiffness of Styrolux ® / GPPS blends; modulus of elasticity much more powerful fracture stresses. The Charpy (ISO 179) flexural
measured to ISO 527. impact test carried out on test specimens of the tougher Styrolux®
grades produces fractures only if the specimens have been previously
V-notched (ISO 179 / 1eA) (Tab. 4).
400
Tensile strain at break [%]

Flexural impact parameters determined on injection-molded test speci-


Transverse mens are higher than those for low-orientation specimens, because
the direction of stress is identical with the preferential direction of
300 orientation. The flexural impact test is therefore mainly used for com-
parative evaluation of product toughness.
Parallel

200

Table 4 Guideline values for impact strengths of Styrolux ®


grades at 23 ° C; nf: no fracture
100 Values in Impact strength Notched impact strength
BASF Aktiengesellschaft

[kJ /  m2] ISO 179 / 1eU ISO 179 / 1eA


656 C 25 2
3G 46 nf 3
0 684 D nf 4
0 20 40 60 80 100 693 D nf 5
Copyright 2007

PS 158 K content in Styrolux® 3G 55 [%]


3G 55 nf > 80-nf

Fig.  24: Tensile strain at break as a function of GPPS content


(PS 158 K) in Styrolux ® 3G 55; measured on 1 mm sheet to ISO 527.
17
Mechanical properties of Styrolux®

Styrolux® and its characteristic properties


Multiaxial impact strength Puncture resistance on sheets made from Styrolux® / GPPS blends
Styrolux® and high-impact polystyrene (HIPS) Like tensile strain at break (see Fig.  24), puncture resistance as a
Stress under practical conditions is much more likely to be multiaxial – function of Styrolux® / GPPS blending ratio reduces with increasing
with no preferential direction – rather than monoaxial. The automated GPPS content. Figure 5 shows this fracture behavior for 1 mm sheet
ISO 6603-2 penetration test relates to this situation, with central made from Styrolux® 693 D / GPPS blends. Here it is clear that the oil-
impact on a flat surface – of an extruded sheet or injection-molded containing polystyrene grade PS 143 E gives higher toughness.
plaque, for example.

The fracture energy is the area below the force-displacement curve,


and this shows that toughness is markedly higher for Styrolux® grades
than for comparable grades of high-impact polystyrene (Fig.  25).

1750 25
Penetration energy e [Nm]
Force [N]

1500
HIPS Styrolux® 20
684 D
1250

15
1000
PS 143 E
750
10
PS 158 K
500
5
250

0 0
0 10 20 30 0 20 40 60 80 100
Displacement [mm] GPPS content in Styrolux® 693 D [%]

Fig.  25: ISO 6603-2 penetration test on disks (diameter 50 mm, Fig.  26: Penetration energy as a function of GPPS content to
thickness 1 mm) for Styrolux ® 684 D compared with high-impact ISO 6603-2; measured on 1 mm sheet.
polystyrene.
BASF Aktiengesellschaft
Copyright 2007

18
Mechanical properties of Styrolux®

Styrolux® and its characteristic properties


Influence of blend components GPPS grades
The mechanical properties of blends are affected both by the GPPS containing lubricant – PS 143 E for example – gives higher
Styrolux® used and by the GPPS grade used. toughness values than oil-free GPPS grades such as PS 158 K.

Styrolux® grades Sheet toughness can be raised further by using a lubricant-modified


The variation in properties of Styrolux® / GPPS blends reflects the polystyrene grade with relatively high molecular weight such as PS
reduction in stiffness and associated increase in toughness within the 165 H, giving the relative values shown in the diagram of Fig.  28 for
Styrolux® line. Styrolux® 3G 55 has particular toughness efficiency the example of a sheet made from Styrolux® 693 D and GPPS blended
properties in blends with GPPS. in a ratio of 40 : 60.

When comparison is made with conventional grades, such as The toughness and transparency properties of the sheet here gener-
Styrolux® 693 D, Styrolux® content in terms of the amount of SBS ally vary in opposite directions, so although sheet produced using
used can be reduced by up to a quarter in blends with GPPS, e.g. PS 165 H is tougher at the same blending ratio a slight loss of trans-
PS 158 K (see Fig.  27). These blends using Styrolux® 3G 55 are just parency has to be accepted.
as stiff as conventional blends. Styrolux® 3G 55 therefore helps to
reduce costs of finished parts made from Styrolux® / GPPS.

70 20
Tensile strain at break [%]
SBS [N]

60
-25% SBS 15

50

10

40

5
30

20 0
Styrolux 693 D
®
Styrolux 3G 55
®
158 K 145 D 143 E 165 H

Fig.  27: For comparable toughness: reduction in Styrolux ® content Fig.  28: Influence of polystyrene grade on toughness of sheet made
by up to 25 % using Styrolux ® 3G 55 (size of circles = measure of from Styrolux ® 693 D and GPPS (blending ratio 40 : 60); measured
toughness). to ISO 527.
BASF Aktiengesellschaft
Copyright 2007

19
Optical properties of Styrolux®

Styrolux® and its characteristic properties


.Optical properties Transmission and Haze
Styrolux® grades
Excellent transparency is one of the key properties of Styrolux® prod- All Styrolux® grades have very good light transmission of about 90 %
ucts. The gloss of moldings made from Styrolux® is also high, compa- in the visible region (400 - 800 nm) (Tab. 6). Haze rises slightly as the
rable with that of GPPS. toughness of the products increases.

Two physical variables describe transpa­rency: light transmission and Blends made from Styrolux® and GPPS
haze. Transmission measures the intensity of light passing through a The transparency of blends made from Styrolux® and GPPS depends
test specimen after taking into account reflection losses at the two on the Styrolux® grade (see Table 6), the blending ratio, the GPPS
surfaces. Haze is the proportion of light scattered by more than 2.5 ° grade, and the homoge­neity of the blend.
from the incident direction on passage through a test specimen.
Blending ratio
Guideline Trans- Haze Refractive The content of the two components has a particular effect on sheet
values mission index transparency. The approximately parabolic function (Fig. 30) has a
[%] [%] n D 23
minimum where the Styrolux® / GPPS blending ratio is about 40 : 60.
656 C 90 1.5 1.58
Other blends have increasing transparency. The relative position of the
3G 46 90 1.0 1.57
transmission values is determined by the GPPS grades used.
684 D 90 1.5 1.58
693 D 89 2 1.57
Haze values likewise follow an approximately parabolic curve with
3G 55 89 3 1.57
increasing content of Styrolux®, this time with a maximum at a 40 : 60
Tab. 6: Transmission, haze, and refractive indices of Styrolux ® to Styrolux® / GPPS blend.
ASTM D 1003; measured on plaques of thickness 2 mm.
Styrolux® 3G 46 can be mixed very well with standard polystyrene
(GPPS). The extremely high transparency and the extremely low haze
95
Transmission [%]

are retained at GPPS levels of up to 40 percent. But even when the


polystyrene makes up more than 40 percent, the visual properties of
Styrolux® 3G 46 are decisively better than those of the comparable
90 SBS grades (styrene-butadiene block copolymers).

GPPS grades
Oil-free GPPS grades such as PS 158 K give the best transparency in
85 blends with Styrolux®. Although toughness increases with oil-contain-
PS 158K ing grades such as PS 143 E at the same blending ratio, transparency
PS 145D reduces. Blends made from Styrolux® and PS 145 D give the best
PS 143E compromise between high toughness and very good transparency.
80 PS 145 D gives higher flowability than PS 158 K and PS 143 E.
For identical blending ratios the sequence of increasing transparency
within the BASF product line is:

75
PS 165 H < 143 E < 145 D ≈ 158 K
0 20 40 60 80 100
Share of Styrolux® [%]
Homogeneity
BASF Aktiengesellschaft

Fig. 30: Transmission of Styrolux ® 684 D as a function of GPPS Inhomogeneity reduces the transparency of Styrolux® / GPPS blends.
content and of GPPS grades; measured on sheet of thickness 1 mm Good mixing performance by the extruder is an important precondition
to ASTM D 1003. for the production of high­quality sheet and high-transparency injection
moldings without flow streaks.
Copyright 2007

20
Thermal and electrical properties of Styrolux®

Styrolux® and its characteristic properties


Thermal properties
120

Vicat A 50 [°C]
The heat distortion resistance of parts made from Styrolux® depends
on the manu­­­­facturing conditions and on the nature and duration of
PS 158 K
thermal stress to which the material is subjected. Table 5 shows
guideline heat resistance values for Styrolux® products under standard
100
test conditions.

Styrolux® grades with higher toughness have lower heat resistance.


Average deflection temperatures of about 70  -  80 °C are achieved for PS 143 E
short exposure to heat with no external load.
80

In most applications, Styrolux® is pro­cessed in a blend with general-


purpose polystyrene (GPPS). Mechanical and optical properties, and
also thermal properties, depend on the mixing ratio and on the GPPS
grade used. For example, heat re­sistance of blends of Styrolux® and
60
GPPS rises linearly with GPPS content. Higher Vicat values can be 0 20 40 60 80 100
achieved with oil-free GPPS grades such as PS 158 K than with oil- GPPS content [%]
modified grades such as PS 143 E (Fig.  29). Average linear coefficient
of thermal expansion for Styrolux® in the range from -20 °C to +70 °C Fig.  29: Vicat softening points of blends of Styrolux ® 684 D and GPPS.
is 80 [10-4 / K], and thermal conductivity is similar to polystyrene at
from 0.15 to 0.17 [W / mK] Values in HDT A HDT B VST/A/50
[°C] ISO 75-2 ISO 75-2 ISO 306
656 C 67 77 90
Electrical properties
3G 46 58 75 81
684 D 65 75 83
Styrolux® is a good electrical insulator, similar to general-purpose
693 D 59 72 81
Polystyrene.
3G 55 51 62 67

Tab.  5: Heat resistance of Styrolux ®


HDT A: Deflection temperature under load of 1.8 MPa
HDT B: Deflection temperature under load of 0.45 MPa
VST / A / 50: Vicat softening point
BASF Aktiengesellschaft
Copyright 2007

21
Rheology,
Chemical resistance and
Stress cracking of Styrolux®

Styrolux® and its characteristic properties


100
Viscosity η [Pa・s]

Extrusion pressure [bar]


105
T = 200 °C 1 Styrolux® 693 D

104 1 2 Styrolux® 684 D 80


3 Styrolux 656 C
®
2
3
103 60

1 270 °C

102 40

101 20 250 °C
2

100 0
100 101 102 103 104 105 106 0 10 20 30 40 50 60
Shear rate [1/s] Extrusion time [min]

Fig. 31: Viscosity of Styrolux ® as a function of the shear rate at 200 °C. Fig. 32: Stability of Styrolux ® 684 D.

Rheology Chemical resistance

Styrolux® features good flow performance. Figure 31 shows an exam- Styrolux® is resistant to water, alkalis and dilute mineral acids, and
ple of dependency of melt viscosity on shear rate for the Styrolux® also to aqueous solutions of most salts. It is solvated or dissolved by
grades 3G 55 and 684 D. organic solvents, in particular chlorinated and aromatic hydrocarbons,
esters, ethers and ketones. Concentrated sulfuric acid and powerful
The recommended processing temperature range of 200 -240 °C oxidizing agents – such as nitric acid – also attack Styrolux®. If parts
should not be ex­ceeded, otherwise crosslinking can occur, resulting made from Styrolux® come into contact with other fluids, resistance
in haze, streaking and gel formation. A specific stabilizer system gives should be tested.
Styrolux® excellent thermal stability and a very low fish-eye level.

Crosslinking can be measured via extrusion pressure at a range of Stress cracking


temperatures (Fig. 32). However, these data do not provide a good
guide to residence times or melt temperatures for processing pur- Substances which generally promote stress cracking in polystyrene,
poses. for example fats and oils based on unsaturated fatty acids, can also
damage Styrolux®. The extent of damage depends on the type of
processing used, and on the external stress to which the moldings are
exposed. When blends of Styrolux® and standard polysty­rene are used
with fluids that cause stress cracking, the best possible compromise
BASF Aktiengesellschaft

has to be devised between mechanical properties and stress cracking


resistance.
Copyright 2007

22
Permeability, Organoleptic properties, Aging and
Sterilizability of Styrolux®

Styrolux® and its characteristic properties


20 Permeability
Permeability (g 100 µm)/(m2d) 23°C/85 -> 0% r.h.

Compared with other plastics, Styrolux® has very high permeability to


gases and vapors (Figures 33 and 34). This has to be considered for
15 example when packaging contents with strong odor or flavor. Changes
in the packaged product can occur due to outward diffusion of aroma
components or ingress of oxygen. However, this very high permeability
10 of Styrolux® can also be extremely useful for fresh-food packaging.
An example – in packs for fruit and vegetables Styrolux® permits
exchange of gases and moisture with the immediate environment so
that natural ripening processes can continue.
5

Organoleptic properties

0
Styrolux® has been used successfully for many years as a packaging

A
A
6

PS

PP
OH

PE
T-
M

PV

material in the food sector. However, before Styrolux® is used to pack


PA

olu

GP

HD
EV
PM

PE
yr

flavor-sensitive foods it is advisable to test for organoleptic effects. We


St

do not recommend sealed containers. We recommend a coextruded


Fig. 33: Water vapor permeability of various plastics. composite with PETG as barrier layer when packaging products con-
taining oils or fats.

3000 Aging
Permeability (cm3 100 µm)/(m2d bar) 23°C/0% r.h.

Styrolux® has effective stabilization to inhibit aging on exposure to


2500
oxygen and high temperature. In diffuse light, parts made from
Styrolux® retain their optical and mechanical properties for many
2000 years. However in outdoor applications the material can be degraded
by the high energy content of sunlight, resulting in yellowing and
1500 deterioration of mechanical properties. Styrolux® is not recommended
for outdoor applications. The time to onset of yellowing can be conside­
rably prolonged by using UV stabilizers.
1000

500 Sterilizability

Styrolux® can be sterilized either with high-energy radiation (g- or b-


0
radiation) or with ethylene oxide (ETO). Styrolux® retains most of its

A
PS

6
PP

OH
PE

T-
M

PV

mechanical properties during this process.


PA
olu

GP

HD

PM

EV
PE
yr
St

BASF Aktiengesellschaft

Fig. 34: Oxygen vapor permeability of various plastics.


Copyright 2007

23
General information

Processing of Polystyrene and Styrolux ®


General information Polystyrene regrind is fully reprocessible as long as the recycled mate-
rial has not been damaged by excessively high shear or temperature.
Polystyrene can be processed by all techniques customarily used for The usability of regrind should nevertheless be carefully checked in
thermoplastics. It has good thermal stability and can be processed each case for parts which have high quality requirements.
under a wide range of conditions.
Indications of product damaging having occurred are:
Predrying An increase in the monostyrene content
Polystyrene molding compositions do not normally have to be predried A decrease in the molecular weight of the matrix
before injection molding, but predrying is advisable if they have been Rubber crosslinking
stored in an outdoor hopper. (predrying at 60 - 80 °C for 2 - 3 hours.) A change in the rubber morphology (fragmentation)
Conspicuous tendency to yellowing.
Since even small amounts of moisture can cause problems in In such a case, advice should be sought from BASF’s Technical Ser-
extrusion, it is always advisable to carry out predrying or to employ vice team.
vacuum-vented screws.
The regrind must be free of contamination. To protect the regions of
Compatibility the processing machine which come into contact with the melt, it
All Polystyrene grades are compatible with one another. It is possible should where possible be passed through a magnetic sieve before
to change from one Polystyrene grade to another, e.g. from semi- being introduced into the feed hopper. Regrind with particles of widely
high-impact to high-impact Polystyrene, without any special measures differing substance and with a low bulk density can cause problems in
being needed. On the other hand, Polystyrene is incompatible with maintaining a stable extruder throughput.
acrylonitrile-containing products and with polyethylene, polyamide,
polyester, acetylcellulose and other thermoplastics. In these cases, the Fines have a particularly detrimental effect, resulting in screw slip.
machinery must be thoroughly purged before a change of material. They should be removed in a cyclone.

Recycling Injection molding


Scrap is obtained in the form of trimmings in extrusion, punching Polystyrene molding compositions are injection molded predominantly
scrap in thermoforming, sprues in injection molding, flash in blow on screw-type machines. Only in exceptional cases (e.g. moldings with
molding and reject parts in all four processing methods. These can a marble effect) are injection molding machines with special screws or
add up to a total of as much as 50 %. plungers employed.

Owing to their amorphous structure, Polystyrene molding compositions


have not only a wide processing range but also low tendency to distort
and low shrinkage.
BASF Aktiengesellschaft
Copyright 2007

24
Injection unit and
Injection molding tools

Processing of Polystyrene and Styrolux ®


Injection unit Demolding
As a rule, Polystyrene can be demolded without difficulty.
Screw geometry
Conventional all-purpose screws can be used. Good results are A taper of 1:100 or 30’ on one side is a sufficiently large draft. In fact,
obtained using three-zone screws having an L : D ratio of from 16 :1 if the mold is polished in the machine direction, drafts of down to 10’
to 20 :1 and the features indicated in Table 5. Although longer screws are adequate.
melt the granules more uniformly, they at the same time increase the
residence time of the molding composition in the barrel. Use of inserts
Metal inserts do not obstruct the smooth flow of Polystyrene, but they
Nonreturn valves should be heated to 80 -120 °C before being placed in the mold in
The only reliable means of ensuring a constant cushioning effect and order to avoid molded-in stresses. They must be thoroughly degreased
follow-up pressure is to install a nonreturn valve that prevents the melt and secured in the mold by means of milled edges, circumferential
from flowing backward into the front screw flights during the in­jection grooves or the like. The metal edges should be well rounded off.
and follow-up phases. Since de­signs giving excellent flow are avail-
able, a nonreturn valve should always be used as a matter of principle Mold temperature control
when manufacturing precision parts. However, the screw must then not A well-designed mold temperature control system is of great impor-
be allowed to rotate during injection, since otherwise damage to the tance because the effective surface temperature of the mold exerts a
machine may result. critical effect on the finish (gloss, brilliance and absence of flow lines),
the strength of weld lines, the resistance to warpage, the shrinkage
Nozzle and the adherence to tolerances.
Since Polystyrene melts are more viscous than, say, nylon melts, they
allow open nozzles to be used. Open nozzles offer the advantage of a Depending on requirements, temperatures of from 10 to 70 °C are
very simple design that favors easy flow. customary. Very thin-walled parts which have to be produced with
short cycle times can also be injection molded at mold surface tem-
Nozzles with shutoff devices can be recommended if the back pres- peratures of less than 10 °C. At even lower mold temperatures, brine
sure is high, cobwebbing is to be avoided and moldings with thick has to be used as coolant.
walls are to be produced.
One means of counteracting any tendency of the molding to warp is to
Thick-walled moldings frequently require cycle times of several cool the two halves of the mold separately to different temperatures.
minutes. If, in such cases, the injection molding composition is not
removed completely from the nozzle bore, it may cool excessively
there and thus give rise to streaking in the next shot. Best results
have been given by nozzles with mechanically or hydraulically actu-
ated needle valves, although the pressure drop in such a nozzle is not Table 7 Typical values for the screw geometry (injection molding)
inconsiderable. Length of function sections Depths of flights

Total length L 16 - 20 D D* h f hm


mm mm mm
Injection molding tools Feed section Lf 0.5 L 30 5 2.5
Compression section LC 0.3 L 50 6 3
Gating and mold design Metering section Lm 0.2 L 70 8 4
In principle, all conventional types of gating are possible. The gate 100 10 5
cross section must be sufficiently large to avoid unnecessarily high 130 12 6
D* = screw diameter
BASF Aktiengesellschaft

h f = depth of flights in the feed section


melt temperatures and injection pressures which could lead to streak- h m = depth of flights in metering section
ing, burn marks, voids and sink marks. The VDI 2006 guidelines for
gating and mold design also apply to the Polystyrene molding com-
pounds.
Copyright 2007

25
Injection molding / Polystyrene

Processing of Polystyrene and Styrolux ®


Injection molding / Polystyrene Feed characteristics
The feed characteristics of Polystyrene are influenced by screw geo­
Injection temperature metry and rotational speed, back pressure, the temperature settings in
Polystyrene can be injection molded at melt temperatures between the plastification and feed sections and also by the shape and nature
180 °C and 260 °C. of the granules (externally lubricated or unlubricated).

The melt temperature has a significant influence on the toughness of As a rule, Polystyrenes can be plastified uniformly and without thermal
the finished parts, particularly that of the rubber-modified Polystyrene degradation even at high screw speeds. Normally, the plastification
molding composition. capacity increases with a rise in temperature.

If the residence time of the melt in the barrel is relatively long, the Frequently, the individual heating zones of the plastification barrel can
temperature should not be in the upper end of the range or even be set to the same temperature. However, if the processing tempera-
above it, since otherwise thermal degradation and /or an increase in ture is in the upper end of the batch and /or if the cycle times are
the residual styrene content can result (Fig. 35). long, the temperature of the first heating strip (close to the hopper)
should be set at a somewhat lower value. This prevents premature
Thermal degradation can usually be recognized by silver streaks or melting of the granules in the feed section (bridging).
burn marks. A change in color can also occur. The melt temperature
is best monitored by means of a penetration thermometer on the
pumped-out composition.
Monostyrene [%]

1.0

0.8
Mean residence time 3 min
Mean residence time 10 min
0.6

0.4

0.2

0
200 220 240 260 280 300
Melt temperature [°C]

Fig. 35: Monomeric styrene content as a function of melt temperature


BASF Aktiengesellschaft

and residence time.


Copyright 2007

26
Injection molding / Polystyrene

Processing of Polystyrene and Styrolux ®


Filling of the mold Steps must be taken to ensure that air can easily escape from the
A general rule for Polystyrene is that the mold must be filled as rapidly mold at suitable points to prevent burning as a result of compressed
as possible to prevent marks at the weld lines and to ensure that the air (diesel effect).
weld lines are as strong as possible. Another advantage of a high
injection rate for most Polystyrenes is that it yields glossy and brilliant To obtain perfect injection-molded parts and to prevent void formation,
moldings. The only Polystyrenes for which very fast injection can have the follow-up pressure and screw forward time must be sufficiently
a detrimental effect are the high-impact grades with high heat distor- high to compensate for the volume contraction on cooling of the melt.
tion resistance, in which case matt concentric zones around the screw This requires the gates to be large enough to prevent the melt from
may occur under some circumstances. Dark-colored products are par- solidifying in their vicinity before the screw forward time has elapsed
ticularly prone to this effect. Fluctuations in the injection rate may also and thereby stopping the follow-up pressure from acting on the mold-
cause matt streaks in these products. In such cases, slower injection ing while it is still plastic in the interior. However, the volume expansion
at higher melt and mold temperatures leads to more uniform flow and experienced by Polystyrene as a result of heating can be more than
improves the surface. compensated for by high pressure. The dependence of the specific
volume vs on temperature T and pressure p is shown for general-pur-
pose Polystyrene in Fig. 36.
Specific volume [cm3/g]

1.06 0
It can be seen from this graph that the volume expansion caused by
heating from 20 °C to 200 °C is just compensated at a pressure of
1.04
200 1400 bar. If the melt solidifies at a point of higher pressure within the
1.02
400 mold cavity, the volume element concerned has to accommodate more
compound than it actually can. This state is known as overloading.
600
1.00 800
Overloading gives rise to molded-in stresses which may cause gen-
1000
0.98 eral-purpose Polystyrene moldings to rupture on demolding. The
1200
1400 impact-modified grades, on the other hand, can take up the stresses
0.96 1600 more readily because of their higher ductility. The risk of overloading
1800
0.94 2000 exists mainly in the vicinity of the sprue at high injection rates and
high follow-up pressures.
0.92
pressure p bar

0.90
0 50 100 150 200 250
Temperature [°C]

Fig. 36: Specific volume of general-purpose Polystyrene as a function


of temperature and pressure.
BASF Aktiengesellschaft
Copyright 2007

27
Injection molding / Polystyrene

Processing of Polystyrene and Styrolux ®


600 600
Flow distance [mm]

Flow distance [mm]


500 500
Polystyrene Polystyrene
400 400 495 F
143 E

158 K 486 M
300 300

200 200 Melt temperature = 220 °C


Melt temperature = 220 °C Mold surface
Mold surface temperature = 45 °C temperature = 45 °C
100 100
Injection pressure = 1000 bar Injection pressure = 1000 bar

Screw advance rate = 50 mm/s Screw advance rate = 50 mm/s


0 0
0 0.5 1.0 1.5 2.0 2.5 3.0 0 0.5 1.0 1.5 2.0 2.5 3.0
Thickness [mm] Thickness [mm]

Fig. 37: Flow in a spiral mold, general-purpose Polystyrene. Fig. 38: Flow in a spiral mold, high-impact Polystyrene.

Flow Shrinkage
The Polystyrene product line includes grades having different flow Polystyrene undergoes considerably less shrinkage than partially crys-
characteristics. The measure usually used for the flow is the melt vol- talline plastics. Although it is primarily a material property, it is also
ume index in accordance with ISO 1133. The product overview at the decisively influenced by the geometry of the moldings (restricted or
end of the brochure gives information about the flow behavior of the free shrinkage) and by processing conditions such as melt tempera-
individual Polystyrene grades. ture, mold surface temperature and follow-up pressure.

Information of great practical significance is obtained from flow tests Local interplay between these parameters may cause great differ-
in which coils of various thicknesses are produced in a spiral mold ences in shrinkage within one and the same molding.
(Figs. 37 and 38). At a given melt temperature, mold surface tempera-
ture, screw advance rate and the corresponding injection pressure, the As a rule, the processing shrinkage is between 0.4 and 0.7 %, but in
length of the spiral can be regarded as a measure of the flow of the exceptional cases it can be significantly below 0.4 %. It may even be
product. zero in zones within the molding that are subjected to a high follow-up
pressure (vicinity of the sprue).
Cycle time
A factor that decidedly affects the duration of the injection cycle is After-shrinkage can be neglected in most applications; it accounts for
the time taken for the Polystyrene to cool from the melt temperature about 10 % of total shrinkage.
to the solidification point. The lower this temperature difference, the
shorter the cooling time and thus usually also the cycle time. The dif-
ference between melt temperature and solidification point depends on
BASF Aktiengesellschaft

the particular Polystyrene grade.

A measure of the solidification point is the Vicat softening temperature.

The higher the flow of Polystyrene, the lower the temperature at which
Copyright 2007

it can be processed, so Polystyrene grades which flow easily and at


the same time solidify rapidly can be processed most quickly.

28
Injection molding / Styrolux®

Processing of Polystyrene and Styrolux ®


Processing by injection molding Processing instructions
Generally speaking, a low ratio of the barrel contents to the shot vol-
The tough and rigid Styrolux® grades 656 C and 684 D are the pre- ume, a low rotational speed of the screw and working with little or no
ferred choices for injection molding. In order to improve the stiffness back pressure are advantageous.
and dimensional stability under heat, in injection molding as well,
Styrolux® is sometimes blended with up to 40 % general-purpose In the case of short production downtimes, it is usually sufficient to
polystyrene (GPPS); the production of highly transparent parts calls for lower the melt temperature and then to pump off the melt; at the end
a plasticising unit that is capable of good mixing. of longer pauses, in contrast, we recommend flushing with high-vis-
cosity general-purpose polystyrene.
Injection molding unit
Universal screws with a length of 16 D to 20 D are suitable. The pitch The melt temperatures should not exceed 250 °C [482 °F] and the
along the entire length should be constant at a value between 0.8 D residence time in the cylinder should not be too long. An injection time
and 1 D. that is as high as possible is a decisive factor for the optimal trans-
parency and brilliance of injection molded parts. Here, a slight loss in
Injection molding tools toughness will have to be accepted.
The shaping tool surfaces have a great influence on the transparency
and gloss of the injection molded parts. The tiniest flaws on the tool Any commonly employed type of gate, also hot runner systems, can
surfaces are reproduced, as a result of which high-gloss and polished be employed. With a hot runner system, the configuration must be
surfaces are recommended. Care should be taken to ensure that such that no localized overheating (T > 250 °C [482 °F]) can occur.
the draft is at least 1°. For the mold parting surfaces, a compromise Adequately dimensioned runners and gates prevent thermal overloads.
should be sought between a tight seal – for the eventuality of flashes –
 and sufficient venting.

The tool surface temperatures should be set between 20 °C and


50 °C [68 °F and 122 °F], depending on the grade of Styrolux®. Too
low a temperature can give rise to streaks and flow marks. Too high a
temperature leads to adhesion, which also causes cracks or fissures.
Here, mention should be made once again of the polish in the de-
molding direction in order to effectuate the best possible de-molding.

BASF Aktiengesellschaft
Copyright 2007

29
Injection molding / Styrolux®

Processing of Polystyrene and Styrolux ®


Feed characteristics In comparison to general-purpose and high-impact polystyrene, the
The feed characteristics of Styrolux® are not problematic. It is best for lower dimensional stability and softening temperature of Styrolux®
the temperature gradient from the hopper to the tip of the screw to mean that the cooling times, and hence the cycle times, will be longer,
rise slightly. The cross head must be cooled. even in the case of intense cooling. The demolding behavior can also
be improved by adding Styrolux® Batch ASE in an amount of 2 % to 4 %.
Flow characteristics
The flow test with the test spiral at wall thicknesses of 1 mm to 2 mm Shrinkage
reveals an almost linear dependence of the flow lengths on the melt The shrinkage values of Styrolux® lie between 0.3 % and about 1%.
temperature (Fig. 39). At a wall thickness of less than 1 mm, only short They are the lowest parallel to the direction of flow, somewhat higher
flow lengths are possible since the flow resistance rises disproportion- transversally to the direction of flow near the gate and highest far
ately as the wall thickness decreases. away from the gate (Fig. 40). The shrinkage and the shrinkage differ-
Melt temperatures of more than 250 °C [482 °F] cause cross-linking ences can be influenced by regulating the melt temperature. High melt
of the material and consequently the flowability drops once again. temperatures yield lower shrinkage values and smaller differences
The onset of cross-linking is also indicated by turbidity and yellowing. between the positions near and far away from the gate.

De-molding The temperature of the tool surface and the injection speed are less
Owing to its morphology, Styrolux® adheres more strongly to steel decisive for the shrinkage.
surfaces than high-impact polystyrene does. Therefore, it re­quires a
greater force in order to overcome the static friction during the first Compressibility and warpage
phase of de-molding. It is helpful to select a high injection pressure Styrolux® is considerably more compressible than high-impact poly-
and back pressure. Due to the high compressibility of Styrolux®, the styrene. This is why centrally gated rectangular parts can exhibit larger
part is slightly compressed. Following pressure relief, the part relaxes internal stress differences between the shortest and the longest flow
and is easier to release from the core. Excessive injection pressure distances. In conjunction with the lower dimensional stability, the
and back pressure cause greater deformations in the part. A possible molded parts can undergo warpage even hours after the de-molding.
consequence after the pressure relief is that the part could become Since there is a direct relationship between the warpage and the
jammed in the mold cavity. This should be optimized by means of modulus of elasticity, a Styrolux® grade with a high modulus of elastic-
experimentation. ity should be selected for parts where low warpage is critical.

1200 1.0
Length [mm]

Mean shrinkage [%]

Wall thickness of
flow spiral: 2 mm far away from the gate/
1000 transverse
0.8
656 C near the gate/
800 transverse
684 D
0.6

600 656 C
684 D 0.4
near the gate/
400 parallel
Wall thickness of
BASF Aktiengesellschaft

flow spiral: 1 mm 0.2


200

0 0
0 230 250 0 20 40 60 80 100
Copyright 2007

Temperature [°C] Time after de-molding [h]

Fig. 39: Flowability of Styrolux® in the spiral flow test, injection pres- Fig. 40: Shrinkage of Styrolux® 656 C.
sure of 1500 bar.
30
Extrusion / Polystyrene

Processing of Polystyrene and Styrolux ®


Extrusion / Polystyrene

Bursting index [bar • sec]


Polystyrene
The most suitable Polystyrenes for extrusion are those with a high vis- 486 M/165 H
30
cosity, i.e. products with a melt volume index MVI 200 / 5 in the lower
end. However, materials with a higher MVI are also used for multilayer
composites.

The desired ratio of rigidity to toughness can be obtained by blending 20


Conventional high-impact
high-impact and general-purpose Polystyrene. An important point to Polystyrene/165 H
observe for ensuring a homogeneous melt is that the flow charac-
teristics of the blend components do not differ too widely (the flow is
indicated by the final letter in the product designation). 10
Equipment items required are a metering and mixing device upstream
of the extruder inlet and a mixing element in the melt region upstream
of the die.
0
Examples of preferred combinations for packaging material are: 30 40 50 60
Proportion of normal PS [%]
Polystyrene 486 M and Polystyrene 165 H
Fig. 41: Bursting pressure test on drinking cups.
Polystyrene 145 D combined with impact-resistant polystyrene is
particularly well-suited for FFS films.

If Polystyrene 143 E is already being used for the extrusion of The bursting pressure test on finished, thermoformed cups gives a
high-gloss composites, it can also be blended with 486 M to good guide to the toughness of the material used. The bursting index
reduce inventories. as a function of the mixing ratio is shown for two examples of blends
in Fig. 41. This demonstrates the advantage of the higher impact
On the other hand, Polystyrene 158 K could be considered for toughness of 486 M in blends with 165 H compared to mixtures of
blending with 486 M if the heat distortion resistance of the mixture 165 H and conventional high-impact polystyrene.
is to be increased at the same time. The mixing ratio depends on
the application and is usually between 1:1 and 4 :1 (= PS-I : PS).

BASF Aktiengesellschaft
Copyright 2007

31
Extrusion / Polystyrene

Processing of Polystyrene and Styrolux ®


Processing conditions In many cases, a shear ring is installed at the end of the first screw
The processing temperatures for Polystyrenes lie between 180 and section to aid venting. The geometry of the shear ring has to be
240 °C, in individual cases even a little higher. As a rule, the grades matched to the plastic in order to avoid thermal degradation of the
with a higher viscosity are extruded at a higher temperature. Pressure material; this applies particularly when processing SBS copolymers
and temperature of the polymer should be measured where possible (Styrolux®).
by means of suitable devices. In practice, the screw pressure ranges
from 100 to 200 bar. For safety reasons, a maximum pressure warn- In the upper range of screw speeds, some of the air present in the
ing device should be fitted. interstices between the granules may no longer be able to escape
through the feed hopper. The trapped air leads to bubbles and holes in
Vented extruders the extrudate. The vents on high-performance extruders should there-
Vented extruders allow the extraction of volatile constituents (e.g. low fore be designed with generous dimensions. The vent should be hori-
molecular weight fractions, moisture) from the melt and the removal of zontal or inclined slightly downward to prevent condensed, thermally
entrapped air. degraded material from falling back into the screw channel.

The “classicial” vented extruder screw can be likened to two three- In principle, Polystyrene can also be extruded without the use of a
zone screws arranged in tandem (Fig. 42). The length of modern vent- vented extruder. In this case, the granules should be predried, depend-
ed extruders is in the range 30 - 36 D. The compression ratio should ing on the Vicat softening temperature of the Polystyrene used, at
generally be between 1: 2 and 1: 2.5 for Polystyrene. temperatures of 60 - 70 °C for 3 - 4 hours, e.g. in a hot air drier or a
vacuum drying oven.
Compression ratios of 1: 3 can also be employed when processing up
to 50 % of regrind. It has been found in practise that predried granules cause fewer pro-
duction and quality problems in the long term, although films which
Venting occurs between the two screw sections; substances are col- have been produced without the use of a vented extruder have inferior
lected in the form of liquids or pastes in the condenser between the organoleptic characteristics.
venting port and the vacuum pump. The venting effect is initiated by
the pressure drop that occurs downstream of the first metering section
and is reinforced by a partial pressure increase that is brought about
by raising the melt temperature in front of the venting section.

Vent Shear ring


BASF Aktiengesellschaft

Compres- Compres-
Metering 2 sion 2 Venting Metering 1 sion 1 Feed
Copyright 2007

Fig. 42: “Classical” vented extruder screw.

32
Extrusion / Polystyrene

Processing of Polystyrene and Styrolux ®


Design of vented extruder screws Experience has shown that both phenomena can be described with
Vented extruder screws generally have smooth feed sections. Lightly sufficient accuracy by means of a screw simulation program (REX).
grooved feed sections are sometimes also used for better and more The decisive parameter is the pressure profile in the region of the
stable feed and transport behavior. Virtually no use is made of actual extruder through which melt flows. Fig. 43 shows the two pressure
grooved bushings, e.g. with rectangular grooves, since melting in the profiles for flooding (pressure at the vent is too high) and surging
first stage and transport in the second stage are generally unsatisfac- (pressure buildup is too late). The figure also shows an ideal pressure
tory for the high grooved bushing throughputs. Moreover, extrusion of profile between the these two phenomena.
recycled material (regrind from extrusion of thermoforming and other
sheet) comes up against processing limits (constancy of transport) Melt pump
when grooved bushings are employed. A melt pump is a further extruder component which can improve
the quality of the extrudate. Installation of a melt pump enables the
Since both stages of a vented extruder screw are rigidly coupled to throughput to be made uniform and the second screw section is
one another, the throughputs of the two screw sections have to be largely relieved of the task of building up the pressure to overcome
matched. If this is not the case, the followig problems occur: the resistance of the die. Only the minimum pressure for trouble-free
operation of the melt pump has to be generated, thus lowering the
Melt may exude from the vent if the throughput of the first screw pressure in the extruder.
section is too high (flooding)
Consequently, high-performance screws for vented extruders with melt
Surging if the throughput of the first screw section is too low pumps can be designed for higher plastification capacities than those
(excessively large partially filled regions in the second stage). for vented extruders without melt pumps. However, this means that a
higher melting capacity is required in the first screw section. It is also
necessary to take into account that the melt pump introduces shear
and thereby slightly increases the melt temperature.
Pressure

Surging

Flooding
BASF Aktiengesellschaft
Copyright 2007

Fig. 43: Different axial pressure profiles.

33
Extrusion / Polystyrene

Processing of Polystyrene and Styrolux ®


Melting Design variants
Apart from achieving the desired throughput (without flooding or surg- Relatively recent screw concepts or modifications (e.g. barrier zones
ing), complete and correct melting is of decisive importance in judg- or increases in pitch) are being tested with the aim of further increas-
ing a plastification unit. There is little value in achieving a maximum ing the throughput or melting capacity at the same screw diameter.
throughput unless complete melting can be achieved before the vent A higher throughput necessitates a simultaneously higher melting
so that satisfactory venting can take place. capacity.

The percentage of melt and the dimensionless solids bed width Y are Fig. 45 shows the effect of a higher pitch in the second screw section
calculated by means of the simulation program. Y is defined as the on the pressure profile under otherwise identical conditions (same
solids bed width X divided by the channel width b (based on the solids throughput). In this example, the increase in pitch can prevent flooding
channel in the case of barrier screws). Fig. 44 shows an example of a of the vent.
calculated melting profile.
A further possible design of vented extruder screws incorporates bar-
The melting profile enables predictions to be made as to the ratio of rier zones in the first screw section so as to ensure complete melting
transport and melting capacity of the screw and also makes possible a by the end of the first screw section.
qualitative estimate of the achievable homogeneity of the melt in front
of the screw.

1 100 constant pitch


with increase in pitch
Y=_x
b
Proportion of melt [%]
Solids bed width Y

Pressure

x
b

0 0
BASF Aktiengesellschaft

Fig. 44: Examples of a calculated melting profile (material: PS 486 M). Fig. 45 Effect of pitch on the pressure profile (material: PS 486 M).
Copyright 2007

34
Extrusion / Polystyrene

Processing of Polystyrene and Styrolux ®


Barrier screws Advantages of the barrier section are the controlled melting process
Owing to the relatively uncomplicated extrusion behavior of Poly­ and the increased number of degrees of freedom in the design of the
styrene, barrier screws have rarely been encountered on the market. screw geometry. The latter feature enables the screw geometry to be
Nevertheless, in particular cases they can be an interesting alternative more closely matched to a particular application, although the system
because of their specific melting characteristics. does also have more possible sources of error which have to be ruled
out.
All barrier zone extruders function in the same way. The characteristic
feature is the division of the screw channel into a solids channel and Good results have been achieved in recent years in the extrusion
a melt channel (Fig. 46). The solids channel is separated from the of other thermoplastics using the barrier screw concept. Efforts are
melt channel by the barrier flight. The gap between the barrier flight being made at present to apply this experience to the field of vented
and the barrel is greater than for the main flight so that only molten extruder screws with the object of increasing plastification.
material or particles which are (at least in one direction) smaller than
the gap can get into the melt channel. When passing over the barrier Vented extruder screws with barrier zones should, like other screw
flight, these particles are subjected to additional, defined shear which designs too, be provided with a mixing section at the tip of the screw
leads to further melting of the remaining solid particles. In addition, in order to achieve sufficient homogeneization when processing
the barrier flight contributes to homogenization of the melt. blends.

Barrier section

Barrier section Standard section

Solids channel Melt channel Solids bed Melt


BASF Aktiengesellschaft

Fig. 46: In-principle illustration of a vented extruder screw with barrier section.


Copyright 2007

35
Extrusion / Polystyrene

Processing of Polystyrene and Styrolux ®


Mixing elements Dies
Examples of proven dynamic mixers are faceted mixing sections and Slit dies are used for the extrusion of both flat film and sheet.
toothed disk or slotted disk mixing sections (Fig. 47), but other types
are also used. The mixing sections should cause as low as possible a In both cases, the length of the parallel zone is about 20 times the slit
pressure drop so that the throughput of the second screw section is width. Sheets are usually produced using an adjustable choker bar,
not reduced too much. while films are produced without it. When a choker bar is employed, it
is set obliquely as shown in Fig. 48.
Particularly in the case of retrofitting, the homogeneity of the melt can
be increased by means of a static mixer which can be used in addition The lower lip is interchangeable in order to cover a greater thickness
to the dynamic mixing section. range.

Flex-Lip Adjusting screw for choke bar

Toothed disk mixing section Faceted mixing section

Fig. 47: Examples of mixing sections.

Interchangable Choke bar


die lip

Fig. 48: Sheet die with choker bar and flex-lip. BASF Aktiengesellschaft
Copyright 2007

36
Extrusion / Polystyrene

Processing of Polystyrene and Styrolux ®


Calibration rolls Coextrusion
On leaving the die, extruded sheet is led through calibration rolls. The Coextrusion enables the properties of several materials to be com-
roll temperature should be as high as possible to keep molding-in bined. It requires matching of the flow properties of the materials
stresses to a minimum during cooling. A rule of thumb is that the tem- used. The extruded product is a multilayer composite in which the
perature at the surface of the center roll should be about 5 K below individual layers should adhere to one another. If the adhesion of the
the limit at which the extruded sheet sticks to the surface of the steel. layers to be combined is nonexistent or inadequate, a layer of bonding
This gives an idea of the most favorable temperature settings on all agent has to be interposed. A distinction is made between adapter and
the rolls for a given product under given conditions. If the melt is fed die coextrusion. In adapter coextrusion, the composite is built up in
downward, the temperature of the upper roll should be set to a value front of the die and is extruded as if it were a single-layer melt.
well below that of the center roll, e.g. 10 K, because of the small con-
tact area at the upper roll (theoretically, the contact is merely linear). In die coextrusion, the layers are formed separately in a special die
The temperature setting on the lower roll should be between those on and are subsequently joined. General-purpose Polystyrene is often
the upper and center rolls. used as a gloss layer on a high-impact substrate. In this combination
with high-impact Polystyrene, no bonding agent is necessary. In most
If curvature of the sheet occurs after passing through the rolls, the other cases, a bonding agent has to be used and the choice depends
temperature settings need to be optimized. As a general rule: the con- on the components of the composite.
cave side corresponds to a roll which is too hot and, conversely, the
convex side corresponds to a roll which is too cold. Workplace emission and venting residues
An exhaust hood with condenser and collector should be installed
Orientation above the die.
The orientation or even prestressing of sheet intended for further
shaping can be assessed by heat treatment as described in ISO 11501. Under normal extrusion conditions, the condensed residues from the
Increasing the melt temperature is the most effective means of vent amount to 100 - 300 ppm of the product throughput, the actual
achieving low shrinkage, but this must obviously be kept to a level figure depending on the melt temperature and the shear.
which does not cause appreciable degradation of the product. The condensed products consist essentially of water, lubricants, stabi-
lizer, monostyrene and oligomeric styrene.
Other available parameters, which have varying degrees of effective-
ness, are die gap, distance between die and roll, roll temperature and The nonaqueous fraction of the condensate can be disposed of under
tension on the sheet. the same conditions that apply to waste oil. However, it should not be
mixed with waste oil, since the latter is usually reprocessed.

There have been no reports of adverse effects on health which have


resulted from correct processing of Polystyrene in well-ventilated
areas. BASF Aktiengesellschaft
Copyright 2007

37
Blow molding, Thermoforming and further
processing methods of Polystyrene

Processing of Polystyrene and Styrolux ®


Blow molding This high drawing capability can be seen particularly clearly in Fig. 49
which shows a plot of the AGK 5 hot elongation.
The optimum conditions for blow molding bottles and other articles
depend greatly on the type of machine and the nature of the mold- In this test, loads of 2 g / mm2 are applied to test strips which are
ing and should always be determined beforehand. As in the case of heated at 50 °C / h in an oven. The elongation is recorded as a func-
injection molding and extrusion, changing the color of a given molding tion of temperature. Together with ABS, Polystyrene displays the most
compound may require alterations in the processing conditions. uniform increase in elongation and thus offers a wider processing
window even at relatively high draw ratios than do the polyolefins. In
the latter, the increase in elongation is significantly more abrupt, as a
Thermoforming result of which the wall thickness distribution is considerably more dif-
ficult to control by means of different heater temperatures.
Owing to their wide viscoelastic range, Polystyrene sheet and film
are particularly suitable for thermoforming. The forming temperature Another advantage of Polystyrene is that it absorbs less heat up to
should be between 130 and 150 °C. the thermoforming temperature, which has a favorable effect on the
energy balance and the cycle time. Furthermore, heat absorption is
Polystyrene extrusion grades can achieve high draw ratios. Thus, draw uniform and can therefore be more easily controlled.
ratios of, for example, 5:1 in production of beakers and in the thermo-
forming of interior containers of refrigerators are common. This value This behavior is shown in graph form in Fig. 50 where the heat capac-
can sometimes be even higher, as for the reinforcing ribs at the bot- ity (enthalpy) is plotted against temperature.
tom of components or the depressions in the corrugations.
Specific heat capacity [kJ/kg]
Elongation [%]

80 Partially crystalline
PS-I 700
HDPE HDPE
70
ABS 600
PP
60
500 PP
50
400 amorphous
40 ABS
300 SB
30 PS
PVC
20 200

10 100

0 0
100 110 120 130 140 150 160 170 180 20 50 100 150 200
BASF Aktiengesellschaft

Temperature [°C] Temperature [°C]

Fig. 49: AGK 5 hot elongation; load = 2 g / mm2, Fig. 50: Heat capacity of thermoplastics (reference point: 20 °C).
heating rate = 50 °C / h.
Copyright 2007

38
Machining

Processing of Polystyrene and Styrolux ®


Machining

Semifinished Polystyrene parts can easily be machined by punching,


sawing, drilling, milling, turning, etc., using the tools and machines
customary for metalworking or woodworking.

Owing to the low thermal conductivity and the relatively low softening
temperature, the cutting surfaces have to be cooled by a current of air
or with water. The high-impact Polystyrenes have a lower tendency to
splinter and can be machined more easily.

Joining methods
Welding
Preference is given to ultrasonic welding.
Adhesive bonding
Polystyrene parts can be bonded together with the aid of solvents
such as toluene or methylene chloride, but only to parts made of
the same material. We recommend that all questions regarding
adhesive bonding be directed to a commercial adhesives manu-
facturer.

Surface treatment
Printing, surface coating
Polystyrene can be easily and durably coated and printed by various
techniques.
We recommend that manufacturers of surface coatings or printing
inks be consulted in individual cases.
Metallizing
Polystyrene articles can be provided with a mirror-like, metallic
surface by high-vacuum metallizing.

BASF Aktiengesellschaft
Copyright 2007

39
Extrusion / Styrolux®

Processing of Polystyrene and Styrolux ®


Processing by extrusion Screws with medium compression ratios (2.5 : 1 to a maximum of 3.5 : 1)
have been found to be optimal, that is to say, universal screws (PE, PP)
Styrolux® / GPPS-blends can also be employed. Excessively high shearing elements (barrier
In extrusion processing, particularly the tough Styrolux® grades 684 D, zones, shear sections), however, can cause damage to the product
693 D and 3G 55 in blends with general-purpose polystyrene (GPPS) (cross-linking, gel specks). Generally, the use of a melt pump is rec-
are extruded to form films and then thermoformed into dimensionally ommended.
stable finished parts. The mechanical and optical properties of the film
and of the deep-drawn parts are determined to a large extent by the Flat film extrusion dies and polishing stacks
Styrolux® grade, by the mixing ratio and by the GPPS type (see techni- Chrome-plated and polished flat film extrusion dies with an adjust-
cal information, “Styrolux®: mechanical and optical properties”). able die gap (flex lip) and choke bars are recommended, and the die
gap should be set at + 5 % to +10 % above the desired film thickness
The biaxial stretching during the thermoforming considerably increases in order to minimize orientation in the film. The line speed should be
the toughness of the finished parts; therefore, highly stretched parts set in such a way that the melt cushion in the bead of plastic mate-
such as, for instance, beverage cups can be successfully manufac- rial remains very small. Otherwise, if a larger melt volume were fed
tured with high contents of GPPS (> 50 %). Blends containing 50 % in, there would be a risk of wave formation and other visible surface
to 80 % Styrolux® have proven their worth for the majority of thermo- flaws. Optimal roller temperature control is important for attaining high
forming applications. quality in terms of the transparency, gloss and surface finish of the
films. It is recommended to initially set the first deflector roller at a
Efforts should be aimed at optimizing the homogenization of the com- temperature up to the sticky limit and then to lower the temperature
ponents, and this is achieved by a good mixing action of the screws by 10 °C [18 °F]. For this purpose, the temperature of the polishing
used. Here, the viscosity of the GPPS component in the blend plays stacks should be regulated individually (up to about 80 °C to 90 °C
a role; it should preferably be close to the viscosity of the Styrolux® [176 °F to 194 °F]. Polishing stacks that are too cold leave markings
and it should lie in the melt volume-flow rate (MVR) range of 8 to on the surface.
16 [cm3 / 10 min].
Production of film reels
Pre-drying When film reels are produced, care should be taken to ensure that the
As a rule, the Styrolux® granules do not have to be pre-dried. How- film temperature is lowered as far as possible, for instance, to about
ever, in the event of unfavorable storage or transportation conditions the ambient temperature (between 25 °C [77 °F] and 35 °C [95 °F] at
involving severe temperature fluctuations, moisture can condense on the maximum) and that the winding tension is kept as low as possible.
the surface of the granules and this then has to be removed in a pre- If the films are wound at a temperature that is too high, then the
drying step. The granules should be pre-dried in a dry-air dryer for 3 shrinkage that occurs during cooling causes high tensions in the roll
to 4 hours at a temperature of about 50 °C [122 °F]. of film. In the worse case, this can lead to a partial or total blockage of
the films. Therefore, if the machines are operated at high through-put
Extruder and Screw geometry rates or if the lines are operated at high speeds, it is generally recom-
Styrolux® and blends with GPPS can be processed on all conventional mended that post-cooling rollers be used.
extrusion installations that are also suitable for high-impact poly­
styrene, polyethylene or PVC. A high L / D ratio is advantageous for Recommended Temperature profile
the homogenization and for reducing the sensitivity to pressure fluc- for the processing of Styrolux® by means of extrusion:
tuations. However, with an eye towards keeping the residence times
short, this ratio should not be too large either. As a rule, L / D ratios zone 1 160 - 180 °C
[374 ° F to 392 ° F]
between 24 : 1 and 36 : 1 meet both of these requirements.
zone 2 190 - 200 °C
[374 ° F to 392 ° F]
BASF Aktiengesellschaft

Vented extruders are recommended for the production of high-quality zone 3 to 5 190 - 200 °C
packaging films. They permit the extraction of volatile components and [374 ° F to 392 ° F]
moisture from the melt as well as the removal of entrapped air. adapter 195 - 210 °C
[374 ° F to 392 ° F]
die 210 - 230 °C
Copyright 2007

[374 ° F to 392 ° F]

Temperatures above 230 °C [446 °F] should be avoided.

40
Extrusion / Styrolux®

Processing of Polystyrene and Styrolux ®


Cleaning the extruder Problems areas: film blocking and unsatisfactory de-stacking
In spite of the outstanding stabilization of Styrolux®, product dam- properties
age can occur in case of long residence times in the extruder (dead The Styrolux® extrusion grades 693 D and 3G 55 contain a very
spots, accumulations in the mixing section). An indication of this is active wax system that markedly reduces the blocking of film reels;
the greater incidence of gel specks, which often only appear for a few nevertheless, we recommend processing Styrolux® 3G 55 by inline
seconds but which nevertheless greatly impair the film quality. Such thermoforming whenever possible. The already recommended high
problems require that the extruder be flushed, preferably with standard roller temperatures also activate the wax system that migrates to the
polystyrene. This procedure is also recommended when the product is surface, where it forms a very thin film. This wax film, however, can be
changed or before the extruder is switched off in order to reduce the a hindrance if the films are going to be printed on or decorated, which
thermal stress to the Styrolux® melt caused by the downtimes. is why a corona treatment might be needed after the extrusion or, if
applicable, immediately before the printing (see above, printing and
Co-extrusion decorating).
The special property of Styrolux®, namely, that it forms a composite
with a number of other plastics even without adhesion promoters, For processing problems that can be ascribed to the blocking of film
makes this material a good choice for co-extrusion. Organoleptically reels or to unsatisfactory de-stacking properties of deep-drawn parts
sensitive products such as chocolate or foods with a high fat content and that cannot be solved satisfactorily through our processing recom-
are best packaged, for example, with composites having PET-G as mendations alone, we also offer additive batches.
the cap layer and Styrolux®-GPPS blends as the carrier layer. The
PET-G layer imparts the composite with a very good stress cracking Styrolux®-Batch NB 10
resistance and increased gas tightness; composite films having such a Styrolux®-Batch NB contains an extremely active wax system, which
structure are odor-proof and neutral in flavor. should be added in amounts of 0,5 - 2  % so as to remedy problems
with film blocking.
In addition symmetrical film composites with Styrolux® GPPS as the
carrier layer and PE-LD or PP as the cap layer, which attain a good Styrolux®-Batch ASE
bond without additional adhesion promoters, have been tested under Highly effective lubricants in Styrolux®-Batch ASE serve primarily to
actual processing conditions. The Styrolux®/PE-LD composite com- improve the de-stacking properties of deep-drawn parts and to reduce
bines the excellent surface gloss and the good shrinkage characteris- the scratch sensitivity of Styrolux®. The addition should not exceed
tics of Styrolux® with the high toughness of PE-LD. The Styrolux®/PP 4 %; in most cases, 2 % is enough to form a lubricating film.
composite unites especially the good sealing behavior and shrinkage
characteristics of Styrolux® with the dimensional stability under heat Thermoforming
of PP. Thanks to their broad visco-elastic range, panels and films made of
Styrolux® / GPPS blends are particularly well-suited for thermoforming
Furthermore, Styrolux® multilayer films with an EVOH/PE barrier layer and very high deep-drawn ratios can be achieved. The thermoform-
have been developed for special packaging solutions (MAP, CAP). ing temperatures should lie between 120 °C and 150 °C [248 °F and
302 °F]. The machine tool accessories as well as the adjustment of
However, cap layers are also often co-extruded in order to improve the the IR radiant heaters or ceramic band heaters and the achievable
scratch resistance and destacking properties. Easy-flowing general- high cycle times correspond to those that are customary for the ther-
purpose polystyrene grades are especially well-suited for this purpose. moforming of GPPS/HIPS blends. In order to obtain highly transparent
In this context, the GPPS cap layers should be uniformly co-extruded molded parts without markings and streaks, the following should be
over the film width at a thickness of not much more than 0.01 mm observed:
since excessively thick cap layers of the brittle GPPS reduce the The geometry of the molded parts should not have excessively sharp
impact resistance of the entire composite. corners or excessively narrow radii and generally speaking, a draft of
BASF Aktiengesellschaft

at least 3 ° is recommended. The thermoforming tools are made of


Cap layers can also serve as carriers of special finishes. For instance, highly polished aluminum and should be well vented. The temperature
it is often both technically and economically advantageous to coex- of the tools should preferably be set between 20 °C and 60 °C [68 °F
trude a thin cap layer of antistatic agents or UV stabilizers as well as and 140 °F], preferably at 40 °C [104 °F]. Uniform temperature control
other additives, for example, that enhance the scratch resistance or and especially cooling are required in order to produce dimensionally
Copyright 2007

the de-stacking properties or that have an antiblocking effect. In this stable molded parts without warpage. The assisting plunger and the
case, the carrier material for the cap layer can be the same as that of top plunger should be made of syntactic foam, polysulfone or PTFE in
the core layer, or else it can have a different composition. order to avoid markings on the inner wall of the molded part.

41
Extrusion / Styrolux®

Processing of Polystyrene and Styrolux ®


Printing and decorating Preference should be given to air cooling rings with a mounted iris
Films or deep-drawn parts made of Styrolux® /GPPS can be printed diaphragm since they improve heat transfer. A small distance (4 mm to
on with the colorants normally used for styrene plastics. Occasional 5 mm) between the die and the lower air cooling ring lip is advanta-
problems of insufficient colorant adhesion can occur due to blooming geous for the film bubble stability. In order to prevent the occurrence
of the antiblock additives or waxes. Therefore, it is recommended that of creases, Styrolux® should be laid flat at a temperature of 50 °C to
surface treatments by oxidation such as corona treatment, plasma 60 °C [122 °F to 140 °F]. A rotating take-off / winding combination or
treatment or flame treatment be carried out whenever possible imme- a rotary extruder create Styrolux® reels that are free from hoops, and
diately before the printing since, as a rule, the wax additives tend to a short film path between the take-off unit and the center winder is
continue to migrate. This phenomenon of blooming depends to a great always advantageous.
extent on the storage conditions.
The mechanical properties of the film are determined to a great extent
Blown film extrusion by the blow-up ratio and the take-off speed. Thus, the elongation at
As a starting point into the realm of blown film extrusion, we rec- break and the tensile stress at yield in the lengthwise and crosswise
ommend Styrolux® 684 D in view of its high melt stability. The film directions rise as the blow-up ratio increases.
properties, also in the case of thin films, depend on the Styrolux®
grade, on the GPPS type – here, primarily the easy-flowing types are Blow molding
employed – and on the mixing ratio; any differences in transparency Under continuous extrusion, Styrolux® 684 D can be processed into
are practically negligible at film thicknesses of 10 µm to 100 µm. For blow-molded parts having a length of up to about 500 mm. Striking
most applications, mixing ratios between 70 % and 100 % Styrolux® aspects here are the smooth, brilliant surface and the uniform and
have proven their worth. The melt temperature is of great relevance good transparency.
for the production of high-quality films; under no circumstances
should it exceed 220 °C [428 °F]. The melt temperature should be between 180 °C and 190 °C [356 °F
and 374 °F]. Here, too, care should be taken to ensure that the flow
Typical processing conditions for Styrolux® are compiled below: channels of the film-blowing die do not have any “dead spots” and
that they are not configured too large. It is recommended to use cen-
Feed °C 140 - 160 ter-fed film-blowing dies dimensioned for rigid PVC. The film-blowing
°F 284 to 320 dies should have a polished surface provided with venting slits of the
Melt zone °C 160 - 180 type employed for polypropylene. The pinch-off areas can be designed
°F 320 to 356 in the same way as for processing high-density polyethylene.
Metering zone °C 160 - 180
°F 320 to 356
Blends with up to about 30 % general-­purpose polystyrene are pos-
Die °C 160 - 180
°F 320 to 356 sible if one is willing to accept a certain reduction in the clarity.
Melt temperature °C 170 -  2 00
°F 320 to 356 Recycling
Blow-up ratio – 1:1.1 bis 1:3 Styrolux® waste generated during processing such as, for example,
Distance between m 2.00 -  4 .00 edge strips or web scrap, can be returned to the process after a
die and nip rolls simple grinding step and thus re-utilized for the same application.
Film thickness µm 10 -  2 50 Conse­quently, hardly any production waste is created that would then
* depends on the throughput and film thickness have to be disposed of properly.

The dies should be configured in such a way that they do not have Styrolux® belongs to the group of particularly processing-stable
large melt volumes or dead spots. The cross section of the channel styrene plastics and can be processed several times with general-
BASF Aktiengesellschaft

tapers towards the die gap. purpose polystyrene (GPPS) as well as with high-impact polystyrene
(HIPS).

When used articles such as, for instance, disposable packaging, are
recycled, Styrolux® can be admixed to the melt stream of polystyrene
Copyright 2007

and it even improves the toughness of the recycled material.

42
Safety precautions during processing,
Food Contact Applications and Medical Devices
and Pharmaceutical Applications

Safety information; Safety precautions during processing


Safety precautions during processing Medical Devices and Pharmaceutical Applications

When Polystyrene and Styrolux® are injection molded, thermoformed The BASF manufactures high-quality styrene polymers that meet the
or extruded, small amounts of monostyrene and other degradation various requirements of its customers. BASF provides its customers
products are given off into the surrounding air; the actual amounts with competent assistance and works together with them to obtain
depend on the processing conditions. innovative results.

Inhalation of relatively high concentrations of styrene can, like other However, BASF has not designed or tested its plastics with respect to
organic solvents, have a reversible effect on the nervous system (tired- all of the special requirements related to their use in medical devices
ness, loss of concentration, etc.). Such effects are not to be expected and pharmaceutical applications.
if the workplace concentrations are below the prescribed threshold
limit value of 20  ml / m3 (ppm) (cf. TRGS 900). In particular, BASF does not supply any of these plastics for the manu-
facture of implants or for applications that fall under Risk Class III
In our experience, the styrene concentration will not exceed 1  ml / m3 according to the Medical Device legislation.
(ppm) if the workplace is well ventilated and extracted (e.g. 5 to 8 air
changes per hour). Subject to an evaluation and a release in each individual case BASF is
prepared to supply plastics for medical applications within Risk Class I
A review of emissions of volatile compounds in the processing of or for pharmaceutical applications such as solid dosage forms for oral
thermoplastics may be found in M. J. Forrest et al., Ann. occup. Hyg. applications.
Vol. 39, No. 1, 35-53 (1995).
Provided an agreement can be reached which takes into account the
The possibility of a carcinogenic effect of styrene has been addressed circumstances of each individual case and a disclaimer is accepted by
in a recently published assessment by leading members of the Ger- the customer BASF is prepared to supply plastics for individual medi-
man Commission on Maximum Workplace Concentrations. They pro- cal applications within Risk Class II (with the exception of implants)
pose classifying styrene in a new category: “Substances which have including packaging of parenteral and ophthalmic products as well as
a carcinogenic and genotoxic action but whose action is considered inhalers.
to be so weak that no appreciable contribution to the cancer risk for
human beings is to be expected if the maximum workplace concentra- Customers themselves must make all decisions, exclusively on their
tion (20  ppm for styrene) is adhered to”. own responsibility, about employing BASF plastics in any particular
medical or pharmaceutical application. All manufacturers of medical
(Published in: Deutsche Forschungsgemeinschaft. MAK- und BAT- devices or products intended for pharmaceutical applications must
Werte-Liste 1998; Senatskommission zur Prüfung gesundheitsschäd- decide on their own responsibility whether the medical device or
licher Arbeitsstoffe; Bulletin 34; Wiley-VCH; p. 121). pharmaceutical product manufactured using BASF plastics is safe,
lawful and technically suitable for the intended use. Therefore BASF
makes no warranties, express or implied, concerning the suitability of
Food Contact Applications any BASF plastics for use in any medical device and pharmaceutical
applications.
The composition of the standard grades of the polystyrene and
Styrolux®­ ­product lines complies with the currently valid legislation in If you are planning such a use in medical applications, please inform
Europe and in the United States pertaining to plastics that come into BASF to this effect at styrenics.infopoint@basf.com.
contact with food. Furthermore, these products are in compliance with
the requirements set forth in the recommendations of the German
BASF Aktiengesellschaft

Federal Institute for Risk Assessment (BfR), formerly Bg V V/ BGA.

Should you need an up-to-date certificate of conformity pertaining to


the currently valid statutory regulations or detailed information about
the food contact status of a specific standard grade, please contact
Copyright 2007

BASF directly. www.PlasticsPortal.com

43
Recycling

Safety information; Safety precautions during processing


Recycling

Plastics offer advantages not only in a great variety of technical prop-


erties but also in terms of ecological considerations. After use, Poly­
styrene and Styrolux® represent a valuable raw materials source and
thus make a contribution to the conservation of fossil resources. There
are various possible recycling methods and the method employed
depends on the nature of the used plastic.

BASF Aktiengesellschaft
Copyright 2007

44
Nomenclature
Colors
Forms supplied and storage

Safety information; Safety precautions during processing


Nomenclature Colors

Each Polystyrene grade is designated by three digits and a letter: Polystyrene and Styrolux® are supplied exclusively in undyed form.
These products can be dyed so as to be transparent or opaque.
1st digit ­(Colorflexx® program). Color batches or color concentrates on the basis
Polystyrene class of Styrolux® or polystyrene can be employed for this purpose. When
1 = general-purpose Polystyrene colorants based on a different polymer are used, it is necessary to
4 = high-impact Polystyrene check whether transparency and brilliance are retained.
6 = Styrolux®

2nd digit Forms supplied and storage


Mechanical properties.
The higher the second digit, the higher the impact toughness of the Polystyrene
material. However, the toughness of the high-impact grades is at a General-purpose Polystyrene and high-impact Polystyrene are normally
fundamentally higher level than that of general-purpose Polystyrene. supplied as Granules 2 (cylindrical granules having a length of about
3 mm and a diameter of about 3 mm). Externally lubricated Granules
3rd digit 21 (same granule size as Granules 2) are also available on request for
Heat distortion resistance. high-impact Polystyrene.
The higher the third digit, the higher the heat distortion resistance of
the product. Extrusion and injection molding are normally carried out using Gra­
nules 2. In particular cases, the externally lubricated Granules 21 can
Letter be employed in injection molding.
Flow.
A indicates the highest flow, The bulk density is
Z the lowest flow. about 0.57 g / cm3 for Granules 2,
[about 0.63 g / cm3 for Granules 21]
Examples:
Polystyrene should be stored in the original containers in a dry place
Polystyrene 143 E which is not too hot. Direct exposure to sunlight must be avoided.
1 = general-purpose Polystyrene Storage in a hopper or silo is also possible
4 = intermediate strength
3 = low heat distortion resistance Styrolux®
E = good flow Styrolux® is supplied as cylindrical granules having a length of 2.5 mm
and a diameter of 2 mm. The bulk density is 0.636 g / cm3 and the
Polystyrene 486 M angle of repose is 21° (approximate figures).
4 = high-impact Polystyrene
8 = high impact toughness Standard packaging:
6 = high heat distortion resistance 25 kg paper sack; can be supplied in bulk on request.
M = normal flow
Styrolux® does not undergo any changes when stored in a dry place at
Styrolux 684 D
®
normal temperatures. The product may absorb moisture under unfa-
6 = Styrolux® vorable conditions but this can be removed again by predrying (see
BASF Aktiengesellschaft

8 = good heat distortion resistance processing section).


D = good flow

Modifications are indicated by adding further letters to the base grade


designation of the product:
Copyright 2007

45
Overview of products

Safety information; Safety precautions during processing


Autofroth®* Polyurethane system PU
Basotect ® Foam from melamine resin MF Please visit our homepage:
Capron® Polyamide PA
Cellasto®* Components made from microcellular PUR elastomers PU
BASF Plastics:
CeoDS®* Multifunctional composits made from Cellasto® components PU
Colorflexx ® Service for the self-coloring of polystyrene and ABS
www.plasticsportal.com (World)
CosyPUR®* PU soft foam system PU www.plasticsportal.eu (Europe)
Ecoflex ® Biodegradable plastic /polyester
Ecovio® Biodegradable plastic /polyester on the basis of renewable raw materials Additional information on
Elastan®* Systems for sports field surfaces PU
specific products:
Elastoclear ®* PU system PU
Elastocoat ®* PU systems as coating and casting compounds PU
www.plasticsportal.eu/name of product
Elastocoast ®* PU systems as coating and casting compounds PU E.g. www.plasticsportal.eu/polystyrene
Elastocore®* PU cast system PU
Elastoflex ®* Soft polyurethane foam systems PU Polyurethane:
Elastofoam®* Soft integral polyurethane foam systems PU
www.elastogran.de
Elastollan®* Thermoplastic polyurethane elastomers PU
Elastolit ®* Rigid integral polyurethane foam systems and RIM systems PU www.basf.com/polyurethanes
Elastonat ®* Flexible integral polyurethane systems PU
Elastopan®* Polyurethane shoe foam systems PU PVC and PVCD:
Elastopir ®* Rigid polyurethane foam systems PU www.solvinpvc.com
Elastopor ®* Rigid polyurethane foam systems PU
ElastoskinTM** Flexible integral polyurethane systems PU
Elastospray ®* PU spray foam system PU
Elasturan®* Systems as cold curing cast elastomers PU
Lupranat ®* Diisocyanates PU
Lupranol®* Polyether polyols PU
Lupranol®* Balance Polyether polyols PU
Lupraphen®* Polyether polyols PU
Luran® Styrene  /acrylonitrile copolymer SAN
Luran® S Acrylonitrile  /styrene  /acrylate polymer ASA
Luran® SC Acrylonitrile  /styrene  /acrylate polymer and polycarbonate ASA  + PC
LuraSkinTM Film for coating components
Miramid® Polyamide PA 6, PA 66 Note
Neopolen® E Polyethylene foam EPE The data contained in this publication
Neopolen® P Polypropylene foam EPP
are based on our current knowledge
Neopor ® Expandable polystyrene PS-E
Palusol® Alkali silicate and experience. In view of the many
PermaSkin® System for coating components factors that may affect processing
Peripor ® Expandable polystyrene PS-E and application of our product, these
PlasticsPortalTM Web-based e-Commerce platform for solutions and information data do not relieve processor from
Pluracol®** Polyether polyols PU
carrying out own investigations and
Polystyrol, impact-modified Polystyrene HIPS PS-I
Polystyrol, standard Polystyrene GPPS PS tests neither do these data imply any
SPSTM* Steel-polyurethane systems PU guarantee for certain properties nor
Styrodur ® C Extruded rigid polystyrene foam XPS the suitability of the product for a
Styroflex ® Styrene / butadiene block copolymer SB
specific purpose. Any descriptions,
Styrolux ® Styrene / butadiene block copolymer SB
drawings, photographies, data, pro-
BASF Aktiengesellschaft

Styropor ® Expandable polystyrene PS-E


Terblend® N Acrylonitrile / butadiene  /styrene polymer and polyamide ABS + PA portions, weights etc. given herein
Terluran® Acrylonitrile / butadiene  /styrene polymer ABS may change without prior information
Terluran® HH Acrylonitrile / butadiene  /styrene polymer ABS and does not constitute the agreed
Terlux ® Methyl methacrylate  /acrylonitrile / butadiene  /styrene polymer MABS
contractual quality of the product. It
Ultradur ® Polybutylene terephthalate PBT, (PBT+  ASA)
Copyright 2007

Ultraform® Polyoxymethylene POM


is the responsibility of the recipient of
Ultramid® Polyamide PA 6, 66, 6  / 66, 6  / 6T our products to ensure that any pro-
Ultrason® E Polyethersulfone PESU prietary rights and existing laws and
Ultrason® S Polysulfone PSU legislation are observed. (July 2007)
® = reg. trademark of BASF Aktiengesellschaft TM = trademark of BASF Aktiengesellschaft 46
®* = reg. trademark of Elastogran GmbH TM* = trademark of Elastogran GmbH
®** resp. TM*= reg. trademark of BASF Corporation

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