ENGINEERING

THERMOPLASTICS
PLASTICS ENGINEERING

Series Editor

Donald E .
Hudgin
Princeton Polymer Laboratories
Plainsboro, New Jersey

1. Plastics Waste: Recovery of Economic Value, Jacob Leidner

2. Polyester Molding Compounds, Robert Burns
3. Carbon Black-Polymer Composites: The Physics of Electrically
Conducting Composites, edited by Enid Keil Sichel
4. The Strength and Stiffness of Polymers, edited by Anagnostis E.
Zachariades and Roger S. Porter
5. Selecting Thermoplastics for Engineering Applications, Charles P.
MacDermott
6. Engineering with Rigid PVC: Processability and Applications, edited
by I. Luis Gomez
1. Computer-Aided Design of Polymers and Composites, D. H. Kaelble
8. Engineering Thermoplastics: Properties and Applications, edited by
James M. Margolis

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ENGINEERING
THERMOPLASTICS
Properties and Applications

Edited by

JAMES M. MARGOLIS
Margolis Marketing and Research Company
New York, New York

MARCEL DEKKER, INC. New York and Basel

Library of Congress Cataloging in Publication Data
Main entry under title:

Engineering thermoplastics.
(Plastics engineering ; 8)
Includes index.
1. Thermoplastics. I. Margolis, James M.
II. Series: Plastics engineering (Marcel Dekker,
Inc.) ; 8.
TA455.P5E54 1985 620.1'923 84-28720
ISBN 0-8247-8051-5

COPYRIGHT © 1985 by MARCEL DEKKER, INC. ALL RIGHTS

RESERVED

Neither this book nor any part may be reproduced or transmitted in

any form by any means, electronic or mechanical, including

or

photocopying,
microfilming, and recording, or by any information storage
and retrieval system, without permission in writing from the publisher.

MARCEL DEKKER, INC.

270 Madison Avenue, New York, New York 10016

Current printing (last digit):

10 9 8 7 6 5 4 3

PRINTED IN THE UNITED STATES OF AMERICA

Engineering Thermoplastics:
Properties and Applications
is dedicated

to my wife, Rena
Preface

Engineering Thermoplastics: Properties Applications is a timely

and
book, answering many vital questions on the
important property
differences
advantagesand of individual engineering thermoplastics.
It is also a basic source and reference for important information on
engineering thermoplastics, which makes it a valuable resource for
executives; managers; design, materials, and sales engineers; and
researchers.
Engineering Thermoplastics: Properties Applications and was

written
by experts the
specific plastics
on book, included in this for
materials and product manufacturers, compounders, and users of
high-performance resins.
The book is also a valuable acquisition for producers of metals and
metal products. Engineering plastics are a viable materials choice for
many metal products.
Each chapter in this work is developed according to resin type and
contains a balance of information prepared by specialists in major
resinproducing companies, with one chapter prepared by the editor.
small part of total plastics
Engineering thermoplastics comprise a
consumption on a tonnage basis, yet the value added to products with
the use of these plastics is essential to the world as we know it.

Without engineering thermoplastics many computer, electronic,

communication,
transportation, and other products would not be able to
be produced at commercial levels of production. Some applications
would not be feasible on any economic basis without these ubiquitous
plastics. Progress in every area of new technology depends on

these plastic materials.

James M. Margolis
Contributors

C. J. Billerbeck Engineering Resins Department, Amoco Chemicals

Corporation, Chicago, Illinois

Don C. Brady Research and Development, Phillips Petroleum

Company,
Bartlesville, Oklahoma

Frances A. Bystry-King* Composite Materials Research, Ciba-Geigy

Corporation, Ardsley, New York

Randall O. Carhart Lexan Product Division, General Electric

Company-Plastics
Group, Pittsfield, Massachusetts

Richard D. Chapman Vydyne Technology, Monsanto Polymer Products

Company, Pensacola, Florida

John L. Chruma Market Development, Plastics, Monsanto Polymer

Products Company, St. Louis, Missouri

George E. Feth Noryl Products Division, General Electric

CompanyPlastics
Group, Pittsfield, Massachusetts

*
Current affiliation: Additives Department, Ciba-Geigy Corporation,
Hawthorne, New York
James E. Harris Specialty Polymers and Composites Division, Union
Carbide Corporation, Bound Brook, New Jersey

Steven J. Henke Department of Research and Development, Amoco

Chemicals Corporation, Naperville, Illinois

H. Wayne Hill, Jr. Research and Development,. Phillips Petroleum

Company, Bartlesville, Oklahoma

Glenn B. Hilton Research and Development, Monsanto Polymer

Products
Company, Louis, St. Missouri

James R, Irish Composite Polymers Products Department, General

Electric Company-Plastics Group, Pittsfield, Massachusetts

Cathleen A. Johnson Marketing Technical Service, Monsanto Polymer

Products Company, St. Louis, Missouri

John J. King Department of Resins, Ciba-Geigy Corporation,

Ardsley,
New York

Louis M. Maresca Specialty Polymers and Composites, Research and

Development, Union Carbide Corporation, Bound Brook, New Jersey

James M. Margolis Margolis Marketing and Research Company, New

York, New York

Rhymer B. Rigby Performance Resins Division, ICI Americas Inc.,

Wilmington, Delaware

Lloyd M. Robeson Specialty Polymers and Composites, Research and

Development, Union Carbide Corporation, Bound Brook, New Jersey

I. William Serfaty ULTEM Products Section, General Electric

CompanyPlastics
Group, Pittsfield, Massachusetts

Allan C. Serle Celanese Engineering Resins, A Division of Celanese

Corporation, Summit, New Jersey
Contents

v
Preface
Contributors
vii

Chapter 1.1TPeorlypht alent

Chapter 2.19TPeolrybpuhtlean

Chapter 3.29Polycarbonte

Chapter 4.83PNlaystoicns

Chapter 5.1OPolypx2heind3l

Chapter Acetals
6.
151

Chapter 7.1Poly7sufone
Chapter 8. Polyphenylene Sulfide
201

Chapter 9. 235
Polyethersulfone

Chapter 10. Polyarylates255

Chapter 11. Polyetherimide283

Chapter 12. Polyetheretherketone299

Chapter 13. Polyimides315

Chapter 14. Acrylonitrile-Butadiene-Styrene335

Chapter 15. Torlon Poly(amide-imide )373

Coomductpanies
of
prList
and
383
Appendix
Index
385
ENGINEERING
THERMOPLASTICS
<br/>
1
Polyethylene Terephthalate

JAMES M. MARGOLIS Margolis Marketing and Research Company,

New York, New York

I. Introduction 1
II. Fiber, Film, and Bottle Grades 5
III. Engineering Pet Resin Grades and Properties 6
IV. Processing Properties and Parameters 12
A. Drying 12
B. Injection-Molding Temperatures and Pressures 13
C. Injection-Molding Equipment Considerations 15
V. Applications 16

I. INTRODUCTION

Polyethylene terephthalate (PET) is a thermoplastic polyester made by

the condensation reaction of ethylene glycol with either (1) terephthalic
acid (TPA) or (2) dimethyl terephthalate (DMT), as shown in the
following reactions.

(1)
 Margolis

(2)

Polyethylene terephthalate production is a two-step process.

Dimethyl
terephthalate ethylene glycol
is heated with
Step
to form a mixture
two is
of dihydroxyethyl terephthalate and higher oligomers.
further heating to 518°F (270°C) under vacuum, with the catalytic
conversion of dihydroxyethyl terephthalate to PET. The catalyst can
be antimony oxide (Sb2O3).
Terephthalic acid is produced by air oxidation of paraxylene. The
terephthalic acid is purified by reacting it with methanol (CH3OH) to
form dimethyl terephthalate.

(3)

glycol
Ethylene (EG) is produced from ethylene oxide, which is
derived gas. Diethylene glycol (DEG)
from ethane by is formed the
condensation
reaction of ethylene glycol with ethylene oxide. DEG
linkages the PET molecule reduce the
melting point
on glass and transition
temperature of PET and affect PET thermal stability.

(4)

A condensation reaction usually refers to a reaction of two or more

reactants in which the polymer product contains fewer atoms in the
repeating unit than the monomer or comonomer reactants. In reactions
(1) and (2) , the polyethylene terephthalate repeating unit contains less
 Polyethylene Terephthalate

(5)

atoms than the ethylene glycol and DMT. The atoms split off to form
water (H2O) in reaction (1) and methanol (CH3OH) in reaction (2) .
PET is produced by continuous melt-phase polymerization followed
by a solid-phase polymerization at high vacuum and temperatures
above 518°F (270°C).
PET was developed in the 1930s at the E. I. du Pont de Nemours
and Company by a research team headed by Dr. W. H.
laboratories
Carothers during the time he developed nylon 6/6 in a research
objective
to produce synthetic fibers to replace silk.
Polyethylene terephthalate is used throughout the world to make
synthetic fibers for fabrics, carpeting, and tire cord; and to make
films for food packaging, photographic film, and video, computer,
and magnetic tapes. In 1977 blow-molded PET bottles became
commercially
soft available for carbonated drinks. In 1984 blow-molded PET
bottles appeared on the market for
liquor products, with applications
for non-beverage foods, pharmaceuticals, and toiletries in the offing.
Conventionally, resin consumption statistics do not include fibers
which amount to approximately 3.5 to 4.0 billion pounds of PET in 1984.
PET resin consumption for film, bottles, and injection molding will top
1 billion pounds (500,000 metric tons) in the United States in the
mid1980s.Films account for nearly half of this total and bottles account
for more than 40%.
This chapter is concerned with engineering-grade PET resins used
for high-performance products where mechanical properties and
dimensional
stability, stiffness, resistance,
such as resistance, warp creep
and tensile strength; dielectric properties; chemical resistance; and
temperature resistance are critical factors.
applications account for 5—10% of PET resin consumption in the
These
United States, mostly for injection-molded products.
The basic polyethylene terephthalate polymer, precursor to fibers,
films, bottles, and engineering thermoplastics, is dramatically changed
to meet the processing and finished product requirements of these four
application groups.
A fundamental difference between the PET resins used for these groups
is the degree of crystallinity of the resin and related parameters such
as glass transition point and melt temperature.
 Engineering grades are highly crystalline, while film and
bottlegrade
PET are amorphous. PET resin is usually produced with
approximately50% crystallinity. At this point, engineering grades are
differentiated from fiber, film, and bottle grades.
Lower molecular weight polyethylene terephthalates show faster
crystallization rates. The reason for this behavior is that lower molecular
weight polymer mobility, which enhances crystallization. The
increases
effect of molecular weight on crystallization rate is illustrated in Table 1.
Faster crystallization permits faster molding cycles and lower
processing
temperatures. The degree of crystallinity is observed by
determining
the ratio of the heat of cold crystallization (ΔHcc) of amorphous
of crystalline polymer. Using
polymer to the heat of fusion
(ΔHf)
differential
scanning calorimetry, ΔHcc is measured during initial heating
and AHf is measured during subsequent heating. The higher the ΔHcc/-
ΔHf value, the more amorphous the resin. A modified fully crystalline
PET yields an ideal ΔHcc/ΔHf ratio of zero, while an amorphous PET
has a ratio up to 0.61.
Engineering-grade PET resins are fiber glass- and mineral-reinforced,
usually with 30—45% by weight reinforcement. Recent grades contain
55% fiber glass, and grades are available with fiber glass + mica
reinforcements.
A key to commercial-grade engineering PET is the use of
rapid-crystallization agents, called nucleating agents, to reduce process
cycle time and permit lower mold temperatures of less than 212°F (100°C).
Nucleating agents speed up crystallization from rates of 15 sec to as low
as 2 sec.

The degree of crystallization achieved during melt processing

depends on the rate of crystallization and the time during which the melt

temperature is maintained.
PET shows slow rates of crystallization above the processing melt
temperatures which are between 518 and 572°F (270 and 300°C). The
lower end of the range is usually preferred to minimize polymer
degradation.Typical commercial-grade PET resins melt at 482—518°F
(250—270°C). Most crystallization occurs between 248 and 428°F (120

TABLE 1 PET Molecular

Weight/Crystallization
Half-Time

PET molecular weight Crystallization

average half-time (min)

15,800 18.5

14,000 15.0

11,200 3.5
and 220°C), with a maximum crystallization rate at 374°F (190°C). A
significant amount of crystallization occurs in the mold cavity.

II. FIBER, FILM, AND BOTTLE GRADES

Since amorphous PET can soften and adhere to a hot extruder screw,
causing slugging, it is practical for the resin to possess some degree
of crystallinity. In the manufacture of fibers and films the PET is
extruded and then quenched rapidly into an amorphous state, followed
with uniaxial orientation for fibers and biaxial orientation for films.
Orientation is carried out at 212—248°F (100—120°C), somewhat higher
than the glass transition point, of 158°F (70°C).
Tg,
In order to attain orientation in nbers and turns the PET melt must
be cast into an amorphous preform by quick quenching. The
quenching
technique
Fine filaments
differs for fine filaments, thin films, and thicker films.
from undrawn yarn
are produced preforms which are
air quenched. provide quenching for thin films,
Water-cooled rolls
and heavier gauges require water-immersion quenching. In order to
induce an amorphous state for fibers and films the preforms are cooled
by quenching close to the glass transition temperature, Tg. Uniaxial
orientation for fibers and biaxial orientation for films follows
quick-quench
cooling.
In the manufacture of bottle-grade PET the high viscosity melt is
converted to clear amorphous resin by rapid quenching PET pellets
in water. The pellets are further polymerized in the solid phase at
temperatures just below the melt point, Tm. This step reduces
aldehyde
content because
aldehyde-forming degradation
reduced at the lower, solid-phase polymerization temperatures.
reaction rates are

Aldehydes
which are formed during the polymerization process step can

impart an beverages in PET bottles. Aldehyde

undesirable taste to
content is kept to less than 2.5 ppm. Solid-phase polymerization is
usually not required for fiber and film production because
aldehydegenerated
taste is not a factor.
in the melt temperature range also
Solid-phase polymerization
reduces
the formation of extractable oligomers, resulting in purer a

higher molecular weight weight polymer, and determining the final

intrinsic viscosity (IV). IV is another distinguishing characteristic
between fiber-, film-, and bottle-grade PET resins. IV, a measure
of molecular weight differences, range from 0.62 to 1.04 for clear PET
resins. Textile fibers are produced with lower IV grades; industrial
fibers, films, and strapping are produced with higher IV grades; and
bottle are molded with PET grades ranging from 0.72 to 0.85 IV, with
average values about 0.72/0.74.
Bottles are produced from amorphous pellet preforms which are
injection
molded in cooled molds, reheated above the glass transition
point, Tg, and stretch-blown in a cold mold to produce biaxially
oriented clear bottles. There are a number of commercial and
developmental
modifications to produce high-quality clarity, sparkle, and
physical properties.

III. ENGINEERING PET RESIN GRADES AND PROPERTIES

Engineering grades of PET are crystalline and contain fiber

reinforcements.
engineering thermoplastics
Most other exception with the of
polyphenylene sulfide are available in unreinforced grades.
Different grades of engineering PET are produced with varying
amounts of fiber glass reinforcement, mineral reinforcement,
particularly
mica, flame retardants, colorants, and other performance
ingredients.
Reinforcements improve strength and dimensional stability,
particularly
tensile strength, flexural strength (stiffness), and warp
resistance. Fiber reinforcements also enhance service temperature
levels and chemical resistance.
The American Society for Testing and Materials (ASTM) Standard
Specification D3220-81 for Reinforced Thermoplastic Polyester Molding
and Extrusion Materials covers fiber glass-reinforced thermoplastic
polyester resins. The two commercially available generic commercial
thermoplastic polyester polyester resins, also called polyterephthalate
resins, are polyethylene terephthalate (PET), which this chapter
covers, and polybutylene terephthalate (PBT), covered in Chap. 2.
ASTM Specification D3220-81 provides the designation of
commercially
available grades based on (1) specific gravity, (2) tensile
strength, (3) flexural modulus, (4) Izod impact strength, and (5)
deflection
temperature under flexural load. Table 2 shows the ranges
for minimum values for the five
according properties to ASTM
SpecificationD3220-81.
Table 3 , from which the above ranges were taken shows ASTM D3220
numerical designations for reinforced and filled thermoplastic polyester,
including additives. (ASTM D3220 includes a numerical designation
"0" for "unspecified property value," but commercial polyethylene
terephthalate grades have specified values for all five properties
shown in Table 3 .)
For example, according to Table 3 , a resin designated 35423 would
have the following properties:

Specific gravity 1.40

Tensile strength
psi 18000
MPa 124

Flexural modulus
psi x 105 10
Gpa 6.9
 Izod impact strength
notched
ft-lb/in. 0.6
J/m 32

Deflection temperature
under load (DTUL)
@ 264 psi (1.82 MPa)
°F 226
°C 130

Three principal United States producers of injection molding fiber

glass-reinforced PET are:

PET Producers Tradename (see Table 4)

E. I. du Pont de Nemours and Co., (Inc.) Rynite
Polymer Products Department
Wilmington, Delaware 19898

Mobay Chemical
Corporation Petlon
Plastics andCoatings Division
Pittsburgh, Pennsylvania
Allied Corporation Petra
Allied Fibers & Plastics Company
Engineered Plastics
P. O. Box 2332R
Morristown, New Jersey 07960

Meocphearnticeasl 2
TABLE
Pr2 Mechanical Properties

Range, room temperature

Property (except DTUL)

Specific gravity 1.30-1.60

Tensile strength 6500-21,000 psi

45-145 MPa

Flexural modulus 330,000-1,500,000 psi

2.3-10.3 GPa

Izod impact strength 0.4-1.5 ft-lb/in.

21-80 J/m

Deflection temperature 122—410°F

Under Load (DTUL) 50—2*10°C
@ 264 psi (1.82 MPa)
 PMreocphearticeasl
TABLE 3 Mechanical Properties

Property

1.30 1.35 1.40 1.50 1.55 1.60

1. Specific gravity
2. Tensile strength
9000 13000 15000 18000 21000
6500
psi 145
45 62 90 103 124
MPa

3. Flexural modulus
5.0 7.0 10.0 12.0 15.0
x 105 3.3
psi 10.3
2.3 3.5 4.8 6.9 8.3
GPa

4. Izod impact strength

Notched
0.8 1.1 1.3 1.5
ft-lb/in. 0.4 0.6
43 59 69 80
J/m 21 32

5. Deflection temperature
Under load (DTUL)
@ 264 psi (1.82 MPa)
266 356 392 410
°F 122 212
130 180 200 210
°C 50 100
TABLE 4 Suppliers' PET Grades

Rynite

430 530/530FR 545 555 935 940/940FB

% Fiber glass by Weight

30% 30%/30% 45% 55% 35% 40% 40%

+ + fiber fiber fiber foamable
flame glass glass glass
toughening
agent retardant + +

mica
+

(impact mica mica

modifier)

Petlon

3530/4530 7530 3550

30%/30% 35% 50%

+ fiber glass
flame +

retardant mica

Petra

130/130FR 145/145FR 155

30%/30% 45%/45% 55%

+ +

flame flame
retardant retardant

In the mid-1980s grades with 40% or more reinforcement are being

widely used, and flame-retardant grades are increasingly in demand
Typical properties of suppliers' grades with the same reinforcement
content are shown in Table 5 .

In order to make precise comparisons it is necessary to know

more

the test parameters for each property value, since ASTM test
procedures
often allow a range for testing procedures.
The addition of mica, a mineral reinforcement, reduces warpage.
Rynite 935 and 940 and Petlon 7530 show low warp. Higher fiber
glass content increases stiffness.
Rynite 555 has a flexural modulus
(stiffness of 2.6 × 106 psi
(18.6 GPa). Higher fiber glass content
also increases strength. Rynite 555, with 55% fiber glass and mica, has a
TABLE 5 PET + 30% Fiber Glass + Flame Retardant Room
Temperature/ASTM Test Procedures

Property Rynite 530FR Petlon 4530 Petra 130FR

Tensilestrength 22000 (152) 18900 (130) 21000 (145)

psi (MPa)
Elongation @ 2.3 2.0 2.0
Break %

Tensile modulus 1.46 (10.1)

psi x 106 (GPa)
Flexuralstrength 32000 (221) 27600 (190) 32000 (221)
psi (MPa)
Flexural modulus 1.5 (10.3) 1.45 (10.0) 1.3 (9.0)
psi x io® (GPa)

Compressive 25000 (172) 21500 (148)

strength
psi (MPa)
Deflection temp, 440 (226) 437 (225) 420 (215)
under load @
264 psi (1.82
MPa) °F (°C)
Izod impact 1.6 (85.4) 1.44 (77) 1.70 (90)
strength notched
ft-lb/in. (J/m)

Melting point 489 (254) 491 (255) 466 (241)

°F (°C) Fisher-Johns
Mold shrinkage
in./in. (mm/mm)
Flow direction 0.002 0.002 0.003-0.005
Transverse 0.009 0.008

Oxygen index % 33 31

UL94 Flammability V-0 V-0 V-0

0.028"
(. 71mm)
Arc resistance sec 117 81

Dielectric 3.6 (106Hz) 4.2 (60Hz) 3.6 (106Hz)

constant tin foil
electrodes
Volume resistivity 10*-® 1015
ohm cm

Surface resis- 10*^ 10^

tivity ohm/sq
Dielectric strength 430 (16.9) 408 (16.1)
volts/mil (KV/mm)* (1/8”) (1/8")

"“Thicker specimens yield lower values.

TABLE 6 Chemical Resistance

Percent original tensile strength retained after 28 days

Chemical Petlon 3530/4530

Sulfuric acid (36%) 102%/101%

Acetic acid (5%) 95/76
Hydrochloric acid (10%) 89/95
Ammonium hydroxide (10%) 67/87
Sodium hydroxide (10%) 96/95
Calgonite detergent (10%) 89/89

Isopropyl alcohol 104/105

Heptane 100/99
Turpentine 97/99
Toluene 92/86
Ethyl acetate 86/90
Methyl ethyl ketone 78/84
Methylene chloride 41/35
Automotive fluids
Ethyl alcohol (10%) 105/101
Gasoline 98-102/96-100
Motor oil 101/95
Brake fluid 99/102
Kerosene 99/98
Ethylene glycol 100/92
Transmission fluid 96/100
tensile strength psi (197 MPa), which is about the same
of 28,500
as unreinforced ultrahigh-performance polyamide-imide Torlon 4203,
and a DTUL/264 psi (1.82 MPa) of 445°F (229°C).
In order to increase resin stiffness with fiber glass or a mineral
reinforcementsuch as mica, the reinforcing agent must be chemically
coupled to the resin. The surface of the reinforcing material is
chemically
treated to react with the polymer resin to form a bond. An
alternative is to produce chemically coupled resin. Without chemical
coupling the reinforcing effect is reduced.
Flame-retardant grades are becoming widely used for electrical
applicationssuch
reinforcement
grades
as30%electrical connectors. PET with
or flame retardant are general-purpose
fiber
glass and no mica
grades. Rynite 530, Petlon 3530, and Petra 130 are general-purpose
grades. Rynite 430 is an impact-resistant grade containing a
toughening
agent (impact modifier).
Fiber glass-reinforced PET has excellent resistance to automotive
fluids, including gasoline and oils; many commonly used alcohols and
other organic solvents, including heptane and turpentine; and weak
acids and bases. Table 6 shows chemical resistance of 30% fiber glass
PET based on Petlon 3530/4530.
Polyethylene terephthalate is available in a broad range of colors,
although all colors are not standard in all grades. Custom colors can
be ordered to meet specifications. Typically, standard colors include
gray, white, standard black and weatherable black, red, orange,
yellow,
green, and blue in
particular tones.

IV. PROCESSING PROPERTIES AND PARAMETERS

A. Drying
PET is hygroscopic, and in its melt state the resin hydrolyzes. It is
important to distinguish between moisture absorption (hygroscopic) and
hydrolysis, which is the reaction of a condensation polymer with water,
resulting in polymer degradation (a cleavage of the main oxygen bond).
Polymer degradation is a reduction in the molecular weight with a
decrease in viscosity, with a corresponding increase in melt flow.
Polymer
degradation also causes a reduction in strength and toughness of
finished parts. An increase in melt flow can cause: (a) overpacking
during injection molding, (b) sticking in the runners and mold cavity,
and (c) flash.
Virgin PET resin supplied in moisture-proof containers can have a
moisture content up to 0.04%, but hydrolysis can occur at a moisture
level above 0.02%. Therefore, even virgin PET direct from the
supplier's
containers, as well as regrind, should be dried to a level of
less than 0.02% and maintained at that level. The reaction of moisture
with PET is rapid. Dehumidifier hopper drier equipment is
recommended
with injection-molded PET.
TABLE 7 Drying Conditions for PET

1. Air flow rate Approximately 1 ft3/min/lb PET/hr

(Approximately 3 m3/hr/kg PET/hr)
2. Air temperature 275°F (135°C)

3. Air dew point 0°F (-18°C) or less

The three principal variables to monitor in dehumidified hopper

driersare: (a) air flow, (b) air temperature, and (c) air dew point.
Typical values for these variables are shown in Table 7 .

Drying time varies from 4 hr for wet resin to 2 hr for virgin resin.
Extended time should be carried out at lower temperatures,
drying
about 225°F (107°C) to avoid possible loss of volatile additives in the
PET compound.

B. Injection-Molding Temperatures and Pressures

Although resin grades from the same supplier show the same melt
temperature,
suppliers PET from different shows different melt
temperatures,
as illustrated in Table 8 . The melt range for Petra is similar
to Rynite.
Recommended typical injection-molding cylinder temperatures also
differ between suppliers, as shown in Table 9 .

Typical injection-molding conditions can be illustrated with Petlon

PET ( Table 10 ).
Injection pressure for Ryrate is 8000—12000 psi (55—83 MPa) by way
of comparison. Screw speeds which are excessive can reduce fiber
glass length and reduce mechanical properties of the finished part.
A significant degree of crystallinity occurs in the mold. Therefore,
mold temperatures should be selected carefully in order to enhance
crystalline formation (nucleation). Mold temperature also influences
cycle time and product quality, particularly warpage, shrinkage,
surface
gloss, depth of color, and chemical resistance.
The selection of mold temperature is related to wall thickness. Thin
walls require higher mold temperature. The temperature of a thin wall

TABLE 8 Injection Molding Melt Temperature Range

PET Melt temperature range

Petlon 495—530°F (257—277°C)

Rynite 530—590°F (277—310°C)

TABLE 9 Injection Cylinder Temperatures

Barrel
section Petlon Rynite Petra

Temperature Range °F (°C)

Rear 460-480(238-249) 510-570(266-299) 550(288)

Center 465-485(240-252) 510-570(266-299) 550-590(288-310)

Front 480-500(249-260) 510-560(266-293) 440-590(288-310)

Nozzle 480-500(249-260) 500-570(266-299) 550-290(288-310)

Mold 190-250(88-121) 185-250(85-121) 180-210(82-99)

aRynite 555 temperature settings are slightly higher.

0.06 in. (1.52 mm) or less can decrease at a rate that is too fast to
permit maximum crystallization when the mold temperature is too low.
A thicker wall will cool at a lower rate, permitting more uniform
crystallization
and the desired degree of crystallinity. Mold temperatures
for thin wall construction should be set at 210—250°F (99— 121°C).
However, mold temperatures above 185°F (85°C) for some PET resins
can result in poorer surface appearance, and parts dimensional change

will be greater. Higher mold temperatures can be achieved with oil

heaters or with electric cartridge heaters built into the mold.

TABLE 10 Injection-Molding Processing Conditions

Processing conditions

Injection pressure 6000-12000 psi (41-83 MPa)

Hold pressure 50% to 75% of injection pressure
Back pressure 25-60 psi (172-414 kPa)
Screw speed 45—75 rpm

Fill rate 1—4 sec

Cushion up to 0.125 in. (3.2 mm)

TABLE 11 Mold Dimensions for Rynite

Approximate dimensions
Mold section (in. [mm])

Runners
Full round or trapezoidal 0.15-0.28 (3.8-7.11)
entrance diameter

Gates
Round (tunnel gates) >0.020 (0.508)
3-Plate molds <0.090 (2.30)
Rectangular
Thickness >50% part thickness
Width 1.5—2 times part thickness

Vents 0.002 (0.51) deep, min At 0.03 in

(0.076 mm) from the cavity, vents
are deepened to about 0.125 in.
(3.17 mm) and extended to the
edge of the mold

Taper (draft angle)

Ribs, bosses, sides, sprues 0.5-1°

C. Injection-Molding Equipment Considerations

Typical injection-molding equipment uses Xaloy 800 or equivalent lined

barrels, general-purpose chrome-plated Colmony 56 screws to minimize
abrasion by fiber glass, and mica reinforcements. Screw configurations
with L/D ratios of 18:1—25:1 are satisfactory. However, higher ratios
(longer screws) are avoided in order to minimize fiber glass damage
and unnecessary melt residence time.
Conventional straight-bore nozzles with a 1:1 land length orifice
ratio
and 3/16 in. (4.8 mm) minimum diameter orifice satisfactory
are a

trade-off to avoid drool or freeze-off. Nozzle temperature is critical

for producing quality products, and the temperature should be
adjusted
according grade
Mold cavities
to PET in order to prevent drool or

constructed from hardened tool-steel cavities, cores,

are
freeze-off.

runners, and sprues to minimize abrasion and wear from fiber glass
and mica.
Mold design recommendations are available from suppliers. In order
to describe mold design parameters for PET resins Table 11 shows mold
design consideration for
Rynite.
Basic design considerations and equations for viscoelastic materials
apply to polyethylene terephthalate. These equations can be used as
models for computer-aided design/computer-aided manufacture (CAD/-
CAM) of PET parts.
Recommended fillet radii for wall intersections, bosses, and ribs is
1/8 the thickness (of the wall, boss, or rib at the base) with a
minimum
of 0.15 in. (3.81mm).
Walls, bosses, and ribs should have a taper of 0.1-1.0° to facilitate
removal from the mold cavity.

V. APPLICATIONS

The final selection of a specific engineering thermoplastic grade is a

three-step process: (a) elimination of resins that do not qualify for

a given application such as mechanical, electrical, or thermal

properties,
or chemical resistance; (b) trade-off between various advantages

of the remaining resins and their benefits for a given application; and
(c) the final selection.
Every resin has certain outstanding properties, and each grade has
more specific benefits for a given application.

The advantages of PET are its stiffness and warp resistance, and
its benefit is dimensional stability. PET has excellent chemical
resistance
to automotive chemicals and many other chemicals.
Flameretardant
grades (assigned by Laboratory, Inc.) Underwriters of
UL94 V-0 are used in
applications such as transformers in appliances
and computers. Toughened PET grades with higher Izod impact
strength are used in housings for power tools and chemical pumps.
Fiber glass-reinforced PET is used in a wide variety of applications,
including medical devices, furniture, gears, sporting goods, small
kitchen and personal care appliances, and business machines as well
as automotive and electronic products.
Flame-retardant 30% fiber glass PET with a deflection temperature
under load (DTUL) @ 264 psi (1.82 MPa) of 435°F (224°C) is used in
multipin integrated circuit sockets, electrical switches, transformer
coil bobbins, relay components, and telecommunications connectors.
This PET grade is used in seven-way connectors for the additional
benefits of stress crack resistance and high voltage tracking rate.
PET connectors are virtually warp-free, which is especially
important
prevent dislodgement of
to pins. connector PET connectors
can be assembled by wave and vapor phase soldering, which
soldering
subjects the part to 419°F (215°C) and 500°F (260°C) for 2-5 secs.
PET can also be snap-fit assembled.
Rymte 530FR (30% fiber glass flame-retarded PET) has obtained
provisional
Underwriters Laboratories UL Standard 1446 Class 180 (H)
recognition for use in electrical insulating products which are

subjectedto a hot
spot operating temperature 180°C). of This
recognition
increase the
can of PET for transformers and in automotive
use
applications.
 Polyethylene Terephthalate I 17

Other electrical/electronic applications include internal TV com­

ponents, electronic ignition rotor and housings, and electric motor
end caps.
Nonelectric automotive applications include exterior parts such as
windshield wiper components, exterior rear view mirror housings,
and hinges. Forty percent fiber glass plus mica foamable PET is used
for side rails in "F" cars (Firebird and Camaro) to minimize sink marks
opposite bosses. Brakemaster air deflectors are also made from PET.
Personal care and small kitchen appliance applications include hair
curlers and dryers and bases for toasters, corn poppers, coffee
makers, and waffle irons.
Other applications to illustrate the breadth and depth of PET uses
include air rifle, air piston, and trigger lock; monolithic keyboards;
instrument gauge gears, pinions, and housings; and filament spools
for grass-and -weed trimmers. These applications use the high stiff­
ness which is characteristic of engineering PET . Many applications
use PET stiffness and warp resistance to permit precision assembly of
components.
A new crystallizable homopolymer PET sheet was introduced in 1984,
which is vacuum formed into hot-food service trays. The PET is sup­
plied by Eastman Chemical Products, Inc. (Tenite 5132) and Goodyear
Tire & Rubber Company, Chemical Division (Cleartuf 1006). These
companies produce blow-molding grades for PET bottles. The two re­
cent vacuum-formable grades have IV values of O. 8 (Tenite 5132) and
1.0 (Cleartuf 1006).
A key factor to the favorable processing economics for these two
formable PET grades is the same factor that applies to injection-molding
engineering PET grades-rapid crystallization. Crystallization time is
shortened from 15 to less than 4 sec by using nucleating agents.
Nucleation is the formation of lamellar fibrils which grow into spheri­
cal shapes called spherulites. Lamellar fibrils are small regions on the
molecule which crystallize by folding into orderly packets. The rate
of spherulite formation determines the size of the spherulites and the
rate of crystallization. Smaller spherulites are formed with faster
cooling rates (within a range) and with faster nucleation. Smaller
spherulites produce improved mechanical properties as well as per­
mitting faster cycles.
Therefore, nucleation is a paramount factor in the future develop­
ment of engineering polyethylene terephthalate for both improved proc­
ess economics and quality finished products.
120 I Chapman and Chruma

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 Polyetherimide I 297

IX. CONCLUSION

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332 I Bystry-King and King

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