the effect of temperature and other factors on plastics...
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5 Polyimides
This chapter covers a series of plastics of which
the imide group is an important part of the molecule.
The imide group is formed by a condensation reac-
tion of an aromatic anhydride group with an aromatic
amine as shown in Figure 5.1.
This group is very much thermally stable.
Aliphatic imides are possible, but the thermal stabil-
ity is reduced, and thermal stability is one of the
main reasons to use an imide type of polymer.
5.1 Polyimide (PI)
PIs are high-temperature engineering polymers
originally developed by the DuPont Company. PIs
exhibit an exceptional combination of thermal sta-
bility (.500°C), mechanical toughness, and chemi-
cal resistance. They have excellent dielectric
properties and an inherently low coefficient of ther-
mal expansion. They are formed from diamines and
dianhydrides such as the two shown in Figure 5.2.
Many other diamines and several other dia-
nhydrides may be chosen to tailor the final proper-
ties of a polymer whose structure is like that shown
in Figure 5.3.
DuPont makes a PI called “thermoplastic poly-
imide.” The structure of this polymer is shown in
Figure 5.4 and might be called a polyetherimide.
The data for polyimides is split into two parts,
one for typical PIs (like Figure 5.3) and the other
for thermoplastic polyimides (like Figure 5.4)
Manufacturers and trade names: DuPont
Kapton®, Vespel®, Ube Industries Upilex®-S, Upitol®.
Applications and uses: aerospace, flexible printedcircuits, automotive, heaters, bar code labels, pressure-
sensitive tape, electrical insulation, and safety.
5.1.1 Standard PIs
Data for standard PI polymers are contained in
Figures 5.5�5.32.
5.1.2 Thermoplastic PIs
Data for thermoplastic PI polymers are contained
in Table 5.1 and Figures 5.33�5.46.
5.2 Polyamide�Imide (PAI)
PAIs are thermoplastic amorphous polymers that
have useful properties:
• Exceptional chemical resistance
• Outstanding mechanical strength
• Excellent thermal stability
• Performs from cryogenic up to 260°C
• Excellent electrical properties
The monomers used to make PAI resin are
shown in Figure 5.47.
When these monomers are reacted, carbon dioxide,
rather than water, is generated. The closer the mono-
mer ratio is to 1:1, the higher the molecular weight of
the polymer shown in Figure 5.48. Other monomer
combinations are shown in Tables 5.2 and 5.3.
Manufacturers and trade names: Solvay
Advanced Polymers Torlon®.
Applications and uses: electrical connectors,
switches and relays, thrust washers, spline liners,
valve seats, bushings, bearings, wear rings, cams,
and other applications requiring strength at high
temperature and resistance to wear.
Data for PAI polymers are contained in
Tables 5.4�5.8 and Figures 5.49�5.57.
Composition details of Solvay Torlon® PAIs
used in Tables 5.4�5.8 and Figures 5.49�5.57:
• Torlon® 4203L: 3% titanium dioxide, 0.5%
fluorocarbon
• Torlon® 4301: 12% graphite powder, 3%
fluorocarbon
199
McKeen: The Effect of Temperature and other Factors on Plastics and Elastomers.
DOI: http://dx.doi.org/10.1016/B978-0-323-31016-1.00005-2
© 2014 Elsevier Inc. All rights reserved.
4,4�-Diaminodiphenyl etheroxydianiline (ODA)
Pyromellitic dianhydride (PMDA)
Figure 5.2 Chemical structures of monomers used to make PIs.
Figure 5.1 Reaction of amine with anhydride to form an imide.
Figure 5.3 Chemical structure of a typical PI.
Figure 5.4 Chemical structure of the thermoplastic PI DuPont Vespel® TP-8000 series [1].
200 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.5 Stress vs. strain at
23°C in compression for DuPont
Vespel® machined PI [2].
Figure 5.6 Stress vs. strain at
300°C in compression for DuPont
Vespel® machined PI [2].
Figure 5.7 Stress vs. strain at
23°C in compression parallel to
forming for DuPont Vespel®
direct-formed PI [2].
2015: POLYIMIDES
Figure 5.8 Stress vs. strain at
260°C in tension parallel to
forming for DuPont Vespel®
direct-formed PI [2].
Figure 5.9 Stress vs. strain at
23°C in tension perpendicular to
forming for DuPont Vespel®
direct-formed PI [2].
Figure 5.10 Stress vs. strain at
23°C in tension perpendicular to
forming for DuPont Vespel®
machined PI [2].
202 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.11 Stress vs. strain at
260°C in tension for DuPont
Vespel® machined PI [2].
Figure 5.12 Flexural modulus
vs. temperature for Mitsui
Chemicals Aurum® PI resins.
Figure 5.13 Flexural modulus
vs. temperature for DuPont
Vespel® direct-formed PI [2].
2035: POLYIMIDES
Figure 5.14 Flexural modulus
vs. temperature for DuPont
Vespel® machined PI [2].
Figure 5.15 Flexural modulus
vs. temperature for Ube
Industries Upitol® SA 101 PI.
Figure 5.16 Flexural strength
vs. temperature for Ube
Industries Upitol® SA 101 PI.
204 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.17 Tensile strength
vs. temperature for DuPont
Vespel® direct-formed PI [2].
Figure 5.18 Tensile strength
vs. temperature for DuPont
Vespel® machined PI [2].
Figure 5.19 Tensile strength
vs. temperature for Ube
Industries Upitol® SA 101 PI.
2055: POLYIMIDES
Figure 5.20 Tensile strength
vs. temperature for DuPont
Vespel® SP-21 and ST-2010 PI
resins [3].
Figure 5.21 Compressive
strength vs. temperature for
DuPont Vespel® SP-21 and ST-
2010 PI resins [3].
Figure 5.22 Elongation
vs. temperature for DuPont
Vespel® SP-21 and ST-2010 PI
resins [3].
206 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.23 Dimension change
vs. relative humidity at 23°C for
DuPont Vespel® direct-formed
PI [2].
Figure 5.24 Dimension change
vs. relative humidity at 23°C for
DuPont Vespel® machined PI [2].
Figure 5.25 Dimension change
vs. temperature perpendicular to
forming for DuPont Vespel®
direct-formed PI [2].
2075: POLYIMIDES
Figure 5.26 Dimension change
vs. temperature for DuPont
Vespel® machined PI [2].
Figure 5.27 Dielectric constant
vs. temperature for DuPont
Vespel® SP1 PI [2].
Figure 5.28 Dielectric strength
vs. temperature for DuPont
Vespel® SP1 PI [2].
208 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.29 Dielectric strength
vs. thickness for DuPont Vespel®
SP1 PI [2].
Figure 5.30 Dissipation factor
vs. temperature and frequency
for DuPont Vespel® SP1 PI [2].
Figure 5.31 Surface resistivity
vs. temperature for DuPont
Vespel® SP1 PI [2].
2095: POLYIMIDES
• Torlon® 5030: 30% glass fiber, 1% fluorocarbon
• Torlon® 7130: 30% carbon fiber
• Torlon® 4275: PTFE and graphite
• Torlon® 4630: PTFE and graphite
• Torlon® 4435: PTFE and graphite
• Torlon® 4645: PTFE and carbon fiber
5.3 Polyetherimide (PEI)
PEI is an amorphous engineering thermoplastic.
Thermoplastic PEIs provide the strength, heat resis-
tance, and flame retardancy of traditional PIs with the
ease of simple melt processing seen in standard
injection-molding resins like polycarbonate and ABS.
The key performance features of PEI resins
include:
• Excellent dimensional stability at high tem-
peratures under load
• Smooth as-molded surfaces
• Transparency, though slightly yellow
• Good optical properties
• Very high strength and modulus
• High continuous-use temperature
• Inherent ignition resistance without the use of
additives
• Good electrical properties with low ion
content
There are several different polymers that are
offered in various PEI plastics. Their structures are
shown in Figures 5.58�5.62 with references to one
of the product lines that utilize that molecule.
The acid dianhydride used to make most of the
PEIs is 4,40-bisphenol A dianhydride (BPADA), the
structure of which is shown in Figure 5.63.
Some of the other monomers used in these PEIs
are shown in Figure 5.64.
Manufacturers and trade names: SABIC
Innovative Plastics Ultem®, DuPont Aurum®.
Applications and uses: surgical probes, pharma-
ceutical process equipment manifolds, high-frequency
insulators used in microwave communications
equipment, clamps used to connect printed circuit
boards to video display units used in airplanes, tanks,
and ships.
Data for PEI polymers are contained in
Figures 5.65�5.83.
Figure 5.32 Volume resistivity vs. temperature for DuPont Vespel® SP1 PI [2].
210 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Table 5.1 Mechanical Properties at Various Temperatures of DuPont Vespel® TP-8000 Series PI Compounds [1]
Properties/Temperature(°C)
TP-8054Unfilled
TP-8395PTFEand
Graphite
TP-821230%Glass
TP-813030%
CarbonFiber
TP-831110%
CarbonFiber
TP-854930%
CarbonFiber
TP-879215%
CarbonFiber,15%PTFE
Tensile Strength (MPa)
240 106 86 158 223 243 257 194
23 85 68 147 203 174 208 181
100 50 48 98 160 144 154 155
150 48 38 96 132 127 138 126
Tensile Elongation (%)
240 13 92 1 1 1 2
23 92 14 2 1 2 1 2
100 102 7 1 1 2 1 2
150 94 8 1 1 2 1 1
Tensile Modulus (MPa)
240 1520 1470 10,200 26,100 28,300 27,000 14,400
23 1120 1210 10,200 22,500 11,200 24,300 16,600
100 742 1040 6500 21,900 10,700 22,800 15,400
150 621 804 6000 21,000 13,300 19,100 14,900
Flexural Strength (MPa)
0 � � � 353 273 380 294
23 137 117 241 336 258 358 278
150 88 � 172 227 191 212 198
Flexural Modulus (MPa)
0 � � � 20,670 9853 21,690 13,504
23 2942 2598 9646 21,042 10,349 21,648 14,104
150 2549 � 8268 19,664 9584 19,113 13,270
Compressive Strength (MPa)
0 � � � 309 229 305 203
23 256 233 331 310 219 306 205
150 154 144 220 220 149 191 145
Compressive Modulus (MPa)
0 � � � 410 348 426 403
23 197 197 391 445 413 417 387
150 166 182 365 434 365 388 389
2115: POLYIMIDES
Figure 5.33 Stress vs. strain in
tension at various temperatures
for DuPont Vespel® TP-8054
unfilled thermoplastic PI [1].
Figure 5.34 Stress vs. strain in
compression at various
temperatures for DuPont Vespel®
TP-8054 unfilled thermoplastic
PI [1].
Figure 5.35 Stress vs. strain in
tension at various temperatures
for DuPont Vespel® TP-8130
containing 30% carbon fiber
thermoplastic PI [1].
212 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.36 Stress vs. strain in
compression at various
temperatures for DuPont Vespel®
TP-8130 containing 30% carbon
fiber thermoplastic PI [1].
Figure 5.37 Stress vs. strain in
tension at various temperatures
for DuPont Vespel® TP-8212
with 30% glass thermoplastic
PI [1].
Figure 5.38 Stress vs. strain in
compression at various
temperatures for DuPont Vespel®
TP-8212 with 30% glass
thermoplastic PI [1].
2135: POLYIMIDES
Figure 5.39 Stress vs. strain in
tension at various temperatures
for DuPont Vespel® TP-8311
with 10% carbon fiber
thermoplastic PI [1].
Figure 5.40 Stress vs. strain in
compression at various
temperatures for DuPont Vespel®
TP-8311 with 10% carbon fiber
thermoplastic PI [1].
Figure 5.41 Stress vs. strain in
tension at various temperatures
for DuPont Vespel® TP-8395
with PTFE and graphite
thermoplastic PI [1].
214 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.42 Stress vs. strain in
compression at various
temperatures for DuPont Vespel®
TP-8395 with PTFE and graphite
thermoplastic PI [1].
Figure 5.43 Stress vs. strain in
tension at various temperatures
for DuPont Vespel® TP-8549
with 30% carbon fiber
thermoplastic PI [1].
Figure 5.44 Stress vs. strain in
compression at various
temperatures for DuPont Vespel®
TP-8549 with 30% carbon fiber
thermoplastic PI [1].
2155: POLYIMIDES
Figure 5.45 Stress vs. strain in
tension at various temperatures
for DuPont Vespel® TP-8792
with 15% carbon fiber and 15%
PTFE thermoplastic PI [1].
Figure 5.46 Stress vs. strain in
compression at various
temperatures for DuPont Vespel®
TP-8792 with 15% carbon fiber
and 15% PTFE thermoplastic
PI [1].
4,4�-Diphenyl methane diisocyanate (MDI) Trimellitic anhydride (TMA)
Figure 5.47 Chemical structures of monomers used to make PAIs.
216 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Table 5.2 The Polymer Units of Various Amide�Imide Polymers (Refer to Figure 5.48 for Polymer Structure)
PAI Code R1 from Acid Anhydride R2 from Diisocyanate
PAI(TMI/DPA)
PAI(TMI/HEA)
PAI(TMI/TFA)
PAI(TMI/CDA)
PAI(PMI/CDA)
Table 5.3 The Polymer Units of More Amide�Imide Polymers (Refer to Figure 5.48 for Polymer Structure) [4]
PAI Code R1 from Acid Anhydride R2 from Diisocyanate
PAP
PAO
PAM
PAD
PAT
218 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Table 5.4 Compressive Properties for Solvay Advanced Polymers Torlon® PAI Resins at VariousTemperatures per ASTM D695 [5]
Property/Temperature (°C)
Grade
4203L 4601 4630 4645 5030 7130
Compressive Strength (MPa)
23 172 165 96 124 214 234
100 131 124 83 124 165 186
150 103 103 76 110 138 158
200 83 83 62 90 110 124
Compressive Modulus (MPa)
23 3163 3114 4706 5236 4892 6139
100 2191 2122 2026 3645 3273 3803
150 2136 2067 2115 3149 3087 3790
200 2067 2046 2019 3383 3121 3645
Table 5.5 Tensile Properties for Solvay Advanced Polymers Torlon® PAI Resins at Various Temperatures perASTM D1708 [5]
Property/Temperature (°C)
Grade
4203L 4301 4275 4435 5030 7130
Tensile Strength (MPa)
23 192 164 131 110 205 203
135 117 113 116 90 160 158
232 66 73 56 52 113 108
Tensile Elongation at Break (%)
23 15 7 7 6 7 6
135 21 20 15 4 15 14
232 22 17 17 3 12 11
Tensile Modulus (GPa)
23 4.5 6.8 8.8 14.5 14.6 16.5
Table 5.6 Flexural Modulus (in GPa) at Various Temperatures of Solvay Advanced Polymers Torlon® PAIResins [5]
Temperature (°C)
Torlon® Grade
High Strength Grades Wear Resistant Grades
4203L 5030 7130 4301 4275 4435 4630 4645
2196 7.9 14.1 24.6 9.6
23 5.0 11.7 19.9 6.9 7.3 14.8 6.8 12.4
135 3.9 10.7 15.6 5.5 5.6 11.2
232 3.6 9.9 13.1 4.5 5.1 10.3
Note: ASTM Test Method D790.
2195: POLYIMIDES
Table 5.7 Flexural Strength (in MPa) at Various Temperatures of Solvay Advanced Polymers Torlon® PAIResins [5]
Temperature (°C)
Torlon® Grade
High Strength Grades Wear Resistant Grades
4203L 5030 7130 4301 4275 4435 4630 4645
2196 282 374 310 200
23 244 338 355 219 212 152 131 154
135 174 251 263 165 157 129
232 120 184 177 113 111 91
Note: ASTM Test Method D790.
Table 5.8 Specific Heat at Various Temperatures of Solvay Advanced Polymers Torlon® PAI Resins [5]
Temperature (°C)
Specific Heat (cal/gm°C)
Grade
4203L 4301 5030 7130
25 0.242 0.240 0.229 0.230
100 0.298 0.298 0.276 0.285
200 0.362 0.359 0.327 0.346
250 0.394 0.385 0.353 0.375
Figure 5.48 Chemical structure of a typical PAI.
220 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.49 Stress vs. strain
detail in tension at 23°C tested
on ASTM D638 type 1
specimens for Solvay Advanced
Polymers Torlon® PAI resins [5].
Figure 5.50 Stress vs. strain in
tension at 23°C tested on ASTM
D638 type 1 specimens for
Solvay Advanced Polymers
Torlon® PAI resins [5].
Figure 5.51 Stress vs. strain in
tension for various Solvay
Advanced Polymers Torlon® PAI
resins at 135°C.
2215: POLYIMIDES
Figure 5.52 Stress vs. strain in
tension for various Solvay
Advanced Polymers Torlon®
PAI resins at 200°C [5].
Figure 5.53 Stress vs. strain in
tension for Solvay Advanced
Polymers Torlon® 4203LF PAI at
various temperatures [5].
Figure 5.54 Flexural modulus
vs. temperature for Solvay
Advanced Polymers Torlon®
PAI resins [5].
222 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.55 Flexural strength vs.
temperature for Solvay Advanced
Polymers Torlon® PAI resins [5].
Figure 5.56 Tensile strength vs.
temperature for Solvay Advanced
Polymers Torlon® PAI resins [5].
Figure 5.57 Moisture absorption
vs. relative humidity for Solvay
Advanced Polymers Torlon®
PAI resins [5].
2235: POLYIMIDES
Figure 5.58 Chemical structure of BPADA-PPD PEI (SABIC Innovative Plastics Ultem® 5000 series).
Figure 5.59 Chemical structure of biphenol diamine PMDA PEI (DuPont Aurum®).
Figure 5.60 Chemical structure of BPADA-DDS PEI sulfone (SABIC Innovative Plastics Ultem® XH6050).
Figure 5.61 Chemical structure of BPADA-MPD PEI (SABIC Innovative Plastics Ultem® 1000 series).
Figure 5.62 Chemical structure of BPADA-PMDA-MPD co-PEI (SABIC Innovative Plastics Ultem® 6000 series).
224 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.63 Chemical structure of BPADA monomer.
Oxydianiline(ODA)
Diamino diphenyl sulfone(DDS)
m-Phenylene diamine(MPD)
Biphenol diamine(BP diamine)
p-Phenylene diamine(PDA)
Methylene dianiline(MDA)
Pyromellitic dianhydride (PMDA)
Figure 5.64 Chemical structures of some other monomers used to make PEIs.
2255: POLYIMIDES
Figure 5.65 Stress vs. strain at
various temperatures for SABIC
Innovative Plastics Ultem®
1000—general purpose
PEI resin.
Figure 5.66 Stress vs. strain at
various temperatures for SABIC
Innovative Plastics Ultem®
2100—10% glass reinforced
PEI resin.
Figure 5.67 Stress vs. strain at
various temperatures for SABIC
Innovative Plastics Ultem®
2200—20% glass reinforced
PEI resin.
226 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.68 Stress vs. strain at
various temperatures for SABIC
Innovative Plastics Ultem®
2300—30% glass reinforced
PEI resin.
Figure 5.69 Stress vs. strain at
various temperatures for SABIC
Innovative Plastics Ultem®
2400—40% glass reinforced
PEI resin.
Figure 5.70 Stress vs. strain at
various temperatures for SABIC
Innovative Plastics Ultem®
3452—45% glass/mineral
reinforced PEI resin.
2275: POLYIMIDES
Figure 5.71 Stress vs. strain at
various temperatures for SABIC
Innovative Plastics Ultem®
4000—wear resistant, 25%
glass, 15% PTFE PEI resin.
Figure 5.72 Stress vs. strain at
23°C for several SABIC
Innovative Plastics Ultem®
PEI resins.
Figure 5.73 Stress vs. strain in
compression for SABIC
Innovative Plastics Ultem®
1000—general purpose
PEI resin.
228 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.74 Flexural modulus
vs. temperature for several
SABIC Innovative Plastics
Ultem® glass reinforced
PEI resins.
Figure 5.75 Shear modulus vs.
temperature for several SABIC
Innovative Plastics Ultem® glass
reinforced PEI resins.
Figure 5.76 Tensile strength vs.
temperature for several SABIC
Innovative Plastics Ultem®
PEI resins [6].
2295: POLYIMIDES
Figure 5.77 Specific strength at
elevated temperatures for
Extem® XH resin vs. cast
aluminum [7].
Figure 5.78 Storage modulus of
unfilled Extem® XH resin vs.
other unfilled polymers as a
function of temperature by
DMA [7].
Figure 5.79 Pressure-specific
volume�temperature (PVT) for
SABIC Innovative Plastics
Ultem® 1000—general purpose
PEI resin.
230 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS
Figure 5.80 Moisture absorption
vs. relative humidity for SABIC
Innovative Plastics Ultem®
1000—general purpose
PEI resin.
Figure 5.81 Dielectric constant
vs. frequency and temperature
for SABIC Innovative Plastics
Ultem® PEI resin [6].
Figure 5.82 Dielectric constant
vs. temperature and frequency
for SABIC Innovative Plastics
Ultem® PEI resin [6].
2315: POLYIMIDES
References
[1] DuPontt Vespel® TP-8000 series design hand-
book. DuPont; 2007.
[2] Properties of DuPont VESPEL® parts. DuPont;
1997.
[3] Introducing the new generation in high-
temperature components—technical informa-
tion. DuPont; 2000.
[4] Cao X, Lu F. Structure/permeability relation-
ships of polyamide�imides. J Appl Polym Sci
1994;54:1965�70.
[5] Torlon® PAI design guide. Solvay Specialty
Polymers; 2013.
[6] SABIC Innovative Plastics engineering thermo-
plastics product guide, Ultem® PEI resin.
SABIC Innovative Plastics; 2008.
[7] Extem® resins products, markets and proces-
sing guide extreme performance made easy.
SABIC Innovative Plastics; 2008.
Figure 5.83 Dissipation factor
vs. temperature and frequency
for SABIC Innovative Plastics
Ultem® PEI resin [6].
232 THE EFFECT OF TEMPERATURE AND OTHER FACTORS ON PLASTICS AND ELASTOMERS