477

Polymers
3.3. Polymers

3.3.1 Structural Units of Polymers ................ 480

The physical properties of polymers depend not
only on the kind of material but also on the
molar mass, the molar-mass distribution, the
kind of branching, the degree of branching,
the crystallinity (amorphous or crystalline), the
tacticity, the end groups, any superstructure,
and any other kind of molecular architecture. In
3.3.2 Abbreviations..................................... 482
3.3.3 Tables and Figures.............................. 483
3.3.3.1 Polyolefines............................ 483
3.3.3.2 Vinyl Polymers ........................ 489
3.3.3.3 Fluoropolymers ....................... 492
3.3.3.4 Polyacrylics and Polyacetals...... 497

the case of copolymers, the physical properties
are additionally influenced by the type of
arrangement of the monomers (statistical,
random, alternating, periodic, block, or graft).
Furthermore, the properties of polymers are
influenced if they are mixed with other polymers
(polymer blends), with fibers (glass fibers,
carbon fibers, or metal fibers), or with other
fillers (cellulose, inorganic materials, or organic
materials).
The tables and figures include the physical
and physicochemical properties of those polymers,
copolymers, and polymer blends which are widely
used for scientific applications and in industry.
The figures include mainly the following physical
properties: stress versus strain, viscosity versus
Part 3 3
3.3.3.5 Polyamides ............................ 501
3.3.3.6 Polyesters............................... 503
3.3.3.7 Polysulfones and Polysulfides ... 506
3.3.3.8 Polyimides
and Polyether Ketones ............. 508
3.3.3.9 Cellulose ................................ 509
3.3.3.10 Polyurethanes ........................ 511
3.3.3.11 Thermosets............................. 512
3.3.3.12 Polymer Blends ....................... 515
References .................................................. 522
shear rate, and creep modulus versus time. How-
ever, other physical properties are also included.
Additionally, the most relevant applications of the
materials are given.

The tables and figures include the physical and physico-
chemical properties of the most important polymers,
copolymers, and polymer blends. Most important here
means that these materials are widely used for sci-
entific applications and in industry. The values in the
main tables are given for room temperature, that is,
25 C; otherwise, the temperature is given in parenthe-
ses. The tables and figures include the following physical
properties:

Melting temperature Tm : heating rate 10 K/min (ISO 11357).

Enthalpy of fusion Hu : the amount of enthalpy (given per monomer unit of the polymer) needed for the transition of
the polymer from the solid state to the molten state.
Entropy of fusion Su : amount of entropy (given per monomer unit of the polymer) which is needed for the transition
of a polymer from the solid state to the molten state.
Heat capacity cp = (H/T ) p H/T ; H = quantity of heat per mass unit, T = temperature increase.
Enthalpy of combustion Hc : amount of enthalpy released in flaming combustion per unit mass of the polymer.
Glass transition temperature Tg : heating rate 10 K/min (ISO 11357).
Vicat softening temperature : TV 10/50, force 10 N, heating rate 50 K/h; TV 50/50, force 50 N,
heating rate 50 K/h (ISO 306).
478 Part 3 Classes of Materials

Thermal conductivity : dq/ dt = A dT/ dx; dq/ dt = heat flux, A = area, dT/ dx = temperature gradient.
Density  = m/V (ISO 1183).
Coefficient of expansion = (1/V0 )(V/T ) p : T = 2355 C (ISO 11359).
Compressibility = (1/V)(V/ p)T .
Elastic modulus E = / ( = stress, = strain (elongation)); elongation rate 1 mm/min (ISO 527).
Shear modulus G = / ( = shear stress, = shear angle).
Poissons ratio = 0.5[1 (E/)(V/V)]; V/V = relative volume change.
Stress at yield y , strain (elongation) at yield y : see Fig. 3.3-1; elongation rate 50 mm/min (ISO 527).
Stress at 50% strain (elongation) 50 : see Fig. 3.3-1; elongation rate 50 mm/min (ISO 527).
Stress at fracture b , strain (elongation) at fracture b : see Fig. 3.3-1; elongation rate 5 mm/min (ISO 527).
Impact strength, and notched impact strength (Charpy) (ISO 179).
Part 3 3

Sound velocity vs , longitudinal (long) and transverse (trans).

Shore hardness A, D (ISO 868).
Volume resistivity e , surface resistivity e : contact electrodes, voltage 500 V (DIN 0303 T30, ISO 93, IEC 60093).
Electric strength E B : specimen of thickness 1.0 0.1 mm (ISO 10350, IEC 60243).
Relative permittivity r , dielectric loss (dissipation factor) tan (IEC 60250).
Refractive index n D , temperature coefficient of refractive index dn D / dT .
Steam permeation: 2025 C, 85% relative humidity gradient (DIN 53122, ISO 15106).
Gas permeation: 2025 C, reduced to 23 C, 1 bar (ISO 2556, DIN 53380, ISO 15105).
Melt-viscositymolar-mass relation.
Viscositymolar-mass relation: [] = K M a means []/[0 ] = K(M/M0 )a , where [0 ] = 1 cm3 /g, M0 = 1 g/mol,
and [] = intrinsic viscosity number at concentration C = 0 g/cm3 [3.1] (DIN 53726, DIN 53727).
Stress (, T ); = strain (elongation), T = temperature (ISO 527).
Viscosity ( d/ dt, T ); d/ dt = shear rate, T = temperature (ISO 11443).
Creep modulus E tc (t, p, T ); t = time, p = pressure, T = temperature; E tc = tc /(t) (tc = creep stress,
(t) = creep strain (creep elongation)); strain 0.5% (ISO 899).

For selected polymers, the temperature dependence Stress

of some physical properties is given. Additionally, the
most relevant applications of the materials are given. b
The tables and figures include the physical properties y
given in the table below (see [3.13]).
As the physical and physicochemical properties of
50
each polymer vary with its molecular architecture, the
tables show the ranges of the physical and physico-
chemical properties, whereas the diagrams show the
functional relationships for a typical species of the poly-
mer, copolymer, or polymer blend. The table on page b y 50% Strain
479 shows the selected 77 polymers, copolymers and
polymer blends. Fig. 3.3-1 Stress as a function of the strain for different
kinds of polymers (see page 478)
 Polymers 479

3.3.3.1 Polyolefines
Polyolefines I
Polyethylene: high density HDPE, medium density MDPE, low density LDPE, linear low density LLDPE, ultra high
molecular weight UHMWPE
Polyolefines II
Poly(ethylene-co-vinylacetate) EVA, Polyethylene ionomer EIM, Cycloolefine copolymer COC [Poly(ethylene-co-
norbornene)], Poly(ethylene-co-acrylic acid) EAA
Polyolefines III
Polypropylene PP, Polybutene-1 PB, Polyisobutylene PIB, Poly(4-methylpentene-1) PMP
3.3.3.2 Vinylpolymers
Vinylpolymers I
Polystyrene PS, Poly(styrene-co-butadiene) SB, Poly(styrene-co-acrylonitrile) SAN

Part 3 3
Vinylpolymers II
Poly(vinyl carbazole) PVK, Poly(acrylonitrile-co-butadiene-co-styrene) ABS,
Poly(acrylonitrile-co-styrene-co-acrylester) ASA
Vinylpolymers III
Poly(vinyl chloride): unplastisized PVC-U, plastisized (75/25) PVC-P1, plastisized (60/40) PVC-P2
3.3.3.3 Fluoropolymers
Polytetrafluoroethylene PTFE, Polychlorotrifluoroethylene PCTFE, Poly(tetrafluoroethylene-co-hexafluoropro- pylene)
FEP, Poly(ethylene-co-tetrafluoroethylene) ETFE, Poly(ethylene-co-chlorotrifluoroethylene), ECTFE
3.3.3.4 Polyacrylics, Polyacetals
Poly(methyl methacrylate) PMMA; Poly(oxymethylene) POM-H, Poly(oxymethylene-co-ethylene) POM-R
3.3.3.5 Polyamides
Polyamide 6 PA6, Polyamide 66 PA66, Polyamide 11 PA11, Polyamide 12 PA12, Polyamide 610 PA610
3.3.3.6 Polyesters
Polycarbonate PC, Poly(ethylene terephthalate) PET, Poly(butylene terephthalate) PBT, Poly(phenylene ether) PPE
3.3.3.7 Polysulfones, Polysulfides
Polysulfon PSU, Poly(phenylene sulfide) PPS, Poly(ether sulfone) PES
3.3.3.8 Polyimides, Polyether ketones
Poly(amide imide), PAI; Poly(ether imide), PEI; Polyimide, PI; Poly(ether ether ketone), PEEK
3.3.3.9 Cellulose
Cellulose acetate CA, Cellulose propionate CP, Cellulose acetobutyrate CAB, Ethyl cellulose EC, Vulcanized fiber VF
3.3.3.10 Polyurethanes
Polyurethane PUR, Thermoplastic polyurethane elastomer TPU
3.3.3.11 Thermosets
Thermosets I
Phenol formaldehyde PF, Urea formaldehyde UF, Melamine formaldehyde MF
Thermosets II
Unsaturated polyester UP, Diallylphthalat DAP, Silicone resin SI, Epoxy resin EP
3.3.3.12 Polymer Blends
Polymer Blends I
Polypropylene + Ethylene/propylene/diene-rubber PP + EPDM, Poly(acrylonitrile-co-butadiene-co-styrene) +
Polycarbonate ABS + PC, Poly(acrylonitrile-co-butadiene-co-styrene) + Polyamide ABS + PA, Poly(acrylonitrile-
co-butadiene-co-acrylester) + Polycarbonate ASA + PC
480 Part 3 Classes of Materials

Polymer Blends II
Poly(vinyl chloride) + Poly(vinylchloride-co-acrylate) PVC + VC/A, Poly(vinyl chloride) + chlorinated Polyethylene
PVC + PE-C, Poly(vinyl chloride) + Poly(acrylonitrile-co-butadiene-co-acrylester) PVC + ASA
Polymer Blends III
Polycarbonate + Poly(ethylene terephthalate) PC + PET, Polycarbonate + Liquid crystall polymer PC + LCP, Polycar-
bonate + Poly(butylene terephthalate) PC + PBT, Poly(ethylene terephthalate) + Polystyrene PET + PS, Poly(butylene
terephthalate) + Polystyrene PBT + PS
Polymer Blends IV
Poly(butylene terephthalate) + Poly(acrylonitrile-co-butadiene-co-acrylester) PBT + ASA, Polysulfon +
Poly(acrylonitrile-co-butadiene-co-styrene) PSU + ABS, Poly(phenylene ether) + Poly(styrene-co-butadiene)
PPE + SB, Poly(phenylene ether) + Polyamide 66 PPE + PA66, Poly(phenylene ether) + Polystyrene PPE + PS
Part 3 3.1

3.3.1 Structural Units of Polymers

The polymers given in this chapter are divided into poly- Poly(acrylonitrile), PAN: CH2 CH
olefines, vinyl polymers, fluoropolymers, polyacrylics, CN
polyacetals, polyamides, polyesters, polysulfones, poly- Poly(vinyl acetate), PVAC: CH2 CH
sulfides, polyimides, polyether ketones, cellulose, O
polyurethanes, and thermosets. The structural units of CO
the polymers are as follows: CH3
Polyolefines Poly(vinyl chloride), PVC: CH2 CH
Polyethylene, PE: CH2 CH2 Cl
Poly(vinyl carbazole), PVK: CH2 CH
Polypropylene, PP: CH2 CH
CH3 N
Poly(butene-1), PB: CH2 CH
CH2
CH3 Fluoropolymers
Poly(tetrafluoroethylene), PTFE: CF2 CF2
Poly(isobutylene), PIB: CH3
Poly(chlorotrifluoroethylene), PCTFE: CFCl CF2
CH2 C
CH3 Poly(hexafluoropropylene): CF2 CF
Poly(4-methylpentene-1), PMP: CH2 CH CF3
CH2 Polyacrylics and Polyacetals
H3C CH Poly(methyl methacrylate), PMMA: CH3
CH3
CH2 C
Polynorbornene: COOCH3
CH CH
Poly(acrylic acid), PAA: H
Poly(1,4-butadiene), BR: CH2 CH CH CH2 CH2 C
COO-
Vinyl Polymers
Poly(oxymethylene), POM: CH2 O
Polystyrene, PS: CH2 CH
Polyamides
Polyamide 6, PA6: CO (CH2)5 NH
 Polymers 3.1 Structural Units of Polymers 481

Polyamide 66, PA66: Poly(ether imide), PEI:

NH (CH2)6 NH CO (CH2)4 CO O O
C C
Polyamide 11, PA11: CO (CH2)10 NH N CH3 N
C O C O C
Polyamide 12, PA12: CO (CH2)11 NH O CH3 O
Polyamide 610, PA610: O O
NH (CH2)6 NH CO (CH2)8 CO C C
Polyimide, PI: N N O
Polyamide 612, PA612: C C
NH (CH2)6 NH CO (CH2)10 CO O O
Poly(ether ether ketone), PEEK:
Polyesters
Polycarbonate, PC: CH3 C O O

Part 3 3.1
O C O C O
CH3 O
Poly(ethylene terephthalate), PET: Cellulose
C C O CH2 CH2 O OR
O O OR

Poly(butylene terephthalate), PBT: ROH2C O O

C C O CH2 4O Cellulose acetate, CA: R = COCH3
O O
Cellulose propionate, CP: R = COCH2 CH3
Poly(phenylene ether), PPE: CH3
Cellulose acetobutyrate, CAB: R = COCH3 and
O
R = COCH2 CH2 CH3
CH3 Ethyl cellulose, EC: R = CH2 CH3
Polysulfones and Polysulfides Polyurethanes
Polysulfone, PSU: Polyurethane, PUR, TPU:
CH3 O
CO NH (CH2)6 NH CO O (CH2)4 O
C O S O
CH3 O
Thermosets
Poly(phenylene sulfide), PPS: Phenol formaldehyde, PF: OH OH
S
CH2
Poly(ether sulfone), PES: O
S O
O Urea formaldehyde, UF: CH2 N
Polyimides and Polyether Ketones C O
Poly(amide imide), PAI: N CH2
O O H H O O Melamine formaldehyde, MF: H2C N CH2
C C N R N C C C
N N R N N
C C N C C N
O O N
482 Part 3 Classes of Materials

3.3.2 Abbreviations
The following abbreviations are used in this chapter. The THF tetrahydrofuran
abbreviations are in accordance with international rules. trans transverse
am amorphous
C chlorinated DSC differential scanning calorimetry
co copolymer DTA differential thermal analysis
cr crystalline
DOP dioctyl phthalate CFa carbon fiber content = a mass%, e.g.
HI high impact (modifier) PS-CF20 means polystyrene with 20%
iso isotactic carbon fiber
Part 3 3.2

long longitudinal GBa content of glass beads, spheres, or

LCP liquid crystal polymer balls = a mass%, e.g. PS-GB20 means
mu monomer unit polystyrene with 20% glass beads
pcr partially crystalline GFa glass fiber content = a mass%, e.g. PS-GF20
syn syndiotactic means polystyrene with 20% glass fiber
str strained MeFa metal fiber content = a mass%

Abbreviated notations for polymer names

ABS Poly(acrylonitrile-co-butadiene-co-styrene) PEI Poly(ether imide)
ASA Poly(acrylonitrile-co-styrene-co-acrylester) PES Poly(ether sulfone)
CA Cellulose acetate PET Poly(ethylene terephthalate)
CAB Cellulose acetobutyrate PF Phenol formaldehyde
COC Cycloolefine copolymer PI Polyimide
CP Cellulosepropionate PIB Poly(isobutylene)
DAP Diallylphthalat PMMA Poly(methyl methacrylate)
EAA Poly(ethylene-co-acrylic acid) PMP Poly(4-methylpenten-1)
EC Ethylcellulose POM Poly(oxymethylene)
ECTFE Poly(ethylene-co-chlorotrifluoroethylene) PP Polypropylene
EPDM Ethylene/propylene/diene-rubber PPE Poly(phenylene ether)
EIM Polyethylene ionomer PPS Poly(phenylene sulfide)
EP Epoxide; epoxy PTFE Poly(tetrafluoro ethylene)
ETFE Poly(ethylene-co-tetrafluoroethylene) PVC-P Poly(vinyl chloride), plastisized with DOP
EVA Poly(ethylene-co-vinylacetate) PVC-U Poly(vinyl chloride), unplastisized
FEP Poly(tetrafluoroethylene-co-hexafluoropropylene) PVK Poly(vinyl carbazole)
HDPE High density polyethylene PS Polystyrene
LDPE Low density polyethylene PSU Polysulfone
LLDPE Linear low density polyethylene PUR Polyurethane
MDPE Medium density polyethylene SAN Poly(styrene-co-acrylonitrile)
MF Melamine formaldehyde SB Poly(styrene-co-butadiene)
 Polymers 3.3 Tables and Figures 483

PA Polyamide SI Silicone resin

PAI Poly(amide imide) TPU Thermoplastic polyurethane elastomer
PB Polybutene-1 UF Urea formaldehyde
PBT Poly(butylene terephthalate) UHMWPE Ultra high molecular weight polyethylene
PC Polycarbonate UP Unsaturated polyester
PCTFE Poly(trifluorochloroethylene) VC/A Poly(vinyl chloride-co-acrylate)
PE Polyethylene VF Vulcanized fiber
PEEK Poly(ether ether ketone)

3.3.3 Tables and Figures
The following tables and diagrams contain physical
and physicochemical properties of common polymers,
copolymers, and polymer blends. The materials are ar-
ranged according to increasing number of functional
groups, i. e. polyolefines, vinyl polymers, fluoropoly-
mers, polyacrylics, polyacetals, polyamides, polyesters,
and polymers with special functional groups [3.216].
Part 3 3.3
3.3.3.1 Polyolefines
Polyethylene, HDPE, MDPE. Applications: injection
molding for domestic parts and industrial parts; blow
molding for containers and sports goods; extrusion
for pressure pipes, pipes, electrical insulating material,
bags, envelopes, and tissue.

Stress (MPa) Viscosity (Pa s)

30
B = fracture (break) point 23 C 200 C
103 240 C
40 C
B 60 C 280 C

20
B

B
10 102

0
0 2 4 6 8 10 12 100 101 102 103 104
Strain (%) Shear rate d/dt (s 1)
Fig. 3.3-2 Polyethylene, HDPE: stress versus strain Fig. 3.3-3 Polyethylene, HDPE: viscosity versus shear rate
484 Part 3 Classes of Materials

Table 3.3-1 Polyethylene: high-density, HDPE; medium-density, MDPE; low-density, LDPE; linear low-density, LLDPE;
ultrahigh-molecular-weight, UHMWPE
HDPE MDPE LDPE LLDPE UHMWPE
Melting temperature Tm ( C) 126135 120 125 105118 126 130 135
Enthalpy of fusion Hu (kJ/mol) (mu) 3.94.1 3.94.1
Entropy of fusion Su (J/(K mol)) (mu) 9.69.9 9.69.9
Heat capacity c p (kJ/(kg K)) 2.12.7 2.12.5 1.71.8
Temperature coefficient dc p / dT (kJ/(kg K2 ))
Enthalpy of combustion Hc (kJ/g) 46.4 46.5 46.5
Glass transition temperature Tg ( C) 110 110 110 110
Vicat softening temperature TV 50/50 ( C) 6080 4560 74
Thermal conductivity (W/(m K))
Part 3 3.3

0.380.51 0.320.40 0.41

Density  (g/cm3 ) 0.940.96 0.925 0.935 0.9150.92 0.935 0.93 0.94
Coefficient of thermal expansion 1418 18 23 2325 18 20 15 20
(105 /K) (linear) (296 328 K)
Compressibility (104 /MPa) (cubic) 2.2
Elastic modulus E (GPa) 0.61.4 0.40.8 0.20.4 0.30.7 0.70.8
Shear modulus G (GPa) 0.85 0.66 0.160.25
Poissons ratio
Stress at yield y (MPa) 1830 11 18 8 10 20 30 22
Stress at 50% strain 50 (MPa)
Strain at yield y (%) 812 10 15 20 15 15
Stress at fracture b (MPa) 1835 8 23
Strain at fracture b (%) 1001000 3001000
Impact strength (Charpy) (kJ/m2 ) 1325
Notched impact strength (Charpy) (kJ/m2 ) 3 5
Sound velocity vs (m/s) (longitudinal) 2430 2400
Sound velocity vs (m/s) (transverse) 950 1150
Shore hardness D 5863 45 60 4551 38 60 62
Volume resistivity e ( m) > 1015 > 1015 > 1015 > 1015 > 1015
Surface resistivity e () > 1014 > 1014 > 1014 > 1014 > 1014
Electric strength E B (kV/mm) 3040 30 40 3040 30 40 30 40
Relative permittivity r (100 Hz) 2.4 2.3 2.3 2.3 22.4
Dielectric loss tan (104 ) (100 Hz) 12 2 2 2.4 2 2
Refractive index n D (589 nm) 1.53 1.511.42
Temperature coefficient dn D / dT (104 /K)
Steam permeation (g/(m2 d)) 0.9 (40 m) 1 (100 m)
Gas permeation (cm3 /(m2 d bar)), 700 (N2 ) 700 (N2 )
23 C, 100 m 1800 (O2 ) 2000 (O2 )
10 000 (CO2 ) 10 000 (CO2 )
1100 (air) 1100 (air)
Melt viscositymolar-mass relation
Viscositymolar-mass relation [] = 62 103 M 0.70 (decalin, 135 C)
[] = 51 103 M 0.725 (tetralin, 130 C)
 Polymers 3.3 Tables and Figures 485

Table 3.3-2 Polyethylene, HDPE: heat capacity, thermal conductivity, and coefficient of thermal expansion

Temperature T ( C) 200 150 100 50 0 20 50 100 150

Heat capacity c p (kJ/(kg K)) 0.55 0.84 1.10 1.34 1.64 2.05 2.86
Thermal conductivity (W/(m K)) 0.62 0.56 0.50 0.44 0.38 0.32 0.25
Coefficient of thermal expansion 4.5 6.8 9.5 12.4 16.9 33.0 69.0
(105 /K) (linear)

Table 3.3-3 Polyethylene, LDPE: heat capacity and thermal conductivity

Temperature T ( C) 200 150 100 50 0 20 50 100 150

Heat capacity c p (kJ/(kg K)) 0.55 0.84 1.10 1.43 1.90 2.73
Thermal conductivity (W/(m K)) 0.36 0.38 0.38 0.35 0.31 0.24 0.25

Part 3 3.3
Creep modulus Etc (MPa) Shear modulus G (MPa)
0.5 MPa
800 1.0 MPa
1.5 MPa 10 3
2.0 MPa
2.5 MPa
3.0 MPa
600 4.0 MPa
5.0 MPa

10 2
400

200 10 1
10 0 10 1 10 2 10 3 10 4 100 50 0 50 100 150
Time t (h) Temperature T (C)

Fig. 3.3-4 Polyethylene, HDPE: creep modulus versus Fig. 3.3-5 Polyethylene, HDPE: shear modulus versus
time, at 23 C temperature

Stress (MPa) Viscosity (Pa s)

30 10 4
40 C 150 C
20 C 210 C
0 C 270 C
23 C 10 3
40 C
20

10 2

10
10 1

0 10 0 1
0 1 2 3 4 10 10 0 10 1 10 2 10 3 10 4 10 5
Strain (%) Shear rate d /dt (s1)
Fig. 3.3-6 Polyethylene, LDPE: stress versus strain Fig. 3.3-7 Polyethylene, LDPE: viscosity versus shear rate
 522 Part 3 Classes of Materials

References

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3.4 J. Brandrup, E. H. Immergut, E. A. Grulke (Eds.): 1996)
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Handbook (AIP, Woodbury 1996) 1978 1984)
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(Hanser, Munich 1987) J. I. Kroschwitz: Encyclopedia of Polymer Sci-
3.7 H. Saechtling: Kunststoff Taschenbuch (Hanser, ence and Engineering (Wiley, New York 1985
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Munich 1998) 1990)

3.8 W. Hellerich, G. Harsch, S. Haenle: Werkstoff-Fhrer 3.15 Werkstoff-Datenbank POLYMAT, Deutsches Kunst-
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1995) VDI-Wrmeatlas, 8th edn. (VDI, Dsseldorf 1997)