477

Polymers
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 the case of copolymers, the physical properties are additionally inuenced by the type of arrangement of the monomers (statistical, random, alternating, periodic, block, or graft). Furthermore, the properties of polymers are inuenced if they are mixed with other polymers (polymer blends), with bers (glass bers, carbon bers, or metal bers), or with other llers (cellulose, inorganic materials, or organic materials). The tables and gures include the physical and physicochemical properties of those polymers, copolymers, and polymer blends which are widely used for scientic applications and in industry. The gures include mainly the following physical properties: stress versus strain, viscosity versus

3.3. Polymers

3.3.1 Structural Units of Polymers ................ 480 3.3.2 Abbreviations..................................... 482 3.3.3 Tables and Figures.............................. 3.3.3.1 Polyolenes............................ 3.3.3.2 Vinyl Polymers ........................ 3.3.3.3 Fluoropolymers ....................... 3.3.3.4 Polyacrylics and Polyacetals...... 3.3.3.5 Polyamides ............................ 3.3.3.6 Polyesters............................... 3.3.3.7 Polysulfones and Polysuldes ... 3.3.3.8 Polyimides and Polyether Ketones ............. 3.3.3.9 Cellulose ................................ 3.3.3.10 Polyurethanes ........................ 3.3.3.11 Thermosets............................. 3.3.3.12 Polymer Blends ....................... 483 483 489 492 497 501 503 506 508 509 511 512 515

Part 3 3

References .................................................. 522

shear rate, and creep modulus versus time. However, other physical properties are also included. Additionally, the most relevant applications of the materials are given.

The tables and gures include the physical and physicochemical properties of the most important polymers, copolymers, and polymer blends. Most important here means that these materials are widely used for scientic 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 parentheses. The tables and gures 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 aming 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

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Thermal conductivity : dq/ dt = A dT/ dx; dq/ dt = heat ux, A = area, dT/ dx = temperature gradient. Density = m/V (ISO 1183). Coefcient 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). 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 coefcient 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 of some physical properties is given. Additionally, the most relevant applications of the materials are given. The tables and gures include the physical properties given in the table below (see [3.13]). As the physical and physicochemical properties of each polymer vary with its molecular architecture, the tables show the ranges of the physical and physicochemical properties, whereas the diagrams show the functional relationships for a typical species of the polymer, copolymer, or polymer blend. The table on page 479 shows the selected 77 polymers, copolymers and polymer blends.
Stress b y 50

Part 3 3

50% Strain

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 Polyolenes Polyolenes I Polyethylene: high density HDPE, medium density MDPE, low density LDPE, linear low density LLDPE, ultra high molecular weight UHMWPE Polyolenes II Poly(ethylene-co-vinylacetate) EVA, Polyethylene ionomer EIM, Cycloolene copolymer COC [Poly(ethylene-conorbornene)], Poly(ethylene-co-acrylic acid) EAA Polyolenes 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 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 Polytetrauoroethylene PTFE, Polychlorotriuoroethylene PCTFE, Poly(tetrauoroethylene-co-hexauoropro- pylene) FEP, Poly(ethylene-co-tetrauoroethylene) ETFE, Poly(ethylene-co-chlorotriuoroethylene), 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, Polysuldes Polysulfon PSU, Poly(phenylene sulde) 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 ber 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(acrylonitrileco-butadiene-co-acrylester) + Polycarbonate ASA + PC

Part 3 3

480

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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, Polycarbonate + 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 polyolenes, vinyl polymers, uoropolymers, polyacrylics, polyacetals, polyamides, polyesters, polysulfones, polysuldes, polyimides, polyether ketones, cellulose, polyurethanes, and thermosets. The structural units of the polymers are as follows:
Polyolenes Polyethylene, PE:

Poly(acrylonitrile), PAN: Poly(vinyl acetate), PVAC:

CH2 CH CN CH2 CH O CO CH3 CH2 CH Cl CH2 CH N

Poly(vinyl chloride), PVC:

CH2 CH2 CH2 CH CH3 CH2 CH CH2 CH3 CH3 CH2 C CH3 CH2 CH CH2 H3C CH CH3 CH CH
Poly(vinyl carbazole), PVK:

Polypropylene, PP: Poly(butene-1), PB:

Poly(isobutylene), PIB:

Fluoropolymers Poly(tetrauoroethylene), PTFE:

CF2 CF2 CFCl CF2 CF2 CF CF3 CH3 CH2 C COOCH3 H CH2 C COOCH2 O CO (CH2)5 NH

Poly(chlorotriuoroethylene), PCTFE: Poly(hexauoropropylene):

Polyacrylics and Polyacetals Poly(methyl methacrylate), PMMA:

Poly(4-methylpentene-1), PMP:

Polynorbornene: Poly(1,4-butadiene), BR:

Vinyl Polymers Polystyrene, PS:

Poly(acrylic acid), PAA:

CH2 CH CH CH2
Poly(oxymethylene), POM:
Polyamides Polyamide 6, PA6:

CH2 CH

Polymers

3.1 Structural Units of Polymers

481

Polyamide 66, PA66:

Poly(ether imide), PEI:

O C N C O O

NH (CH2)6 NH CO (CH2)4 CO
Polyamide 11, PA11: Polyamide 12, PA12: Polyamide 610, PA610:

CO (CH2)10 NH CO (CH2)11 NH

CH3 C CH3

O C N C O

NH (CH2)6 NH CO (CH2)8 CO
Polyamide 612, PA612: Polyimide, PI:

NH (CH2)6 NH CO (CH2)10 CO
Polyesters Polycarbonate, PC:

O C N C O

O C N C O

Poly(ether ether ketone), PEEK:

O
Poly(ethylene terephthalate), PET:

CH3 C CH3

O C O
Cellulose

C O

O Part 3 3.1

C O

C O CH2 CH2 O O ROH2C C O CH2 4O O CH3 O CH3

OR OR O O
R = COCH3 R = COCH2 CH3

Poly(butylene terephthalate), PBT:

C O
Poly(phenylene ether), PPE:

Cellulose acetate, CA: Cellulose propionate, CP:

Cellulose acetobutyrate, CAB: R = COCH3 and R = COCH2 CH2 CH3 Ethyl cellulose, EC:
Polyurethanes Polyurethane, PUR, TPU:

R = CH2 CH3

Polysulfones and Polysuldes Polysulfone, PSU:

CH3 C CH3

O S O

CO NH (CH2)6 NH CO O (CH2)4 O
Thermosets Phenol formaldehyde, PF:

Poly(phenylene sulde), PPS: Poly(ether sulfone), PES:

S O S O O

OH CH2

OH

Urea formaldehyde, UF:

Polyimides and Polyether Ketones Poly(amide imide), PAI:

CH2 N C O N CH2 H2C N CH2 C N N N C C N N

O C N C O

O H H O C N R N C

O C N R C O

Melamine formaldehyde, MF:

482

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3.3.2 Abbreviations
The following abbreviations are used in this chapter. The abbreviations are in accordance with international rules. am C co cr DOP HI iso long LCP mu pcr syn str amorphous chlorinated copolymer crystalline dioctyl phthalate high impact (modier) isotactic longitudinal liquid crystal polymer monomer unit partially crystalline syndiotactic strained MeFa GFa GBa CFa carbon ber content = a mass%, e.g. PS-CF20 means polystyrene with 20% carbon ber content of glass beads, spheres, or balls = a mass%, e.g. PS-GB20 means polystyrene with 20% glass beads glass ber content = a mass%, e.g. PS-GF20 means polystyrene with 20% glass ber metal ber content = a mass% DSC DTA differential scanning calorimetry differential thermal analysis THF trans tetrahydrofuran transverse

Part 3 3.2

Abbreviated notations for polymer names ABS Poly(acrylonitrile-co-butadiene-co-styrene) ASA Poly(acrylonitrile-co-styrene-co-acrylester) CA Cellulose acetate CAB Cellulose acetobutyrate COC Cycloolene copolymer CP Cellulosepropionate DAP Diallylphthalat EAA Poly(ethylene-co-acrylic acid) EC Ethylcellulose ECTFE Poly(ethylene-co-chlorotriuoroethylene) EPDM Ethylene/propylene/diene-rubber EIM Polyethylene ionomer EP Epoxide; epoxy ETFE Poly(ethylene-co-tetrauoroethylene) EVA Poly(ethylene-co-vinylacetate) FEP Poly(tetrauoroethylene-co-hexauoropropylene) HDPE High density polyethylene LDPE Low density polyethylene LLDPE Linear low density polyethylene MDPE Medium density polyethylene MF Melamine formaldehyde

PEI PES PET PF PI PIB PMMA PMP POM PP PPE PPS PTFE PVC-P PVC-U PVK PS PSU PUR SAN SB

Poly(ether imide) Poly(ether sulfone) Poly(ethylene terephthalate) Phenol formaldehyde Polyimide Poly(isobutylene) Poly(methyl methacrylate) Poly(4-methylpenten-1) Poly(oxymethylene) Polypropylene Poly(phenylene ether) Poly(phenylene sulde) Poly(tetrauoro ethylene) Poly(vinyl chloride), plastisized with DOP Poly(vinyl chloride), unplastisized Poly(vinyl carbazole) Polystyrene Polysulfone Polyurethane Poly(styrene-co-acrylonitrile) Poly(styrene-co-butadiene)

Polymers

3.3 Tables and Figures

483

PA PAI PB PBT PC PCTFE PE PEEK

Polyamide Poly(amide imide) Polybutene-1 Poly(butylene terephthalate) Polycarbonate Poly(triuorochloroethylene) Polyethylene Poly(ether ether ketone)

SI TPU UF UHMWPE UP VC/A VF

Silicone resin Thermoplastic polyurethane elastomer Urea formaldehyde Ultra high molecular weight polyethylene Unsaturated polyester Poly(vinyl chloride-co-acrylate) Vulcanized ber

Part 3 3.3

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 arranged according to increasing number of functional groups, i. e. polyolenes, vinyl polymers, uoropolymers, polyacrylics, polyacetals, polyamides, polyesters, and polymers with special functional groups [3.216].
Stress (MPa) 30
B = fracture (break) point B 20 B B 102 23 C 40 C 60 C 10

3.3.3.1 Polyolenes
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.
Viscosity (Pa s)
3

200 C 240 C 280 C

10

10 12 Strain (%)

100

101

102

103 104 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

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Table 3.3-1 Polyethylene: high-density, HDPE; medium-density, MDPE; low-density, LDPE; linear low-density, LLDPE; ultrahigh-molecular-weight, UHMWPE
HDPE Melting temperature Tm ( C) Enthalpy of fusion Hu (kJ/mol) (mu) Entropy of fusion Su (J/(K mol)) (mu) Heat capacity c p (kJ/(kg K)) Temperature coefcient dc p / dT (kJ/(kg K2 )) Enthalpy of combustion Hc (kJ/g) Glass transition temperature Tg ( C) Vicat softening temperature TV 50/50 ( C) Thermal conductivity (W/(m K)) Density (g/cm3 ) Coefcient of thermal expansion (105 /K) (linear) (296 328 K) Compressibility (104 /MPa) (cubic) Elastic modulus E (GPa) Shear modulus G (GPa) Poissons ratio Stress at yield y (MPa) Stress at 50% strain 50 (MPa) Strain at yield y (%) Stress at fracture b (MPa) Strain at fracture b (%) Impact strength (Charpy) (kJ/m2 ) 2430 950 5863 > 1015 > 1015 > 1014 3040 2.4 12 1.53 0.9 (40 m) 700 (N2 ) 1800 (O2 ) 10 000 (CO2 ) 1100 (air) 45 60 > 1015 > 1014 30 40 2.3 2 Notched impact strength (Charpy) (kJ/m2 ) Sound velocity vs (m/s) (longitudinal) Sound velocity vs (m/s) (transverse) Shore hardness D Volume resistivity e ( m) Surface resistivity e () Electric strength E B (kV/mm) Relative permittivity r (100 Hz) Dielectric loss tan (104 ) (100 Hz) Refractive index n D (589 nm) Temperature coefcient dn D / dT (104 /K) Steam permeation (g/(m2 d)) Gas permeation (cm3 /(m2 d bar)), 23 C, 100 m 812 1835 1001000 10 15 20 8 23 3001000 1325 3 5 2400 1150 4551 > 1015 > 1014 3040 2.3 2 2.4 1.511.42 1 (100 m) 700 (N2 ) 2000 (O2 ) 10 000 (CO2 ) 1100 (air) 38 60 > 1015 > 1014 30 40 2.3 2 > 1014 30 40 22.4 2 62 15 15 1830 11 18 8 10 20 30 22 0.61.4 0.85 0.40.8 0.66 126135 3.94.1 9.69.9 2.12.7 46.4 110 6080 0.380.51 0.940.96 1418 0.925 0.935 18 23 46.5 110 4560 0.320.40 0.9150.92 2325 2.2 0.20.4 0.160.25 0.30.7 0.70.8 0.935 18 20 MDPE 120 125 LDPE 105118 3.94.1 9.69.9 2.12.5 46.5 110 110 74 0.41 0.93 0.94 15 20 1.71.8 LLDPE 126 UHMWPE 130 135

Part 3 3.3

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 coefcient of thermal expansion
Temperature T ( C) Heat capacity c p (kJ/(kg K)) Thermal conductivity (W/(m K)) Coefcient of thermal expansion (105 /K) (linear) 4.5 200 0.55 150 0.84 0.62 6.8 100 1.10 0.56 9.5 50 1.34 0.50 12.4 0 1.64 0.44 16.9 20 50 2.05 0.38 33.0 100 2.86 0.32 69.0 0.25 150

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

Temperature T ( C) Heat capacity c p (kJ/(kg K)) Thermal conductivity (W/(m K)) 200 0.55 150 0.84 0.36 100 1.10 0.38 50 1.43 0.38 0 1.90 0.35 20 50 2.73 0.31 0.24 0.25 100 150

Part 3 3.3

Creep modulus Etc (MPa)

800 0.5 MPa 1.0 MPa 1.5 MPa 2.0 MPa 2.5 MPa 3.0 MPa 4.0 MPa 5.0 MPa

Shear modulus G (MPa)

10 3

600

10 2 400

200 10 0

10 1

10 2

10 3

10 4 Time t (h)

10 1 100

50

50

100 150 Temperature T (C)

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

Stress (MPa)
40 C 20 C 0 C 23 C 40 C

Fig. 3.3-5 Polyethylene, HDPE: shear modulus versus

temperature
Viscosity (Pa s) 10 4
150 C 210 C 270 C

30

10 3

20

10 2 10 10 1

4 Strain (%)

10 0 1 10

10 0

10 1

10 2

10 3 10 4 10 5 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

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References
3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 M. D. Lechner, K. Gehrke, E. H. Nordmeier: Makromolekulare Chemie (Birkhuser, Basel 2003) G. W. Becker, D. Braun (Eds.): Kunststoff Handbuch (Hanser, Munich 1969 1990) Kunststoffdatenbank CAMPUS, M-Base, Aachen (www.m-base.de) J. Brandrup, E. H. Immergut, E. A. Grulke (Eds.): Polymer Handbook (Wiley, New York 1999) J. E. Mark (Ed.): Physical Properties of Polymers Handbook (AIP, Woodbury 1996) C. C. Ku, R. Liepins: Electrical Properties of Polymers (Hanser, Munich 1987) H. Saechtling: Kunststoff Taschenbuch (Hanser, Munich 1998) W. Hellerich, G. Harsch, S. Haenle: Werkstoff-Fhrer Kunststoffe (Hanser, Munich 1996) B. Carlowitz: Kunststoff Tabellen (Hanser, Munich 1995) 3.10 3.11 3.12 G. Allen, J. C. Bevington (Eds.): Comprehensive Polymer Science (Pergamon, Oxford 1989) H. Domininghaus: Die Kunststoffe und ihre Eigenschaften (VDI, Dsseldorf 1992) H. J. Arpe (Ed.): Ullmanns Encyclopedia of Industrial Chemistry, 5th edn. (VCH, Weinheim 1985 1996) R. E. Kirk, D. F. Othmer (Eds.): Encyclopedia of Chemical Technology, 4th edn. (Wiley, New York 1978 1984) H. F. Mark, N. Bikales, C. G. Overberger, G. Menges, J. I. Kroschwitz: Encyclopedia of Polymer Science and Engineering (Wiley, New York 1985 1990) Werkstoff-Datenbank POLYMAT, Deutsches Kunststoff-Institut, Darmstadt M. Neubronner: Stoffwerte von Kunststoffen. In: VDI-Wrmeatlas, 8th edn. (VDI, Dsseldorf 1997)

3.13

3.14

Part 3 3

3.15 3.16

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