Physics of materials

Polymers
Gabriela Borcia

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023

 Physics of materials − Polymers

I. Generalities
II. Molecular interactions
III. Physical states and state transitions in polymers
IV. Physical properties of polymers

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023

 II.1. Primary and secondary bonds

chemical bonds / principal bonds / primary bonds

valence / valency 1−10 eV / bond 50−100 kcal/mol

molecules finite, stable, well defined

secondary bonds

condensed phases substances, materials

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 1

 II.1. Primary and secondary bonds
primary bonds

heteropolar (electrovalence): between ions with opposite charge

homopolar (covalence) : between neutral atoms

metallic : between neutral metallic atoms

polymers macromolecule

homopolar bonds 1−1.5 Å, ~ 102 kcal/mol

stability of individual macromolecules (chains)

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 2

 II.1. Primary and secondary bonds
cohesion between macromolecules due to secondary /
intermolecular bonds !
(?!)
interaction between groups of atoms / functional groups
PE x − (CH2−CH2)n − y CH2 groups

PP x − (CH−CH2)n − y CH, CH2 and CH3 groups


CH3

PA6 −NH−(CH2)5−CO− NH, CH2 and CO groups

intermolecular + intramolecular bonds

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 3
 II.1. Primary and secondary bonds

larger distance (“bond length”)

secondary bonds
weaker energy

addition effect ! structure

+ cohesion +
macromolecules properties of polymers
(important number of bonds)

van der Waals

secondary bonds
hydrogen bonds (H−bonds)

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 4

 II.1. Primary and secondary bonds

homopolar bonds 1−1.5 Å, ~ 102 kcal/mol

H−bonds 2−3 Å, ~ 101 kcal/mol
van der Waals 3−4 Å, ~ kcal/mol

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 5

 II.1. Primary and secondary bonds

Primary bonds Primary bonds Secondary bonds

Bond (Å) (kcal/mol) Bond (Å) (kcal/mol) Group (Å) (kcal/mol)
C−H 1.08 99 C…
−C 1.40 124 −CH3 3−4 1.78
N−H 1.01 93 C=C 1.35 146 −CH2− 3−4 1.78
O−H 0.96 111 C=N 1.30 147 =CH2 3−4 1.78
C−C 1.54 83 C=O 1.22 179 =CH− 3−4 0.99
C−N 1.47 73 C≡C 1.20 198 ≡CH 3−4 0.99
C−O 1.43 86 C≡N 1.16 213 −OH 2−4 7.25
C−Cl 1.76 81 =CO 2−4 4.27
C−Br 1.94 68 −NH2 2−4 3.53

binding energy ↔ dissociation energy

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 6

 II.1. Primary and secondary bonds

• number of double bonds

• chain length
increasing cohesion • chain symmetry
• degree of orientation of chains
• parallel chains?

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 7

 II.2. van der Waals bonds

3 × mechanisms

• orientation (dipole − dipole), Keesom

• induction (deformation) (dipole − induced dipole), Debye

• dispersion (“induced dipole − induced dipole”), London

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 8

 II.2. van der Waals bonds
Orientation (dipole − dipole)

polar molecules / permanent dipoles

electrostatic theory orientation as to ensure

minimum energy

p
   

E = − p. EL = − p ⋅ EL cos p, EL ( )  
θ
E E L

dipoles orient
(molecules rotate) minimum E ! 0º
aligned dipoles !
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 9
 II.2. van der Waals bonds
Orientation (dipole − dipole)

δ− δ+ δ− δ+
attraction

dipoles orient
(molecules rotate) minimum E ! 0º
aligned dipoles !

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 10

 II.2. van der Waals bonds
Orientation (dipole − dipole)

minimum E ! 0º aligned dipoles limited

degree of orientation
+ thermal agitation vs. T

p12 p22 1 p1 p2
Vo ∝ − 6 ⋅ << KT (low degree of orientation)
r KT r 3

0 ÷ 2 kcal / mol depends on dipole momentum + T

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 11

 II.2. van der Waals bonds
Induction (deformation) (dipole − induced dipole)

polar molecules / induced dipoles in neighboring molecules

permanent dipoles
induced dipoles oriented as to ensure minimum energy
  
E E E
L


−q  + q −q  +q pi = α EL
pi pi

 α11 α12 α13 

α depends on the direction of the interaction  
α jk =  α 21 α 22 α 23 
with respect to the molecule structure α 
 31 α 32 α 33 

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 12

 II.2. van der Waals bonds
Induction (deformation) (dipole − induced dipole)

  α p2
pi = α EL Vi ∝ − 6
0 ÷ 0.5 kcal / mol
r
depends on direction

δ− δ+ δ− δ+ δ− δ+


p Vo + Vi
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 13
 II.2. van der Waals bonds
Dispersion (“induced dipole − induced dipole”)
universal !
interaction between molecules completely lacking polarity

London → quantum mechanics

attraction forces resulting from reciprocal

influence (deformation)
of electronic distribution in atoms

tendency of molecules to have contact on as large surface as possible

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 14

 II.2. van der Waals bonds
Dispersion (“induced dipole − induced dipole”)

mechanism light dispersion

fluctuating dipoles created in atoms due to electrons movement

induced dipoles in neighboring molecules

+ − + − “induced dipole − induced dipole”

+ − + −
+ − + −
+ − + − α1 α 2
Vd ∝ −
temporary induced r6
fluctuating dipole dipole
0.2 ÷ 2 kcal / mol
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 15
 II.2. van der Waals bonds

3 × mechanisms

• orientation (dipole − dipole) 0 ÷ 2 kcal / mol

• induction (dipole − induced dipole) 0 ÷ 0.5 kcal / mol

• dispersion (“induced dipole − induced dipole”) 0.2 ÷ 2 kcal / mol

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 16

 II.3. H−bond
special bond ! H2O ! unique physical and chemical properties

X − HY X−H H Y
normal bond (stronger) hydrogen bond (weaker)

electronegativity > H ! C, N, O, F, Cl, I, S

(> 2.2)

• > 10 kcal/mol “strong”

energy • 3÷10 kcal/mol “medium”
• < 3 kcal/mol “weak”

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 17

 II.3. H−bond
specific angle−dependent ! H δ+
δ δ
association of molecules forced O H O
to adapt to specific spatial orientation δ+

H δ+ H δ+

specific bond angle + < distance between groups

intramolecular bonds

characteristic chain conformation

(helix)

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 18

 II.3. H−bond
specific angle−dependent !

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 19

 II.3. H−bond
specific bond angle + < distance between groups

• proteins
• sugars
• lignine
• gelatin
structure • starch
+ … • density
properties of molecules • molar volume
composing the living • solubility
• viscosity
• thermal conductivity
• acoustic conductivity
• magnetic susceptibility
• melting temperature
…
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 20
 II.3. H−bond
Examples
proteins O
−NH−CHR−CO−
N
N − HO
H
O

N
H

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 21

 II.3. H−bond
Examples

polyamides (PA)  − CO − NH − 
N − HO strong H−bond

 − CO − NH − (CH 2 )x − CO − NH − 

x↑ melting T ↓ ?

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 22

 II.3. H−bond
Examples

polyamides (PA)  − CO − NH − 

N − HO strong H−bond

fibers !

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 23

 II.3. H−bond
Examples

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 24

 II.4. Cohesive energy

V = Vo + Vi + Vd + VH A B
V = − 6 + 12
r r
A B
V =− m + n
r r r
typical
n ? n >10 6−12
potential B
repulsive +
r12
0 r
A B
V = − 6 + 12
r r
A
attractive −
r6

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 25

 II.4. Cohesive energy

molecules (→ gas) V measured directly

V=
heat of vaporization at constant volume

macromolecules (→ gas) T vaporization > T degradation

(decomposition)

V calculated
from studies of low-molecular-weight compounds

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 26

 II.4. Cohesive energy
V calculated
studies of low-molecular-weight compounds
differences between heats of vaporization
lead to numerical values for various molecular groups

group molar attraction constants − G values

G values are additive for a given structure !

calculated cohesive energy

(cohesive energy density) (CED)
(addition of G for all functional groups in a chain)
(mathematical model)
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 27
 II.4. Cohesive energy

G G
Group Group
(kcal/mol) (kcal/mol)
−CH3 1.78 −CF2− 1.80
=CH2 1.78 −CCl2− 3.10
-CH2− 0.99 −NH2 3.53
=CH− 0.99 −SH 4.25
≡CH3 0.99 =CO 4.27
−CH=CH− 1.70 −CHO 4.70
−CH(CH3)− 1.36 −NO2 7.20
−CH(C6H5)− 4.30 −COOCH3 5.60
−O− 1.63 −COOC2H5 6.23
−F 2.06 −OH 7.25
−Cl 3.40 −COOH 8.97
−Br 4.30 −CO−NH2 13.20
−I 5.04 −CO−NH− 16.20

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 28

 II.4. Cohesive energy
calculated cohesive energy
(cohesive energy density) (CED)
(addition of G for all functional groups in a chain)

V ↑ ∝M over a certain range

then, limitation

usually DP ≈ 600 ÷ 800

“huge” dimensions of macromolecules

very high cohesive energy

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 29

 II.4. Cohesive energy

cohesive energy mechanical properties !

(cohesive energy density)

• elastomers
criterion for polymer • plastomers (plastics)
materials classification
• fibers

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 30

 II.4. Cohesive energy

Polymer Structure unit CED (cal/cm3)

PE −CH2−CH2− 62
PIB −CH2−C(CH3)2− 65 elastomers
Polyisoprene −CH2−C(CH3)=CH−CH2− 67
PS −CH2−CH(C6H5)− 74
PMMA −CH2−C(CH3)(COOCH3)− 83
plastomers
PVAC −CH2−CH(OCOCH3)− 88
PVC −CH2−CHCl− 91
PET −(CH2)2−O−CO−C6H4−CO−O− 114
PA 66 −NH−(CH2)6−NH−CO−(CH2)4−CO− 185 fibers
PAN −CH2−CH(CN)− 237

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 31

 II.4. Cohesive energy
Polymer Structure unit CED (cal/cm3)
PE −CH2−CH2− 62
PIB −CH2−C(CH3)2− 65 elastomers
Polyisoprene −CH2−C(CH3)=CH−CH2− 67
PS −CH2−CH(C6H5)− 74
PMMA −CH2−C(CH3)(COOCH3)− 83
PVAC −CH2−CH(OCOCH3)− 88
PVC −CH2−CHCl− 91
PET −(CH2)2−O−CO−C6H4−CO−O− 114
PA 66 −NH−(CH2)6−NH−CO−(CH2)4−CO− 185
PAN −CH2−CH(CN)− 237

• lack of polar groups • weak intermolecular • “flexible” molecules

• “soft” groups − CH, CH2, CH3 forces • deformation

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 32

 II.4. Cohesive energy
Polymer Structure unit CED (cal/cm3)
PE −CH2−CH2− 62
PIB −CH2−C(CH3)2− 65
Polyisoprene −CH2−C(CH3)=CH−CH2− 67
PS −CH2−CH(C6H5)− 74
PMMA −CH2−C(CH3)(COOCH3)− 83
plastomers
PVAC −CH2−CH(OCOCH3)− 88
PVC −CH2−CHCl− 91
PET −(CH2)2−O−CO−C6H4−CO−O− 114
PA 66 −NH−(CH2)6−NH−CO−(CH2)4−CO− 185
PAN −CH2−CH(CN)− 237

• substitution of H atoms in the • higher cohesive • “rigid” molecules

PE chain with polar groups energy • stiffness, hardness

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 33

 II.4. Cohesive energy
Polymer Structure unit CED (cal/cm3)
PE −CH2−CH2− 62
PIB −CH2−C(CH3)2− 65
Polyisoprene −CH2−C(CH3)=CH−CH2− 67
PS −CH2−CH(C6H5)− 74
PMMA −CH2−C(CH3)(COOCH3)− 83
PVAC −CH2−CH(OCOCH3)− 88
PVC −CH2−CHCl− 91
PET −(CH2)2−O−CO−C6H4−CO−O− 114
PA 66 −NH−(CH2)6−NH−CO−(CH2)4−CO− 185 fibers
PAN −CH2−CH(CN)− 237

• high polarity groups

• very resistant to external mechanical stress
• distribution is important !
• superior mechanical properties
• (+ H−bonds)

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 34

 II.4. Cohesive energy
modification of interaction forces between chains

large range of ∆(cohesive energy) ↑ or ↓

• copolymerization → replacement (to a certain extent)
↑ of “soft” groups with polar groups

• copolymerization → adding in the chain structure units

↓ with different “dimensions”
→ perturbation of the regular structure

• substitution (to a certain extent) → ↓ number of

↓ of H atoms with other atoms or groups H−bonds

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 35

 II.4. Cohesive energy

Conclusion

• primary bonds
• secondary bonds
properties of polymers
• geometry of structure unit
• mobility of structure unit
“tunable” materials 

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 36