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

 Introduction

Polymers ? Macromolecular ?

MOLECULE H2C=CH2

macro − MOLECULE x − (CH2−CH2)n − y

n ???

chains “catene”

structural unit repeat unit

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

 Introduction

HCN H C N H−C ≡ N
Hydrogen cyanide
1 4 3
Hydrocyanic acid

Ethylene
Ethene H H
C2 H 4 CH C C
4 1 H H

chemical formula
chemical structure
spatial structure ?

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

 Introduction

chemical bond ↑↓

↑ + ↑ ↑↓

uncompensated spin e− e− pair

nb. uncompensated spin e− ≡ valence = nb. chemical bonds

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 3

 Introduction

E E
2p 2p
2s excitare 2s

6 C
1s 1s
2 ... 4!

6 C: 1s 2
2 s 2
2 p 2
→ 6 C*
: 1s 2
2 s1
2 p 3

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

 Introduction

single bonds σ

σ
π

multiple bonds
π
σ
π π
p p
…

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

 Introduction
σ “overlapping of atomic orbitals”

H2 H H

s s

σ
H F
HF
s p

σ
F F
F2
p p
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 6
 Introduction

http://iverson.cm.utexas.edu/courses/310M/POTD
Sp06/POTDLecture2.html

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

 Introduction
x
π

O σ O z

y p x1 px2

px1 π px2
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 8
 Introduction
π
x

O σ O z
+
y

p p π

single bonds multiple bonds

free rotation free rotation

↓ ↓
mobility, flexibility rigidity, stiffnes
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 9
 Introduction

x
π
px1 π px2
σ π
pz1 pz2
py1 π py2 N σ z
N

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

 Introduction

Hybridization

1 × s + 1 × p → 2 × sp
x
sp
1 × s + 2 × p → 3 × sp 2

x =1, 2, 3
1 × s + 3 × p → 4 × sp 3

x x y x
sp sp d sd
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 11
 Introduction
Hybridization

1× s x×p

( )
x + 1 ) ×
× sp
sp
xx

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

 Introduction
Hybridization

sp x

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 13

 Introduction
Hybridization
180° sp2

linear

sp sp
120°
sp3 sp2
sp2

109,5°
sp3 trigonal planar

sp3
sp3 tetrahedral

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

 Introduction

6 C: 1s 2
2 s 2
2 p 2
→ 6 C*
: 1s 2
2 s1
2 p 3

single bonds σ sp 3

σ
π sp 2

π
multiple bonds σ sp
π

p π p
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 15
 Introduction

4× σ 4 × sp 3

2× σ 3× σ
σ 3 × sp 2
1× π 1× π

1× σ 2× σ
π 2× σ 2 × sp
σ π
1× π 2× π
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 16
 Introduction

C6H6 120° !

3 × sp 2

sp2

120°
sp2
sp2

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 Introduction

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

CH2= C= CH −CH3
H
H

C C C
CH3
H

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

 Introduction

CH2= C= CH −CH3
2
sp H
H
sp3
C C C
CH3
H
sp
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 20
 Introduction
MOLECULE H2C=CH2

macro − MOLECULE x − (CH2−CH2)n − y

polyethylene − CH2−CH2 −

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

 Introduction

polyamide 6 −HN−(CH2)5−CO−

polyamide 6,6 −HN−(CH2)6−NH−CO−(CH2)4−CO−

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