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

 I.1. Macromolecular − Definition

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

 I.1. Macromolecular − Definition
MOLECULE H2C=CH2

macro − MOLECULE x − (CH2−CH2)n − y

polyethylene − CH2−CH2 −

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

 I.1. Macromolecular − Definition

polyamide 6 −HN−(CH2)5−CO−

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

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

 I.1. Macromolecular − Definition
chains “catene”

structural unit repeat unit

precursors monomer(s)

≡ monomer(s)
repeat unit
≈ similar

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

 I.1. Macromolecular − Definition

repeat polymerization
unit
addition polymerization
≡ chain-growth polymerization
monomer(s) chain polymerization

repeat
step-growth polymerization
unit
polycondensation polymerization
≈ polycondensation
similar

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

 I.1. Macromolecular − Definition
chain polymerization

PE polyethylene H2C=CH2 − CH2−CH2 −

PS polystyrene (C6H5)CH=CH2

−(C6H5)CH−CH2−

PEO poly(ethylene oxide)

−O−CH2−CH2−
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 6
 I.1. Macromolecular − Definition
polycondensation

PA 66 polyamide 66

H2N−(CH2)6−NH2
+ −HN−(CH2)6−NH−CO−(CH2)4−CO−
HOOC−(CH2)4−COOH (H, H, OH, OH)

2 × H 2O

polyamide 66 −HN−(CH2)6−NH−CO−(CH2)4−CO−

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

 I.1. Macromolecular − Definition

degree of polymerization

number of structural units in a chain (macromolecule)

DP
M ratio
DP = molecular mass of the (macro)molecule /
m molecular mass of structural unit

average values !
homologuous series
macromolecular
homologuous polymers

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

 I.1. Macromolecular − Definition

macromolecular homologuous series

homologuous polymers

x − (CH2−CH2)n − y
x − (CH2−CH2)m − y homologuous series
x − (CH2−CH2)p − y x, y − end-groups
…

low DP ⇒ oligomers n = 2, 3, 4 ...

macromolecular domain limit ? (lower limit)

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 9

 I.1. Macromolecular − Definition

small molecules macromolecular DP ?

usually ?! DP >100 physical properties !

fibers
mechanical properties ! elastomers
plastomers

DP ↑ continuous modification of the properties

upper limit ! M ~ 10 ÷ 10 u ( Da )
5 7

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

 I.1. Macromolecular − Definition

Melting temperature Tm vs. DP

for the homologuous series of ethane

units Compound
M Tm (°C)
−CH2−CH2− at 25°C
1 30 -169 gas
6 170 -12 liquid
35 1000 37 grease
140 4000 93 paste
430 12000 104 hard resin
750 21000 110 "
1350 38000 112 "

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

 I.1. Macromolecular − Definition
units Compound
M Tm (°C)
−CH2−CH2− at 25°C
1 30 -169 gas
6 170 -12 liquid
35 1000 37 grease
140 4000 93 paste
430 12000 104 hard resin
750 21000 110 "
1350 38000 112 "

DP ~ 450 − 500
DP high ! ↔ low cohesion energy

DP ? ∆(various properties) vs. T

chemical + chain structure !
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 12
 I.2. Molecular mass of polymers

simple chemical substances • melting temperature − melting point

• boiling temperature − boiling point
• refraction index
precise characteristics etc.

rigurously constant molecular mass !

⇒ identification, individualization of substances

mixture of chains
Polymers ?
different DP + strong ∆ of structure

properties ↔ range of variation

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

 I.2. Molecular mass of polymers

Main
• average molecular mass M
information
• molecular mass distribution nb. chains ( M )

4 × M !!! depending on
experimental method + mathematical formula

general equation  Mβ =
∑i i
c M β

∑i i
c M β -1

(weight fraction)
(mass concentration)
∑ ci =1 or ∑ ci =100%
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 14
 I.2. Molecular mass of polymers

4 × M !!! (weighted average mass)

number average molecular weight

Mn NAMW number average molecular mass

weight average molecular weight

Mw WAMW weight average molecular mass

Z−average molecular weight

Mz “Zentrifuge” (in german) (centrifuge)

Mv viscozity average molecular weight

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

 I.2. Molecular mass of polymers

Mβ =
∑i i
c M β

∑i i
c M β -1

β=0 Mn =
∑ ci DP n =
Mn ∑ ci
NAMW
∑ ci / Mi m ∑ ci / DPi

WAMW β =1 Mw =
∑ ci Mi
DP w =
Mw
=
∑ ci DPi
∑ ci m ∑ ci

β=2 Mz β 0.8 ÷ 1
= Mv

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

 I.2. Molecular mass of polymers
Methods used to measure the molecular mass

end-groups counting Mn β =0

osmotic pressure Mn β =0

light diffusion Mw β =1

sedimentation rate in ultracentrifuges Mz β =2

viscometry (
Mv ≈ M w ) β 0.8 ÷ 1
=

chromatography …
Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 17
 I.2. Molecular mass of polymers
homogeneous system Mn = M v = M w = M z
heterogeneous system Mn < M v < M w < M z

polymolecularity / polydispersity

polydispersity index

Mw
PDI = PDI =1 ÷ 2
Mn
https://www.open.edu/openlearn/ocw/mod/oucontent/view.
php?id=3484&extra=thumbnailfigure_idm46528710014080

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

 I.3. Nomenclature of polymers
Science Matters: The Case of Plastics
“The first synthetic polymer was invented in 1869 by John Wesley Hyatt, who was
inspired by a New York firm’s offer of $10,000 for anyone who could provide a
substitute for ivory.
By treating cellulose, derived from cotton fiber, with camphor, Hyatt discovered
a plastic that could be crafted into a variety of shapes and made to imitate
natural substances like tortoiseshell, horn, linen, and ivory.”
https://www.sciencehistory.org/
the-history-and-future-of-plastics#:

keratin

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

 I.3. Nomenclature of polymers
Science Matters: The Case of Plastics
“The first synthetic polymer was invented in 1869 by John Wesley Hyatt, who was
inspired by a New York firm’s offer of $10,000 for anyone who could provide a
substitute for ivory.
By treating cellulose, derived from cotton fiber, with camphor, Hyatt discovered
a plastic that could be crafted into a variety of shapes and made to imitate
natural substances like tortoiseshell, horn, linen, and ivory.”
https://www.sciencehistory.org/
the-history-and-future-of-plastics#:

February 28, 1935

The first example of nylon (nylon 6,6) was produced
on February 28, 1935, at DuPont's research facility at
the DuPont Experimental Station.

Nylon ≡ polyamide

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 20

 I.3. Nomenclature of polymers
huge variety of synthetic polymers general principle ?!
ACS (American Chemical Society)
IUPAC (International Union of Pure and Applied Chemistry)
Committee on Terminology, Nomenclature and Symbols
1952
POLY

source-based nomenclature criticized !

poly(monomer(s)) PEO × 4 −O−CH2−CH2−

structure-based nomenclature
poly(repeat unit/structure unit)

Physics of materials − Polymers (G. Borcia) − 2nd semester, 2022/2023 21
 I.3. Nomenclature of polymers

structure-based nomenclature
poly(repeat unit/structure unit)


+ additional rules

??? (PEO ?)

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

 I.3. Nomenclature of polymers

???

“poli(oxi−1−fluoretilenă)”
fluorinated poly(ethylene oxide)
oxidated poly(vinyl fluoride)

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

 I.3. Nomenclature of polymers
copolymers “co” poly(butadiene−co−styrene)
block copolymers poly(butadiene−b−styrene)
graft copolymers poly(chloroprene−g−styrene)
alternating copolymers poly(………………−alt−………….)
statistical copolymers poly(………………−stat−………….)

isomers “cis−”, “trans−”

isotactic
tacticity syndiotactic
atactic

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

 I.3. Nomenclature of polymers

commercial names ?! commercial ↔ scientific

Nylon → PA

Teflon → PTFE

Kevlar → Aramid fibers (aromatic PAs)

“cut resistant gloves”

Kapton → Polyimide (thermal

insulation)

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

 I.3. Nomenclature of polymers
Polymer Acronym Polymer Acronym
polyethylene PE polyvinyl chloride PVC
polypropylene PP polystyrene PS
polyethylene terephthalate PET polybutadiene PB
poly(methyl methacrylate) PMMA polyvinyl acohol PVA
polytetrafluorethylene PTFE polyacrylonitrile PAN
polyethylene oxide PEO polyamide 6 PA 6

PET

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