Topic IV: Structural Characterization and Identification of Polymers

IV.1. Thermoanalytic methods

- Differential thermal analysis (DTA) & differential scanning calorimetry (DSC) - Thermogravimetric analysis (TGA) - Thermomechanical analysis (TMA)

IV.2. Spectroscopic methods

- IR Spectroscopy IV.3. Microscopic methods - Optical/light Microscopy - Scanning Electron Microscopy IV.4. Diffraction methods - X-Ray Diffraction

Topic IV.1 & 2

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Thermoanalytic Methods

Differential Thermal Analysis (DTA) & Differential Scanning Calorimetry (DSC) Methods based on measurement of heat consumed (endo) up or released (exo) to the surrounding per unit time during isothermal (hold), heating or cooling processes.

Thermogravimetric Analysis (TGA) Measurement of changes of polymer weight as a function of temperature.

Thermomechanical Analysis (TMA) Measurement of dimensional changes during heating or cooling

Topic IV.1 & 2

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Thermoanalytic Methods - DTA Differential Thermal Analysis (DTA)

Sample (~10mg) pan and reference pan are placed in an oven. The oven is usually heated or cooled at a rate ranging from 0.1 to 100 K/min. Temperature difference (T) between sample and reference pan measured and recorded.
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Topic IV.1 & 2

Thermoanalytic Methods - DSC Differential Scanning Calorimetry (DSC)

Sample (~10mg) pan and reference pan are placed in two thermally isolated ovens. The oven is usually heated or cooled at a rate ranging from 0.1 to 1000 K/min. Temperature difference between the sample and the reference pan are energetically compensated to maintain T=0 Supplied energy (power) is measured and recorded.
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Topic IV.1 & 2

Thermoanalytic Methods DTA/DSC Calibration of Temperature and Heat Flux

Indium
exo 5 exo 5

Zinc
Indium Zinc
0

heat flux [W/g]

-5

heat flux [W/g]

TM = 419.6 C
-5

-10

TM = 156.6 C
H100% = 28.45 J/g

-10 endo

-15 endo

-20 130 140 150 160 170 180

-15 380

400

420

440

460

temperature [C]
Topic IV.1 & 2

temperature [C]
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Thermoanalytic Methods DTA/DSC Application of DTA/DSC

Thermal transitions (e.g., glass transition, phase transitions) Melting behavior, -temperature, -enthalpy; specific heat Crystallization behavior; recrystallization Degree of crystallinity Annealing and curing processes; thermal stability Desorption, evaporation, decomposition Efficiency of additives Chemical reaction enthalpy, reaction temperature, reaction kinetics

Topic IV.1 & 2

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Thermoanalytic Methods DTA/DSC Amorphous Polymers Glass Transition

Polycarbonate (PC)
1

PC film 50m

heat flux [W/g]

exo

glass transition

TG = 150C
endo
0

50

100

150

200

temperature [C]
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Amorphous Polymers Glass Transition

ABS/PC blend
exo -6 -7

ABS/PC blend

heat flux [W/g]

-8 -9 -10
ABS PC glass transition

endo

-11 50 100 150

temperature [C]
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Amorphous Polymers Glass Transition

Topic IV.1 & 2

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Thermoanalytic Methods DTA/DSC

Amorphous thermoplastics Polyvinylchloride (PVC) Polystyrene (PS) Polymethylmethacrylate (PMMA) Polycarbonate (PC) Polysulfone (PSU) Polyethersulfone (PES) Polyetherimide (PEI) Glass transition temperature [C] 80 95 105 150 190 230 220

Engineering and high temperature-resistant, amorphous polymers (PC, PSU, PES, PEI, etc.) contain aromatic rings, giving the macromolecule main chain a 2-dimensional (ladder-like) structure.

Athas Databank: http:web.utk.edu/~athas/databank/

Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Semicrystalline Polymers Melting Behaviour

PE-HD
0.0 exo

PE-HD
-0.5

heat flux [W/g]

endo

-1.0 -1.5 -2.0 -2.5 60 80

TM = 135C
100 120 140 160

temperature [C]
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Semicrystalline Polymers Melting Behaviour

PE-HD and PE-LD
0.0 exo -0.5

heat flux [W/g]

-1.0 -1.5 -2.0

PE-HD PE-LD
X

TM = 115C

endo

-2.5 60 80

TM = 135C X
100 120 140 160

temperature [C]
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Semicrystalline Polymers Melting Behaviour

PE-LD / PP blend
-0.3 exo -0.4 -0.5

heat flux [W/g]

-0.6 -0.7 -0.8 -0.9

TM = 115C

endo

-1.0 -1.1 40

PE-LD/PP Blend
60 80 100

TM = 165C X
120 140 160 180 200

temperature [C]
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Semicrystalline Polymers Melting Behaviour

w/o enthalpy relaxation

Blend

with enthalpy relaxation

Topic IV.1 & 2

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Thermoanalytic methods DTA/DSC Semicrystalline Polymers Degree of Crystallinity

PE-HD
0.0 exo

PE-HD
-0.5

heat flux [W/g]

-1.0 -1.5 -2.0

Melting Enthalpy (H) = 188 J/g

endo

-2.5 60 80

TM = 135C X
100 120 140 160

temperature [C]
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Semicrystalline Polymers Degree of Crystallinity

= H / H100%cr
... Degree of crystallinity H ... Measured melting enthalpy H100%cr ... Melting enthalpy for 100% crystalline material

Example PE-HD:

= 188/294 = 64%
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC

Semicrystalline polymer Polyethylene (PE) Polypropylene (PP) Polyoxymethylene (POM) Polyamide 6,6 (PA66) Polyethyleneterephthalate (PET) Polyether ether ketone (PEEK) Poly(vinylidene fluoride) (PVDF) Polytetrafluoroethylene (PTFE) Melting temperature [C] 80 150 165 180 260 270 350 175 325 Melting enthalpy for 100% crystallinity [J/g] 294 207 326 270 153 130 105 41

Athas Data bank: http:web.utk.edu/~athas/databank/ http://athas.prz.rzeszow.pl/databank/welcome-db.html

Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Semicrystalline Polymers Melting vs. Crystallization

PTFE
exo 6 4

TCr = 310 C

PTFE

heat flux [W/g]

2 0 -2

cooling, -10 K/min

heating, 10 K/min

endo

-4 -6 200

TM = 327C
220 240 260 280 300 320 340 360

temperature [C]
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Semicrystalline Polymers Postcrystallization

PET
exo 5 0 -5

TPostCr = 150 C

quenched PET

heat flux [W/g]

TG = 75 C
-10 -15 -20 50 100 150 200

endo

TM = 250 C
250 300

temperature [C]
Topic IV.1 & 2
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Thermoanalytic Methods DTA/DSC Degradation / Oxidation of Polymers - PP

exo

PP film unaged weathered

2 0

heat flux [W/g]

weathering

endo

TOx = 220 C

50

100

150

200

250

temperature [C]

Topic IV.1 & 2

Polyolefines exhibit autooxidation. Oxidation temperature (TOx) is affected by stabilization and ageing.
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Thermoanalytic Methods DTA/DSC Epoxy Resin - Relationship Between Degree of Cure & Glass Transition Temperature
glass transition temperature TgDSC, C
220 200 180 160 140 120 100 80

epoxy resin
60 70 75 80 85 90 95 100

degree of cure DSC, %

Topic IV.1 & 2
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21

Thermoanalytic Methods - TGA Thermogravimetrical Analysis (TGA)

Sample (~10 mg) and crucible, connected to a microbalance, are placed in an oven. The oven is usually heated or cooled at a rate ranging between 0.1 and 100 K/min. The change of weight (m) is measured as a function of temperature.

Topic IV.1 & 2

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Thermoanalytic Methods - TGA Thermogravimetrical analysis (TGA)

100

< 2 wt% water content

Relative mass [%]

95

< 10 wt% phenol resin coating

90

Phenol resin coated mineral wool

85 0 100 200 300 400 500

temperature [C]

Topic IV.1 & 2

Determination of volatile components (e.g., water, solvents, etc.) Determination of mineral filler or reinforcement content of plastics.
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Topic IV: Structural Characterization and Identification of Polymers

IV.1. Thermoanalytic methods
- Differential thermal analysis (DTA) & differential scanning calorimetry (DSC) - Thermogravimetric analysis (TGA) - Thermomechanical analysis (TMA)

IV.2. Spectroscopic methods

- IR Spectroscopy IV.3. Microscopic methods - Optical/light Microscopy - Scanning Electron Microscopy - Atomic force Microscopy IV.4. Diffraction methods - X-Ray Diffraction

Topic IV.1 & 2

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24

Spectroscopy

Spectroscopic methods play an important role in structural analysis of polymers. Spectroscopic phenomena are associated with the absorption or emission of
electromagnetic radiation.

: wavelength
Topic IV.1 & 2
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25

IR - Spectroscopy Infrared spectroscopy (IR)

For the analysis of plastics, infrared radiation with wavelength between

2.5m and 25m is used.

For experimental reasons usually the wavenumber () is used instead of the

wavelength ().

= 1/*10000

: wavenumber in cm-1 and : wavelength in m

Topic IV.1 & 2

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26

IR - Spectroscopy Infrared spectroscopy (IR)

The IR radiation causes rotations and vibrations of molecules and atomic groups. The oscillations are described by spring-mass-systems:
m1 : mass of group 1 (e.g., H, O, N, S, Cl, F, CH3 )

k m2 m1

m2 : mass of group 2 (e.g., C, macromolecule) K : spring constant (e.g., C-H, C-O, C=O, C-N ...)

Absorption occurs when the exciting frequency is equal to the resonance

frequency of the system.

Due to the many different groups in polymers many different oscillations with
specific absorption peaks occur.
Topic IV.1 & 2
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27

IR - Spectroscopy Vibrations of CH2 groups

H H

IR-Spectroscopy

symmetric CH stretching vibration

Antisymmetric CH stretching vibration

H-C-H deformation (bending)

Rotation of CH2 group (twisting) Topic IV.1 & 2

Out-of plane pendulum vibration of the CH2 group (wagging)

In-plane pendulum vibration of the CH2 group (rocking) 28

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IR - Spectroscopy Experimental IR-Spectrophotometer

Heat radiation source

Interferometer

Sample compartment

Detector, Computer

Topic IV.1 & 2

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29

IR-spectroscopy - PE
100 90

transmission [%]

80 70 60 50 40 30 4000

H * C H

H C H
3000
n

CH2
2500 2000
-1

3500

1500

1000

w a v e n u m b e r [c m
Vibration a CH2, s CH2 CH2 CH2
Topic IV.1 & 2

Range 3000-2840 1471 717

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IR-spectroscopy - PP
100

transmission [%]

90

80

H H
70

CH2 CH3

*
60 4000

C C n * H CH3
3500 3000

CH3

2500

2000
-1

1500

1000

w a v e n u m b e r [c m
Vibration a CH2, s CH2 a CH3, s CH3 CH2, a CH3 s CH3
Topic IV.1 & 2

]
Range 1167 997, 973 841

Range 3000-2840 3000-2840 1455 1376

Vibration CH3 C-C CH2

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31

IR-spectroscopy - PS
100 90

transmission [%]

80 70 60 50 40 30 4000 3500 3000 2500 2000

-1

H * C H

H C
n

p h e n y le n e

1500

1000

w a v e n u m b e r [c m
Vibration =CH a CH2, s CH2
Topic IV.1 & 2

]
Vibration =CH =CH Ph Range 906 754 695
32

Range 3150-3000 3000-2840

Vibration Ph =CH =CH

Range 1600-1375 1067 1027

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IR-spectroscopy plasticized PVC

100 95

transmission [%]

90 85 80 75 70 4000

O H

CH2

CH Cl

3500

3000

2500

2000
-1

1500

1000

w a v e n u m b e r [c m
Vibration OH (plasticiser) a CH2, s CH2, CH C(=O)C (plasticiser) CH2
Topic IV.1 & 2

]
Range 1264 1122, 1072 966 742
33

Range 3331 3000-2840 1720 1426

Vibration CH, C-O-C (plast.) C-O (plast.) C-C CH

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IR-spectroscopy PA12
100 90

transmission [%]

80 70 60 50 40 4000

N H

C H 2 N H , N C

*
3500 3000

C O
2500

CH2

NH

*
C =O
1500 1000

2000
-1

w a v e n u m b e r [c m
Vibration NH a CH2 s CH2 C=O
Topic IV.1 & 2

]
Range 1553, 1269 1465 1200 720
34

Range 3287 2918 2850 1634

Vibration NH, CN CH2 CH2, CH2 CH2

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IR-spectroscopy - PET
100

80

transmission [%]

60

O
40

O C O CH2 CH2 O
n

20

O =C
0 4000 3500 3000 2500 2000
-1

p h e n y le n e
1500 1000

w a v e n u m b e r [c m
Vibration a CH2, s CH2 C=O Ph C(=O)O, =CH
Topic IV.1 & 2

]
Range 1095 1017 956, 873 725
35

Range 3000-2840 1713 1600-1325 1242

Vibration O-C, =CH =CH =CH Ph

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IR-spectroscopy PTFE and ETFE

transmission [%] transmission [%]
1 0 0 8 0 6 0 4 0 2 0 1 0 0 8 0 6 0 4 0 2 0

F *
P T F E

F
n

C C F F

*
C F
2

H H F *
E T F E
3 5 0 0

F
n

C C C C H H F F

*
C -F C -C -F
1 0 0 0

4 0 0 0

3 0 0 0

2 0 0 0

1 5 0 0
-1

w a v e n u m b e r [c m

PTFE: Vibration a CF2 s CF2

Range 1200 1145

ETFE: Vibration a CH2, s CH2 s CH2 C-F CH CH2, C-C-F

Range 3000-2840 1453, 1248, 1162 1323, 1038 971 666

36

Topic IV.1 & 2

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IR-spectroscopy PES and PSU

1 0 0

transmission [%]

9 0 8 0 7 0 6 0 1 0 0 9 5 9 0 8 5 8 0
*

p h e n y le n e

O *
P E S

S O

*
S O 2

transmission [%]

CH3 O C CH3 O

O S O
n

P S U
3 5 0 0 3 0 0 0 2 0 0 0 1 5 0 0
-1

4 0 0 0

1 0 0 0

w a v e n u m b e r [c m

Vibration =CH a Me, s Me Ph a Me a SO2, =CH

Topic IV.1 & 2

Range 3086 3000-2840 1600-1320 1486 1293, 1147

Vibration a C-O-C =CH =CH, Me =CH Ph

Range 1233 1103 1012 833 687

37

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IR-spectroscopy PEI and PI

100

transmission [%]

98
O
O C N C O C O

PI
C N

96 94 92 100 98 96 94 92 90 88 4000
* N
C O

im id e

transmission [%]

O C
O

O CH3 C CH3 O C C O
n

NC2
3500 3000
-1

PEI

2000

1500

1000

w a v e n u m b e r [c m

Vibration imide, s Me (PEI) imide, aC-O-C (PI) s NC2 (PEI) s C-O-C =CH (PI) C=O (PEI)
Courtesy of University of Leoben, Austria

Range 1355 1243 1236 1167, 1114, 1082 881, 821 848
38

Vibration =CH a Me & s Me (PEI) a C=O, s C=O Ph imide (PI)

Topic IV.1 & 2

Range 3150-3000 3000-2840 1775, 1725 1600-1300 1375

IR-spectroscopy - EVA
transmission [%]
100 80 60 40 20 0 100 80 60 40 20

CH2

CH O

* CH3

C O

24%

transmission [%]

0 4000

5%
3500 3000 2000 1500
-1

1000

w a v e n u m b e r [c m

Vibration a CH2, s CH2 a CH3, s CH3 C=O CH2, a Me

Topic IV.1 & 2

Range 3000-2840 3000-2840 1740 1469

Vibration s Me C(=O)O O-C, Me CH2

Range 1371 1241 1020 720

39

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IR-spectroscopy - EVA Determination of Vinylacetate (VA) content

H H C H
n

4,0
*
A(1240cm-1 ) / A(1472 cm )

CH2

CH O

* CH3

C H

C O

3,5 3,0 2,5 2,0 1,5 1,0 0,5 5 10 15

VA [%] y = 0,1427x + 0,038 R 2 = 0,9646

-1

Ethylene

Vinylacetate

A = ln (0/)
A...Absorption ...transmission Vinylacetate band: A(1240cm-1)...(C=O)O group Ethylene band: A(1472cm-1)...CH2, CH3 groups
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20

25

Topic IV.1 & 2

40

IR-spectroscopy (ATR) - PE Determination of PE-crystallinity

730 Ia - crystalline 720 Ib - amorphous

absorption [-]
760

740

720

700
-1

680

wave number [cm ]

= 100% * [1-(Ia/Ib)/1.233]/(1+Ia/Ib)
: Ia: I b: 1.233:
Topic IV.1 & 2

crystallinity value Intensity peak area of the 730 cm-1 band Intensity peak area of the 720 cm-1 band area-ratio of pure crystalline polyethylene
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IR-spectroscopy (ATR) - PE
absorption [-]
H * C H H C H
n

81%
*

47%

absorption [-]
3 0 0 0 2 9 0 0 2 8 0 01 5 0 0 1 4 0 0 1 3 0 0 1 2 0 0 1 1 0 0 1 0 0 0

900

800

700

w a v e n u m b e r [c m

-1

Vibration a CH2, s CH2 CH2 CH3

Topic IV.1 & 2

Range 3000-2840 1500-1460 730-720

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