© Fraunhofer LBF

AK

Poly

mera

naly

tik 2

2.3

.2019

Your Partner in Polymer Analytics

Dr. Robert BrüllFraunhofer-Institute for Structural Durability and System Reliability LBFwww.lbf.fraunhofer.de

© Fraunhofer LBF

Seite 2Seite 2

Process↔Structure↔Property Relationships

process

mechanicalproperties

long termproperties

receipe Failure

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Separations

Chromatography (LC)

Field Flow Fractionation (FFF)

CRYSTAF, TREF, CEF

Focus areas: By technique

Spectroscopy

Infrared

Raman

NMR

Thermal

DSC

TGA

Pyrolysis GC-MS

Imaging

Infrared-microscopy

Raman-microscopy

Polarized light microscopy

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Separation techniques

HT SEC

Multidimensional Techniques are essential to analyze the chemical heterogeneity

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Separation modes in liquid chromatography

SEC Mode

LAC Mode

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Multidimensional HT 2D-LC

Sample PreparationHeatable Separation unit(s)

Detection

IRRamanELSDNMR

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Graphite – A magic stationary Phase

Absolutely flat surface

Interactions with the analyte through the full range of electronic interactions

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Interactive Chromatography up to 200 °C

0 5 10 15 20 25

0.0

0.2

0.4

0.6

0.8

1.0

isotactic PP

PE

syndio-

tactic PP

resp

on

se o

f E

LS

D [

Vo

lts]

elution time [minutes]

atactic PP

Start of gradient

Stationary phase: Hypercarb™,Mobile phase: decanol→TCB

Highly selective interactions according to composition and microstructure become possible

10 11 12

0,0

0,5

1,0

Ethylene/1-hexene copolymers

20.7 mol%

13.9 mol%9 mol%

6.3 mol%5.8 mol%

5.1 mol%3.7 mol%

2.2 mol% 1.1 mol%

0.4 mol%

EL

SD

sig

nal [V

]

Elution volume [mL]

PE 260

kg/mol

0 mol%

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EPDM

8,7 9,0 9,3 9,6 9,9 10,2 10,50,0

0,1

0,2

0,3

0,4

0,5

ENB-7.2%,

C2-49 wt.%

ELS

D s

ign

al [V

]

Elution Volume [mL]

ENB-3.8%,

C2-49 wt.%

nm

Separation according to ethylene content and diene content are possible

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Seite 10

HT 2D-LC-IR of Grafted Polyolefins

PP-g-MA (1 mol %) PP-g-MA (1.7 mol %)

Graft products can be separated from non-grafted material

The molar mass distribution of each component can be determined

The graft heterogeneity becomes visible

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Steps for LC → NMR, FTIR and UV/RI (off-line)

Sample LC-ELSD

Replace ELSD by portable automatic fraction collector

Automatic fraction collectorTemperature range 25 – 200 °C

From LC

Sample holder Evaporator with vacuum pump

Transfer to NMR tube

NMR

After evaporation of solvents

9.0 9.5 10.0 10.5 11.0

0.0

0.1

0.2

0.3

0.4

432

EPDM 05090a

C2-61.5 mol %,

C3-36.5 mol %,

ENB-1.8 mol %,

VNB.0.29 mol %

EL

SD

sig

nal [V

]

Elution volume [mL]

1

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Preparative LC

15 16 17 18 19 20 21 22 230.0

0.2

0.4

0.6

0.8

1.0

8 % overlap

32

EL

SD

re

sp

on

se

[V

]

(Are

a n

orm

ali

ze

d)

SEC elution volume [mL]

1

7 % overlap

a)14 15 16 17 18 19 20 21 22 23

0.0

0.2

0.4

0.6

0.8

1.0

1.2

13 % overlap

16 % overlap

12 % overlap

2 543EL

SD

res

po

ns

e [

V]

(Are

a n

orm

alize

d)

SEC elution volume [mL]

1

15 % overlap

b)

3 fractions 5 fractions

8 fractions

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The world of imaging at LBF

Polarized Light RamanInfrared

• Morphology• Crystallinity• Orientation

• Additive• Content• Distribution

• Morphology• Crystallinity• Orientation• Polymorphism

• Morphology• Crystallinity• Orientation• Polymorphism

• Additive• Identification• Distribution

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Seite 14Seite 14

Confocal Raman microscopy (CRM)

Alpha 500 Confocal Raman Microscopy, WITec, Germany

Confocal Volume

266 nm

850 nm

x

y

x

z

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Seite 15Seite 15

Flame Retarded PP (FR PP)

Cross section of FR PP Raman-image of von 25x25 µm2 with 100x100 pixels

PPM triazine

PPM triazine

PP

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x

y

z

Raman Image

CRM

Laser

Sample

How does CRM work?

Objektiv

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High Resolution CRM of Core-Shell Particles in POM

Overlay of original images

Processd high resolution image

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CRM: Depth Profiling

x

y

z

Multilayer Film

CRM

Laser

Objektive

PET

PE

PA6

PP

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NU 100 PP

Volume mapping of additives

PP

NU 100

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Infrared Imaging

µFTIR:

Line Scan, Area Map

Applications

Additive distributions

Time and space resolved

Morphology distributions

0 200 400 600 800 1000

200

400

600

800

1000

1200

1400

1600

1800

2000

Ageing time [h]

Dis

tan

ce f

rom

th

e in

ner

pip

e w

all

[µ

m]

0.000

0.1000

0.2000

0.3000

0.4000

0.5000

0.6000

0.7000

0.8000

0.9000

1.000

C/C0

Chimassorb 944

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Effect of Chlorinated Water on iPP-R Pipes

PP-R 1 PP-R 2

Chlorine (4 mg/l), 95 °C

The time and space dependent concentration of stabilizers can be mapped

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What can we do for you?

Robert.bruell@lbf.fraunhofer.de

Ingo.alig@lbf.fraunhofer.de

Frank.malz@lbf.fraunhofer.de