Chemical Analysis at Teijin AramidIntroduction

Who is Teijin, what is aramid?

The role of analytical chemistryChallenges, problems, solutions

ExamplesChromatography

Atom- and molecular spectroscopy

Other techniques Dr. A.H.M. Schotman

Group Head Analytical Chemistry Department

Teijin LimitedGlobal & technology driven

On Tokyo and Osaka stock exchanges

USD 9.4 billion turnover*

19,000 employees worldwide

Long term dedication to high performancefibers

*March 2009, USD 1=JPY 100

The Aramid Fibers Business Group of Teijin ltd Aramid fibers:

Twaron, Sulfron, Technora, Teijinconex

Production facilities

The Netherlands:Delfzijl: Monomer & PolymerEmmen: Twaron yarn, Twaron pulp, SulfronArnhem: Twaron pulp

Japan:Matsuyama: TechnoraIwakuni: Teijinconex

Twaron, a unique combination of propertiesTwaron para-aramid:

Strength (5x steel, w/w)High modulusCut resistanceImpact resistanceChemical stabilityHeat stability

polyparaphenylene terephthalamide

Aramid Applications

The role of analytical chemistry

Chemical Analysis of Aramids is a challenge in itselfvery resistant to chemicals and high temperaturesonly soluble in 100% sulfuric acid

SolutionsAnalysis as such

e.g. IR, XRFAnalysis while dissolved in sulfuric acid

e.g. SEC and NMRAnalysis after careful destruction

e.g. Atom Spectroscopy, Pyrolysis etc.

Below I will give an impression on Twaron analysis

Anal. Chem~ 50 people3 laboratories

Technology

Manufacturing Marketing

New demands:

Faster, at line, on line, lower levels, new products

SEC-analysis with sulfuric acid as solvent

injector

detector

pump

eluent

columnoven

Principle: separation is based on the different abilities of large and small polymer molecules to penetrate into the pores of a SEC column.

∑∑ ⋅

=i

iin n

MnM

nw MMD /=

∑∑ ⋅

=i

iiw c

McM

lmolnlgc

i

i/:

/:

SEC parameters:

Instrumentation and Principle

2 6 2 8 3 0 3 2 3 4 3 6 3 8 4 0 4 2 4 4 4 6 4 8 5 0 5 2 5 4 5 6 5 8

SEC analysis (2)

Sample code

Twaron (blue)

Competitor (black)

Applications: • Determination of the Molecular Weight Distribution (MWD) of polymers -

like aramides (Twaron, Conex, Technora and others) but also PEEK•Determination of the influence of different process and application

variables on the MWD

Problem: absolute MWD still impossible

Atom Spectrometry

XRFICP-OES

ICP-MS + ETV

Application area:Identification of elements Techniques offers its specific benefitsSolid sampling

Atom spectroscopy 2

Examples:Determination Na and S in Twaron (XRF)check neutralization (we spin from sulfuric acid)Check for sulfonation during spinning (ETV-SS-ICP-MS)

.

S-speciation Twaron/Kevlar by SS-ETV-ICP-MS

0.00E+00

2.00E+04

4.00E+04

6.00E+04

8.00E+04

1.00E+05

1.20E+05

0 10 20 30 40 50 60

Time (s)

Ions

/s.m

g

KevlarTwaron

Sulfonaat---->

<--Na2SO4

S-speciation in aramids

Yarn

Polymer

20MHz NMR

Very suitable for at line production control: fast, non destructive, very reproducible

Pitfall: reproducibly wrong

20MHz NMR analysis

Determination of finish on yarn

by extraction or LR NMRCount Average VAR STDS

LR-NMR 40 0.722 0.0001 0.01ASE extract 40 0.736 0.0025 0.05

The technique is used for characterization of monomers, polymers and finishes

However we find NMR also very useful for identification and quantification of organics in liquids at mg/kg level

High Resolution NMR

We make Twaron polymer in Delfzijl, ship it to Emmen were it is dissolved in sulfuric acid and spun to yarn.

The polymer contains some residual solvent. The sulfuric acid that is used for spinning is recycled, the solvent is destructed.

High Resolution NMR (2)

1.01.52.02.53.03.54.04.5 ppm

H2CO3(CO2)

Left part of the H-NMR spectrum of sulfuric acid recycle feed.

TOC level few 100 mg/kg

~4 mg EG/kg (signals at 3 ppm)

H2CO3 at a level of 100 mg/kg

Hyphenated techniques

Sample introduction GC-MS-IR-AEDSometimes one needs sensitivity, sometimes, specific information, identification or quantification without having a reference compound

Sample introduction of volatiles

Emission fromfinishes

Pyrolysis

Volatilesfrom yarn

In wastewater

Coated stirring bar

8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00

500000

1000000

1500000

2000000

2500000

3000000

3500000

4000000

4500000

5000000

5500000

6000000

6500000

7000000

7500000

8000000

8500000

Time-->

8.51

8.64

8.73 9.07 9.22

9.57

10.48

10.89

11.18 11.30

12.63

12.79 12.87 13.52

13.63

13.70

14.29 14.47

14.58

14.66 14.75

15.04

15.40

15.55 15.77 15.95

16.06

16.22 16.36 16.39

16.50 16.82 17.23 17.55

min10 12 14 16

Counts

50

100

150

200

250

AED1 C, Chlorine 479 (QRA06457\06457A.D)

8.6

02 8

.730

8.8

20

8.8

96 9

.043 9.1

62 9

.308

9.4

15 9

.486

9.9

55

10.2

60

10.

577

10.

739

10.

815

10.

992

11.0

96 1

1.2

29 1

1.330

11.3

97

11.

790

11.

940

12.

059

12.

336

12.

598

12.6

76 1

2.83

6 1

2.90

0 1

2.98

3 1

3.12

3 1

3.2

22 1

3.3

20

13.

533

13.

813

14.

245

14.

293

14.

643

14.7

20 1

4.78

4 1

4.87

2

15.0

47 1

5.20

6

15.

417

15.5

26

15.6

90

16.2

01 1

6.3

40 1

6.4

93 1

6.5

28 1

6.6

40 1

6.71

9 1

6.8

70 1

6.9

74

17.

263

17.3

88 1

7.52

1

min10 12 14 16

Counts

20

30

40

50

60

70

80

90

100

AED1 D, Bromine 478 (QRA06457\06457A.D)

8.3

78 8

.444

8.6

24

8.7

06 8

.820

9.1

62

9.6

64

10.

268

10.

841 1

1.28

9

12.

143

12.

949

13.7

90 1

3.9

15 1

4.0

45 1

4.12

0

14.2

75 1

4.3

80

15.

320

15.

470

15.6

57 1

5.72

6

16.

338

Left TIC chromatogram MS

Levels 10…1000 µg/m3

Left Chlorine trace AED

Left Bromine trace AED

Volatiles in air trapped on Tenax, desorbed and analyzed by GC/MS/AED

The power of aramid

made possible by

The power of analysis