1. Thierry Fouquet, PhD (JSPS fellow, AIST)
ASAHI GLASS CO. (AGC) – Innovative Technology Research Center, July 6
MS & Allied Techniques
for Fluoro(co)polymers
and EVA Copolymers

2. Biographical sketch
Thierry Fouquet (ティエリ フーケ)
29 y.o.
French (officially), World citizen (deep down)
42 papers, 15 talks, h-index 9
2006 – Jun 2015:
Engineering School, MSc, PhD, Post-doc + R&D Eng.
Aix-Marseille University, Public Research Centre Tudor,
Luxembourg Institute of Science and Technology
(France + Luxembourg)
June – Aug 2015:
Wanderlust
Oct 2015 – Oct 2017
Post-doc (JSPS fellow), AIST, Japan
MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 62
Naha, Okinawa

3. もくじ
3
Part 1: MS & DSC for
plasma fluoropolymers
Part 2: MS and KMD
for plasma copolymers
Part 3: MS and KMD for EVA copolymers

4. Part 1
MS & DSC for a plasma fluoropolymer
Evaluation of MW
Luxembourg Institute of
Science and Technology (LIST)

5. Plasma…
5
« Plasma discharge » (b)
(a) C. Tendero et al, Spectrochim. Acta Part B 2006, 61, 2.
(b) U. Kogelschatz, Plasma Chem. Plasma Process. 2003, 23, 1.
Plasma used as an active medium (a)
 « More or less ionized gas »
 Formed of electrons, ions, radicals & neutrals
Electrode
Electrode
MS & Allied techniques for
fluoropolymers and EVA
copolymers – T. Fouquet, July 6

6. Electrode
Electrode
… & plasma polymers (PP)
6
Injection
of precursor
PFDA (perfluorinated)
Plasma-polymer
(a) J. Petersen et al, RSC Advances 2013, 3, 4416.
Plasma-polymerization (a)
(a) T. Fouquet et al, Encyclopedia of Plasma Technology, CRC Press, 2016
DSC (b)
XRD (b)
MALDI-MS
(soluble part) (b)

7. PP & pitfalls
7
ATRP
(controlled
radical
polymerization)
Plasma polymer
（soluble part, 25%)
T. Fouquet et al, Plasma Process. Polymer. 2014, 11, 931.
Dispersity
Low solubility
MW ?
MS & Allied techniques for fluoropolymers
and EVA copolymers – T. Fouquet, July 6

8. MW varies anyway
8
Sample 1
Sample 2
Sample 1
Sample 2
T. Fouquet et al, Plasma Process. Polymer. 2015, 12, 980.
Probably biased Tmelting seems to vary as well
Sample 2

9. ATRP standards
9 T. Fouquet et al, Plasma Process. Polymer. 2015, 12, 980.
“monodisperse” standards

10. Calibration curve
10
Sample 1
Sample 2
From MALDI-MS
T. Fouquet et al, Plasma Process. Polymer. 2015, 12, 980.
From DSC
ATRP standards
MS & Allied techniques for fluoropolymers
and EVA copolymers – T. Fouquet, July 6

11. MW evaluation
11
Sample 1
Sample 2
“DSC corrected”
T. Fouquet et al, Plasma Process. Polymer. 2015, 12, 980.
Sample 1
Sample 2
ATRP vs. PP
Same NMR
Same XRD

12. To go further
12
Sample 2
Controlled radical
polymerization
Free radical
polymerization
T. Fouquet et al, Plasma Process. Polymer. 2015, 12, 980.
MS & Allied techniques for fluoropolymers
and EVA copolymers – T. Fouquet, July 6

13. To go further
13
Controlled radical
polymerization
Free radical
polymerization
Insoluble
part Soluble part (SEC + MS)
T. Fouquet et al, Plasma Process. Polymer. 2015, 12, 980.
Sample 2

14. Part 2
MS & KMD for plasma (co)polymers
Evidence of a copolymerization
Collaboration
Luxembourg Institute of
Science and Technology (LIST)
Dr G. Mertz
(gregory.mertz@list.lu)

15. Plasma (co)polymers
15
Plasma-(CO)polymer
Is it a bilayer ?
Is it a polymer blend ?
Is it a copolymer ?
Injection
of precursor
AND
PFDA (perfluorinated)
(Co-injection)
DOCA (long alkyl)
Electrode
Electrode
MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

16. Co-injecting two precursors
16
Variation of the
melting temperature
+
One melting peak only
=
Copolymer
Evidence at a
molecular level ?
(a) T. Fouquet et al, Plasma Process. Polymer. 2016, 10.1002/ppap.201600053.
DSC, melting point (a)

17. Is MS the tool ?
17 (a) T. Fouquet et al, Plasma Process. Polymer. 2016, 10.1002/ppap.201600053.
Different composition of the feeding mixture →
Different MS fingerprint (a)
Tracking co-oligomers = tedious manual peak picking and assignments

18. Mass defect
• 1st-order mass: Kendrick mass(a)
18
KM(ion) =
)𝑟𝑜𝑢𝑛𝑑(𝑚𝐼𝑈𝑃𝐴𝐶 𝑏𝑎𝑠𝑒 𝑢𝑛𝑖𝑡 , 0
𝑚𝐼𝑈𝑃𝐴𝐶 𝑏𝑎𝑠𝑒 𝑢𝑛𝑖𝑡
∙ 𝑚𝐼𝑈𝑃𝐴𝐶 𝑖𝑜𝑛
IUPAC scale:
mass of C = 12.0000 (base unit)
mass of CH2 = 14.0157
Kendrick scale (base transformation)
mass of CH2 = 14.0000 (base unit)
mass of C = 11.9866
Esso Research and Engineering
Company, New Jersey
(a) E. Kendrick, Anal. Chem. 1963, 35, 2146.
No pic
available
MS & Allied techniques for fluoropolymers and EVA
copolymers – T. Fouquet, July 6

19. MS + mass defect
• Mass defect (KMD)
19
)KMD 𝑖𝑜𝑛 = 𝑟𝑜𝑢𝑛𝑑(KM ion , 0) − KM(ion
Congeners varying by a number of base units only = same KMD
→ KMD plot: KMD vs. NKM
Nominal Kendrick Mass
NKM
Horizontal alignment
a-(X)n-w + Y+
KMD
Base unit = Ｘ
NKM
KMD

20. Application to polymers(a)
20 (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.
a-(PO)n-w + Y+
a-(PO)n-y + Y+
KMD
MS & Allied techniques for
fluoropolymers and EVA
copolymers – T. Fouquet, July 6
Base unit = PO

21. Application to polymers(a)
21 (a) H. Sato et al, J. Am. Soc. Mass Spectrom. 2014, 25, 1346.
a-(PO)n-w + Y+
a-(EO)n-w + Y+
Base unit = PO
MS & Allied techniques for
fluoropolymers and EVA
copolymers – T. Fouquet, July 6

22. Plasma homopolymers
22
w
5a
KMD
KMD analysis is robust enough
KMD

23. Plasma homopolymers
23 MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

24. Of lines…
24 T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

25. … and alignments
25 T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

26. 26
Sum = blend
KMD
NKM
Blend…

27. …Or Copolymer
27
KMD
NKM
Convolution = copolymer

28. Back to MS…
28 T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

29. …But adding the KMD dimension
29 T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

30. …But adding the KMD dimension
30 T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

31. The more the merrier
31 T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

32. Beyond all doubts…
32 T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

33. …it’s a copolymer
33
It’s not flawless:
- Limited to the soluble part of the deposits (< 25-50 wt%)
- No quantitative data (co-monomeric composition)
But: definitive evidence of a plasma copolymerization
T. Fouquet et al, Plasma Process. Polymer. 2016, DOI: 10.1002/ppap.201600053.

34. Part 3
KMD for EVA copolymers
Co-monomeric compositions and aging routes
EVA pellets
EVA as encapsulant
for photovoltaic
modules

35. Ethylene Vinyl Acetate
• EVA copolymers
• Top industrial importance
• Depending on the VA content :
– Hot melt adhesives
– Drug delivery
– Padding
– Solar cells encapsulating materials
35 MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

36. MS for EVA: a main pitfall
36
Low molecular weight oligomers
High resolution MS analyzer
SEC
MALDI
SpiralTOF
Strategy:
EmVAn
13C
13C2
13C2
13C3 13C4
13C3
13C0.06 Da
+
2 Da
3 x E = 84 Da
Em-3VAn+1
Mass defect+

37. KMD for EVA
37
EVA
40 wt% VA
EVA
25 wt% VA
EVA
18 wt% VA
1.
Easy comparison
2.
Evaluation of the
VA content with no
peak assignment
T. Fouquet, S. Nakamura, H. Sato, Rapid Commun. Mass Spectrom. 2016, 30, 973.

38. A foretaste of aging
38
• Hydrolysis of EVA (under basic conditions)
Terpolymer EVAVOH
MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

39. More pitfalls…
39
Solubility
SEC
MALDI
SpiralTOF
Mass defectHydrolysisStrategy:
Isobaric issues
«in vial hydrolysis»

40. SEC-hydrolysis-MALDI-MS
40
IRRAS MALDI
higher m/z
2 min hydrolysis
T. Fouquet, H. Sato, Rapid Commun. Mass Spectrom. 2016, XXX.

41. 41
higher m/z
20 min hydrolysis
T. Fouquet, H. Sato, Rapid Commun. Mass Spectrom. 2016, XXX.
SEC-hydrolysis-MALDI-MS

42. Data mining. The big picture
42
• Base unit ?
E: poorly informative alignments
VA / VOH: interdependent
VA-VOH (CH2CO)
= marker of the hydrolysis
Hydrolysis
VA
VOH
2 min

43. 43
20 min
Data mining. The big picture
Hydrolysis
degree
(centroid)Hydrolysis
VA
VOH

44. 44
Untargeted plot
Data mining. The big picture
Hand-picked data could also
enhance the visualization
MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

45. Data mining. Hand-picking
45
Handpicked data
Hydrolysis
VA
VOH
t=0
(pristine)
MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

46. Data mining. Hand-picking
46
Hydrolysis
VA
VOH
t=0
(pristine)
2 min

47. Data mining. Hand-picking
47
Hydrolysis
VA
VOH
20 min
t=0
(pristine)

48. Another example
48
EVA 25
t = 0
t = 6h
@ 150 deg
• Thermo-oxidative aging of EVA
(hot plate, open air)
MALDI
EVA25 t=0
t = 6h

49. Before/after thermo-oxidation
49
EVA 25
t = 0
t = 1h
@ 150 deg
KMD

50. Too much
50
EVA 25
t = 0
Acetic acid loss
Oxidation
Chain scission
Cyclization (lactones)
…
Too much data
No centroidization
available
(different end-groups)
t = 1h
@ 150 deg

51. Acetic acid loss - Hand-picking
51
C
H2
C
H
O
C
CH3
O
C
H
C
H- CH3COOH
-0.25
-0.2
-0.15
-0.1
-0.05
0
0.05
0.1
750 800 850 900 950 1000 1050
E18VA6
E33VA1
Acetylene (A)
VA
t = 0
Base unit:
CH3COOH
E24VA4

52. 52
-0.25
-0.2
-0.15
-0.1
-0.05
0
0.05
0.1
750 800 850 900 950 1000 1050
C
H2
C
H
O
C
CH3
O
C
H
C
H- CH3COOH
- CH3COOH
E18VA3A3
E24VA2A2
E18VA6
E33VA1
E24VA4
t = 1h
Base unit:
CH3COOH
Acetic acid loss - Hand-picking
Acetylene (A)
VA

53. 53
-0.25
-0.2
-0.15
-0.1
-0.05
0
0.05
0.1
750 800 850 900 950 1000 1050
C
H2
C
H
O
C
CH3
O
C
H
C
H- CH3COOH
E18VA6
E33VA1
E18VA2A4
E24VA1A3
E24VA4
t = 6h
Base unit:
CH3COOH
Acetic acid loss - Hand-picking
Acetylene (A)
VA

54. Next step(s) ?
54
• EVA
– Aging of used PV modules (with NMR)
• Plasma copolymers
– Block copolymers & terpolymers (to be defined)
– KMD and higher-order mass defects (cf. MSSJ talk, June 23rd)
• MS & DSC
– So far, case closed
MS & Allied techniques for fluoropolymers and EVA copolymers – T. Fouquet, July 6

55. ありがとうございます！
thierry.fouquet@aist.go.jp
LinkedIn
Researchgate
Hinode, Fuji-san,
July 3rd 4:30