properties and structure of cyanate ester/polyethersulfone ...€¦ · university of applied...
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SuCoHS project, Grant Agreement N° 769118
9th EASN International Conference on Innovation in Aviation and Space
L. Amirova, F. Schadt, C. Brauner, M. Grob
University of Applied Sciences and Arts Northwestern Switzerland
03-06.09.2019, Athens, Greece
Properties and structure of Cyanate Ester/Polyethersulfone composites
01/10/2019 2
Requirements for the material development
Glass transition temperature > 335°C
Fracture toughness > 0.85 MPa·m1/2
Curing temperature < 185°C
01/10/2019 3
Comparative properties of advanced resins
[Iredale, R. J., Ward, C., & Hamerton, I. (2017). Modern advances in bismaleimide resin technology:
a 21st century perspective on the chemistry of addition polyimides. Progress in Polymer
Science, 69, 1-21.]
01/10/2019 4
Toughening mechanisms
[Wang, J., Liu, R., & Jian, X. (2017). Introduction to
epoxy/thermoplastic blends. Handbook of Epoxy Blends, 429-458.]
01/10/2019 5
Matrix toughening
- Phenoxy resin- Polyphenylsulfone- Acrylic polymers- Epoxy resin toughened with silica nanoparticles- Polyethersulfone (different grades, functionalization,
molecular weight)- Polyetherimide (different grades)
Interlayer toughening
- Phenoxy films- Polyetherimide films
Toughening approaches. Overview
Tg~220°C
Tg~90°C
01/10/2019 6
Investigation of molecular weight, functionalization and content of polyethersulfone
(PES) on thermal and mechanical properties of cyanate ester formulations
Development of accelerated cyanate ester formulation allowing curing at 180°C
Prepreg manufacturing based on the developed formulation
Demonstrator part manufacturing
Objectives of the work
01/10/2019 7
Cyanate ester PT-30 (CE)
T(°C)
time (hour)
260
200
150
Conventional heating cycle
01/10/2019 8
Cure kinetic parameters of PT-30 CE
𝑑𝛼
𝑑𝑡= 𝐴1 exp −
𝐸1𝑅𝑇
1 − 𝛼 𝑛1 + 𝐴2 exp −𝐸2𝑅𝑇
𝛼𝑚 1 − 𝛼 𝑛22
1 + 𝑒𝑥𝑝𝛼 − 𝛼𝑚𝑎𝑥
𝑏
− 1
01/10/2019 9
Parameters PES 1 PES 2 PES 3
Mw, g/mol 16000 33000 42000
Particle size, µm 45 45 45
Glass transition temperature, °C 220 223 227
-OH end groups, per 100 polymer
relating units4.5 - 1.1
Polyethersulfone (PES)
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Methods
Glass transition temperature
Storage modulus
Curing temperatureand enthalpy
Cure kinetics
Fracturetoughness
Morphology
DMA Q800
(TA Instruments)
DSC 25
(TA Instruments)
Hot stage microscope
(Linkam)
Universal testing machine
(Zwick / Roell Z100 )
Laser scanning microscope
(Keyence VK-X200)
Fracture surfacemorphology
01/10/2019 11
Morphology of PT30-PES matrix
15phr PES 2 15phr PES 315phr PES 1
Droplet morphology Sea-island morphology
and phase inversion
Sea-island morphology
and phase inversion
Only certain ratios of molecular weight form a droplet morphology
10 µm 10 µm
Morphology investigation at 180°C
01/10/2019 12
Effect of PES molecular weight and functionalizationon glass transition temperature of CE formulations
20phr PES 1
drop ~35%
PT30
PT30 - 20phr PES 1
PT30 - 20phr PES 2
PT30 - 20phr PES 3
PT30 system Tg PES on,°C ΔE, MPa
Neat resin - -
20phr PES 1 241 818
20phr PES 2 231 1482
20phr PES 3 245 1505
01/10/2019 13
Fracture surface of cured PT30 - 15phr PES 1 sample
Crack propagation20 μm
Fracture toughness of PT30 - PES 1 system
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
K1
C, M
Pa
·m1
/2
PT30
PT30 PES 5%
PT30 PES 10%
PT30 PES 15%
PT30 PES 20%
K1c, M
Pa m
1/2
Increase of 132%
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
K1
C, M
Pa
·m1
/2
PT30
PT30 PES 5%
PT30 PES 10%
PT30 PES 15%
PT30 PES 20%
PT30
PT30-5phr PES
PT30-10phr PES
PT30-15phr PES
PT30-20phr PES
01/10/2019 14
Storage modulus drop at PES
Tg depending on content of PES
For 10 and 15phr PES similar
15phr PES optimum
BUT: Real Tg onset at higher
temperature
Effect of the PES content on glass transition temperatureand storage modulus behaviour of CE formulations
15-20phr PES 1
PT30
PT30 - 5phr PES 1
PT30 - 10phr PES 1
PT30 - 15phr PES 1
PT30 - 20phr PES 1
PES content,
phr
Tg PES on,°C ΔE, MPa
5 241 326
10 240 509
15 237 563
20 241 705
01/10/2019 15
PT30 - 15phr PES 1 dry
PT30 - 15phr PES 1 wet 24 h
PT30 - 15phr PES 1 wet 48 h
Influence of wet conditions on thermomechanicalproperties of PT30 – 15phr PES formulations
Conditions Tg on, °C ΔE, MPa
dry conditions 405 503
24h* 400 520
48h 400 710
* Boiling in water at 80°C
01/10/2019 16
- Estimated optimal content of PES 1 (15phr = 13wt%)
- Developed temperature conditions for impregnation
- Selected carbon fiber type T800
North Thin Ply Technology (NTPT) successfully
manufactured the prepreg based on the
toughened CE
Development of the prepreg based on the toughenedCE system
01/10/2019 17
DMA of unidirectional PT30 – 13wt% PES 1 composite
Relative Young`s modulus vs Temperature for toughened unidirectional PT30 composite
Curing cycle: autoclave 1h@150°C + 3h@200°C + freestanding postcuring 1h@260°C
100%
01/10/2019 18
𝑑𝛼
𝑑𝑡= 𝐴1 exp −
𝐸1𝑅𝑇
1 − 𝛼 𝑛1 + 𝐴2 exp −𝐸2𝑅𝑇
𝛼𝑚 1 − 𝛼 𝑛22
1 + 𝑒𝑥𝑝𝛼 − 𝛼𝑚𝑎𝑥
𝑏
− 1
CE380 – catalyzed CE system based on PT-30 resindeveloped by NTPT together with FHNWCure kinetics
01/10/2019 19
Time, h CE380 Catalyzed
PT30-15phr PES 1
3 70 73
5 75 77
Degree of cure for catalyzed CE systems at 180 °C
+ postcuring at 260 °C
Thermal properties of catalyzed toughened system
01/10/2019 20
Thermomechanical properties of catalyzed CE systems
CE380
Catalyzed PT30-15phr PES 1
01/10/2019 21
Demonstrator part manufacturing
Fully cured part in 1 hour at 260°C
01/10/2019 22
A broad variety of different potential tougheners investigated
Influence of molecular weight and functionalization of PES analyzed
Optimal content ca. of 13wt% PES for 100% of toughness increase
Temperature conditions for prepreg manufacturing established
First toughened thin-ply prepreg manufactured
Prepregs used for demonstrator part manufacturing
Conclusions
01/10/2019 23
This project has received funding from the European Union’s Horizon 2020 research and innovation
programme under grant agreement N° 769178.
Thank you for your attention
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