the amazing meeting between polymer world and two ... · pbat (ecoflex) + go neat pbat pbat 0.05%...
TRANSCRIPT
The amazing meeting between polymer world and two-dimensional
materials
Guilhermino José Macêdo FechineMackGraphe
Universidade Presbiteriana Mackenzie
www.Mackenzie.br/mackgraphe.html
Polymers 2D Materials
MERO
How did they meet?
Science, V.306, p.666 (2004)
Scotch tape & Graphene
First date (2004)
Wedding
(2010)
Andre
Geim
Konstantin
Novoselov
Nobel Prize
How I became friend of the couple?
Advanced 2D Materials and
Graphene Research Centre
January (2013)
Chapter one:
”2D Materials Transfer Methods and crystal exfoliation”
Chapter two:
”Polymer nanocomposites based on 2D material fillers”
Fruits of friendship
1. Direct Dry Transfer of 2D Materials
Challenges
I. Large areas of 2D material;
II. No etching step;
III. No polymer residue;
IV. 2D Material integrity.
WET TRANSFER
Traditional Method to transfer CVD graphene
Polymer residue [3]
[1] Wang et al., Adv. Mater. V.25, p4521 (2013)
[2] Chen et al., Adv. Sci. V. 3, p. 1500343 (2016).
[3] Takashi Matsumae et al. J. Electrochem. Soc. V.163, E159 (2016)
Wrinkles [1]
Cracks [2]
Direct Dry Transfer (DDT) to Polymeric Substrates
Patent: US Application No. 14/631,942 (26/02/2015)
“Method and Apparatus for Transferring Graphene to a Polymeric Substrate”
Phenomena involved
Requirements for a good transfer:
• Chemical Structure of the Polymer
• Bpolymer-Gr >> BGr-Cu
• Good contact (roughness and rheological properties)
Polymer
Adhesion
Simulations
(PE) (PS) (PLA) (PVDF-TrFE)
Improvements (Rheological properties)
120 140 160 180 200
4,0x103
8,0x103
1,2x104
1,6x104
LDPE
HDPE
PS
PLA
PVDF-TrFE
Co
mple
x v
iscosity (
Pa.s
)
Temperature (oC)
120 140 160 180 200
4,0x103
8,0x103
1,2x104
1,6x104
LDPE
HDPE
PS
PLA
PVDF-TrFE
Co
mple
x v
iscosity (
Pa.s
)
Temperature (oC)
Improvements (Contact)
Video
Results (FWHM-2D)
HIPS
PLA
ABS
SBS
PBAT
DDT DDT-SC
2. Direct Dry Transfer by in situ polymerization
Patent Appplication (24/02/2016): TRANSFERÊNCIA DIRETA DE MATERIAIS 2D VIA POLIMERIZAÇÃO IN SITU (BR 10 2016 003973 8)
FWHM-2D
Direct Dry Transfer for others 2D
MoS2 - CVD
WSe2 - CVD
3. Polymer Nanocomposites manufacturing and characterization
Why Polymer Nanocomposite with 2D materials (2DM)?
1. Very high surface area as graphene;
2. Low level of 2D content is needed to reach the desired properties.
3. All special properties of 2DM;
4. We can play with chemical structure of 2DM and polymer matrix;
Big Challenge
Polymeric Matrix Graphene
How can we keep the 2DM structure in a polymeric matrix?
Polymer nanocomposites
preparation methods
Meltmixing
Solventmethod
In situ polimerization
Melt mixing
3. Challenges involved?
Process parameters Filler content
Filler dispersion Filler homogeneity
Our strategies
Solid-Solid Deposition
Liquid-Phase Feeding
”PS and mGOas templates”
Our strategies
- 2D dispersion production; - Characterization;- The insertion of the 2D filler
in to the polymer is carried out based on pre-exfoliated particles
Characterization of Graphite Oxide (GrO)
10 20 30 40
Inte
nsity (
a.u
.)
2 (°)
Gr
Gr-O
11.34°
26.26°
100 200 300 400 500 600 700 800 900 1000
0
20
40
60
80
100
Weig
ht
(%)
Temperature (° C)
Gr
Gr-O
500 1000 1500 2000 2500 3000
Inte
nsity (
a.u
.)
Raman shift (cm-1)
Gr
Gr-O
Characterization of multi-layer Graphene Oxide
(mGO)
Based on these data, the
number of layers of GO is
between 10 and 30 (> 90% of
the population)
Solid-solid Deposition
Liquid phase feeding
Processing parameters
Screw speed (rpm)
2D amount (%)
Temperature profile
PS + mGO (0.5%) / 250 rpm PS + mGO (0.1%) / 350 rpm
PS / mGO morphology
TEM micrographs of the nanocomposites obtained by SSD at 350 rpm
screw speed: (a) PS with 0.1 wt% GO and (b) PS with 0.3 wt% GO.
Arrows indicates GO sheets.
Results
PCL + HA + mGO
PS + MoS2
TPU + mGO
PP + mGO
PLA + HA + mGO
PBAT + mGO
In process…
PBAT + MoS2 PP + hBN
UMWHDPE + mGO LDPE + mGr
PS + MoS2
0 50 100 150 2000
10
20
30
40
50
60
without GO
0,05% GO
0.1% GO
0.5% GO
Str
ess
(MP
a)
Strain (%)
PP + mGO
0
500
1000
1500
2000
2500
3000
3500
without GO 0,05% GO 0,1% GO 0,5%GO
E [M
Pa]
Elastic Modulus
27.2%34.8%
Mechanical Properties
PCL + HA (20%) + mGO (0.1%)
90° Kneading Block Extensional Mixing Elements
L2 L4 S4
TPU + GO (0,25%)
Mechanical Properties
0 100 200 300 400 500 600 700 800 900 1000
0
5
10
15
20
25
30
35
40
Te
nsa
o (
MP
a)
Deformaçao (%)
TPU puro
L2 0,25
L4 0,25
KB 0,25
S4 0,25
Tribological Property
~165
~75
TPU + GO (0,25%)
Surface Property
PLA + HA (20%) + mGO
Surface free energy Dispersive componentDispersive component Polar component
Films
PBAT (Ecoflex) + GO
Neat PBAT
PBAT0.05% GO
PBAT0.10% GO
PBAT0.30% GO
PBAT0.50% GO
Gas permeability analyses are still in process
I hope that Polymers and 2D Materials
keep their love forever…...
Many grandchildren should be born from
this relationship .....
MackGraphe began its activities in 2013 with funding (~US$ 20 millions) from the Mackenzie Presbyterian Institute; FAPESP and CNPq.
Its headquarters building opened on 2 march 2016.
3 areas of interest: Photonics, Energy, Composite materials
About MackGraphe(Graphene and Nanomaterials Research Center)
Seminar room
Offices
Photonics
Energy
Nanocomposites
Clean room,
CVD lab and
multiuser labs
Spin offs
Admin.
Positions available!
MackGraphe
39
https://www.youtube.com/watch?v=0ivEFgbYRy0&t=12s
Research Group
Maiara Araújo
(MSc student)
Gabriela
(MSc student)
Camila Celis
(PhD student)
Mariana Ferraz
(PhDc student)Lícia Maestrelli
(PhD student)
Michele
(MSc student)
Pablo Riveros
(Post-doc)
Gabriel P.
(MSc student)
Éder Henrique
(MSc student)
Gabriel G.
(MSc student)
Acknowledgements
Thank you for your attention!