The amazing meeting between polymer world and two-dimensional - - PowerPoint PPT Presentation

The amazing meeting between polymer world and two-dimensional materials

Guilhermino José Macêdo Fechine

MackGraphe Universidade Presbiteriana Mackenzie www.Mackenzie.br/mackgraphe.html guilherminojmf@mackenzie.br

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 4,0x10

3

8,0x10

3

1,2x10

4

1,6x10

4

LDPE HDPE PS PLA PVDF-TrFE

Complex viscosity (Pa.s) Temperature (

• C)

120 140 160 180 200 4,0x10

3

8,0x10

3

1,2x10

4

1,6x10

4

LDPE HDPE PS PLA PVDF-TrFE

Complex viscosity (Pa.s) Temperature (

• C)

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

Melt mixing

Solvent method

In situ polimerization

Melt mixing

• 3. Challenges involved?

Process parameters Filler content Filler dispersion Filler homogeneity

Ou Our strate tegies gies

Solid-Solid Deposition Liquid-Phase Feeding

”PS and mGO as templates”

Ou Our strate tegies gies

• 2D dispersion production;
• Characterization;
• The insertion of the 2D filler

in to the polymer is carried

• ut based on pre-exfoliated

particles

Characterization of Graphite Oxide (GrO)

10 20 30 40

Intensity (a.u.) 2 (°)

Gr Gr-O 11.34° 26.26° 100 200 300 400 500 600 700 800 900 1000 20 40 60 80 100

Weight (%) Temperature (° C)

Gr Gr-O 500 1000 1500 2000 2500 3000

Intensity (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

Proces

• cessing

sing param amet eter ers

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

50 100 150 200 10 20 30 40 50 60

without GO 0,05% GO 0.1% GO 0.5% GO

Stress (MPa) Strain (%)

PP + mGO

500 1000 1500 2000 2500 3000 3500 without GO 0,05% GO 0,1% GO 0,5%GO

E [MPa]

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

100 200 300 400 500 600 700 800 900 1000 5 10 15 20 25 30 35 40

Tensao (MPa) 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 component Dispersive component Polar component

Films

PBAT (Ecoflex) + GO

Neat PBAT PBAT 0.05% GO PBAT 0.10% GO PBAT 0.30% GO PBAT 0.50% 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!