The amazing meeting between polymer world and two-dimensional

materials

Guilhermino José Macêdo FechineMackGraphe

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

4,0x103

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!