lighter, stronger, better: composites and graphene …...• gfrc tanks made with 0.5wt% matrix 204...

Confidential. Commercial secret of OCSiAl Europe S.A.R.L.1, rue de la PoudrerieL–3364 LeudelangeGrand Duchy of Luxembourg

Lighter, Stronger, Better:Composites and Graphene Nanotubes

1

Founded 2009, 350 employees, headquartered in Luxembourg

World biggest SWCNT producer with 10t/year since 2015

World first REACH-registered SWCNT producer since 2016

World first high-quality & economically viable SWCNTs mass produced

TUBALLTM SWCNT I Overview l OCSiAl 2018

OCSiAl = Core Data

TUBALLTM

Production capacity in t/year

60 t

10 t

1 t

310 t

3000 t

2015 2016 2017-18Years

GR

AP

HE

TR

ON

2.0

50

to

ns

2019-22 20XX

GR

AP

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TR

ON

1.0

10

to

ns

Lu

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mb

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rg p

rod

ucti

on

pla

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25

0 t

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10 t

60 t

310 t


1 t

1 OCSiAl = Production Capacity

Novosibirsk

Columbus

Moscow

Tel-Aviv

India

Seoul

Hong Kong

China

Sales Office

Luxembourg Manufacturing (2019-22)

Luxembourg

Headquarters


Novosibirsk Manufacturing

1 OCSiAl = Locations

TUBALLTM 3D network

SEM

im

ages

SW

CN

T in p

ow

der

form


TUBALLTM-SWCNTs are made from one single graphene sheet and can be described as „Graphene Nano-Tubes“

2 TUBALLTM = Quality & Network

Brandname TUBALLTM

Thickness 1 atom

Diameter 1.6 nm +/- 0.4

Specific surface area 1200 m²/g

Length > 5μm

Length/Diameter ratio 5000

Morphology Flexible


2 TUBALLTM = Dimensions & Distribution

TUBALLTM morphology (long + flexible) enables ultra low loadings starting from 0.01wt%

Ultra low loadings enable improvements without damaging product own properties

Distribution2/3 semiconducting & 1/3 metallic

Ultra low loadings

Electrical conductivity 103 S/cm


Thermal conductivity 6600W/(m∙K)

Thermal resistance 1000 °C

Tensile strength 55 GPa

Elasticmodulus 5,5 TPa

Corrosion & corrosive chemicals

inhibitor

UV-waves & radiationsabsorber

Starting from 0.01wt% loading level

2 TUBALLTM = Core Properties

Permanent, stable & homogenous electrical conductivity

Mechanical properties improvements

Colour maintenance

3 main improvements

In any case TUBALLTM delivers improvements at 10 to more than 1000 times lower concentrations


Needed loading rates to reach the percolation threshold in an elastomer formulation

COMMERCIALFILLERS

Graphite 10 – 15wt%

TUBALLTM SWCNT

0.01 – 0.5wt%

SilverAluminium

20 – 35wt%

NickelNickel-Graphite

22 – 40wt%

Carbon black 25 – 55wt%

Graphene 0.1 – 5wt%

NANOMATERIALS

MWCNT 1 – 6wt%

Carbon fibers 2 – 8wt%

Cellulose Nanowhiskers

3 – 10wt%

2 TUBALLTM = Ultra Efficiency

TUBALL™ IN COMPOSITES: MECHANICAL PROPERTY IMPROVEMENTS

POLYMER COMPOSITE RESISTANCE MODELS

Fiber (longitudinal)Modulus of elasticity: 165 GPaPoisson ratio: 0.28Extension before rupture: 2%

Phase boundary

Polymer matrixModulus of elasticity: 3.93 GPaPoisson ratio: 0.45

Boundary fiber-resin

Fiber (transversal)Modulus of elasticity: 15 GPaPoisson ratio: 0.20F F

Prof. Bodo Fiedler et al.

• Adhesion: crack initiation on

the boundary of fiber–resin

phase

• Cohesion: crack propagation in

the polymer matrix

160 µm

Equivalent stress σvM in MPa

Applie

d s

train

ε %

POLYMER COMPOSITE DESTRUCTION MECHANISMS

Prof. Bodo Fiedler et al.

Standard polymer composite Polymer composite with CNT

• Extraction of carbon nanotubes from the matrix

• Change in the direction of crack growth

• Linear crack development

SEM photographs: Joel S. Fenner et al. Hybrid nanoreinforced carbon/epoxy composites

for enhanced damage tolerance and fatigue life. Composites: Part A 65 (2014) 47–56

NANOMODIFIED POLYMER MATERIALS

Introduction in polymer matrix Application on the fiber surface

Dispersed CNTs create an electrically conductive and reinforcing network in the polymer matrix

2 µm

• Increasing the resin adhesion to fiber• Distributing the mechanical strain at the polymer–fiber

phase boundary

CNT INTRODUCTION METHODS IN POLYMER COMPOSITE

Interlaminar ShearASTM D2344. Short-Beam Strength of Polymer Matrix Composite

Materialsand Their Laminates

Fracture ToughnessASTM D5528-13. Mode I Interlaminar Fracture Toughness of Unidirectional

Fiber-Reinforced Polymer Matrix Composites

Studied properties

TUBALL™ FOR ADDING STRENGTH TO POLYMER COMPOSITES

Materials for polymer composite production

• Fiberglass Armaton QX-1200 (0°/+45°/90°/−45°)• Armatonnon-saturated polyester resin PN-609-21M• CUROX 302 solidifier, cobalt octoate (1%)

Composite plates production method

Hand lay-up followed by hot pressing for 150 minutes, with 5 bar pressure and 30–140°C temperature range

Colin P 200 PV press for polymerization of composite plates

POLYMER COMPOSITE SAMPLE PREPARATION

MECHANICAL PROPERTIES OF FIBER COMPOSITES:

TUBALLTM POTENTIAL

+5–10%improvement

+20–60%improvement

Neat composites

TUBALLTM

Testing machine: Shimadzu AGS-20kNSpecimen size: 40×12×6 mmLoad speed: 1 mm/minute

<<< : position in the testing machine

GFRP: INTERLAMINAR SHEAR STRENGTH (ASTM D2344)

• With 0.15 wt.% of TUBALL™, the GRP polymer composite strength for interlaminar shear increased by 48%

GFRP: FRACTURE TOUGHNESS (ASTM D5528-13)

Testing machine: Shimadzu AGS-20kNSpecimen size: 40×12×6 mmLoad speed: 1 mm/minute

<<< Specimen position in the testing machine

• With 0.05 wt.% of TUBALL™, the GRP polymer composite fracture toughness increased by 51%

Neat

INCREASED IMPACT RESISTANCE

Neat

INCREASED IMPACT RESISTANCE

Material = Vinyl ester SMC +30% glass

Material = Polyester SMC +0.1% Matrix 201 +30% glass

Top Side Top Side

Bottom Side Bottom Side

Results at a car supplier:Better crash performance, even with less expensive resin, when the composite is

TUBALL™ modified.

Grey graph: Neat specimen with 45° fibersPink graph: Specimen with 45° fibers and 0.05 wt% SWCNTs

Black graph: Neat specimen with transverse fibersRed graph: Specimen with transverse fibers and 0.05 wt% SWCNTs

Plot:

Maximum creep compliance difference (J0 – J20) plotted over

applied stress level ( 𝜎𝑚𝑎𝑥𝜎𝑐

) for the transverse and 45° samples in

dependence of the tensile strength→ Small J0 – J20 → Higher creep resistance

Specimen with transverse fibers

Specimen with 45°fibers

Applied stress level in % compared to failure strength

Creep compliance difference

→ Small J0 – J20 means high creep resistance

INCREASED CREEP RESISTANCE

Specimens with transverse fibers:

65 % of UTS → 12.5 % less creep for SWCNT mod. CFRP

80 % of UTS → 33 % less creep for SWCNT mod. CFRP

90 % of UTS → 50 % less creep for SWCNT mod. CFRP

Strong improvement of creeping resistance

Specimen with 45° fibers:

Smaller effect of improvement by SWCNT modification

Reasons:1. Fibers with 45° angle carry part of the load → CNTs

less impact2. Shear loading less critical than pure tension for the

polymer matrix


Creeping properties improvement by SWCNTs:

1. Creep resistance increased in transverse direction in form of the creep compliance up to 50%

2. Less improvement for 45° orientated CFRP3. Relationship between applied stress and the difference of the

resulting creep compliance was shown:→ Higher applied loadings result in better creep

properties for SWCNT modified CFRP

Further possible effects:

1. Higher TUBALL content could intensify the creeping effect

2. Effect might enhance under elevated temperature or moisture

3. SWCNTs could improve the creeping properties even more for polymer systems of less strong and stiff thermoplastics

Great, as creeping mostly occurs at high stress


Polymer：PC Lopuy 1200-22Process : D36，L/D=40, T=280-300, Screw RPM=300Injectionforce=120T,T+280-300C, Speed=20%, Press=15-20%, Tooling T=40C

<<< sample

Benefit VS 10% Glass Fiber • Perfect Surface• Good Toughness• Can be colorful• Better flexible

NEAT PC TUBALL™ (Matrix P861) Glass Fiber Reinforced

TEST 0.10% 0.20% 0.30% 10%

MI (300/1.2) ASTM D 1238 22 19.2 15.3 12.1 13

Tensile Young Modulus, MPA ASTM D 638 2300 2480 2610 2668 -

Tensile strength(Yield), MPA ASTM D 638 60 67 71.3 74.1 78

Break elongation, % ASTM D 638 120 88 67 44 20

Flexural Modulus, MPA ASTM D 790 2410 2820 4340 5420 3530

Flexural strength, MPA ASTM D 790 96 100 108 115 127

Impact (Notched) , J/M ASTM D 256 750 690 520 98 69

RESULTS: THERMOPLASTIC COMPOSITE

Flexural modulus +17%

Hammer impact +14%

Weight of bicycle frame reduced from 750 gr to 600 gr

CARBON FIBER BICYCLE FRAME

TUBALLTM 0.1 wt.% in final composite.

No influence on customers’ formulation on the production line.

INDUSTRIAL CASE

COMPOSITES: Introducing TUBALL™ with sizing

Fiber without sizes Fiber with sizes

STRUCTURAL HEALTH MONITORING FOR COMPOSITES

Practical Application: Structural Health Monitoring for Composites

Main problem of composite materialsis the calculation of the endurance ofthe composite.

To overcome this issue, a permanent structural health monitoring of thecomposites would be a breakthroughfor structural composite applications. For example, in the aircraft, automotive or sports leisure industry.


4 COMPOSITES APPLICATION = SMC electric components

More applications available in the PDF “Success Stories”

COMPANYMahindra CIE, India

PRODUCTSMC electric components made with 0.07wt% MATRIX 204instead of 6wt% carbon black

APPLICATIONAnti-static circuit breakers, junction boxes, electronics cases and housing

KEY BENEFITS• Surface resistivity of 10⁶–10⁸ Ω/sq• Permanent, stable and homogenous anti-static properties without “hot spots”• Bright colours, including white, are possible• Original flame retardancy is maintained


4 COMPOSITES APPLICATION = GFRC rebars


COMPANYPolyCompozit Ltd, Russia

PRODUCTGFRC rebars made with 0.8wt% MATRIX 201 mixedin EP resin to improve mechanical properties only tape

APPLICATIONAlternative to steel in concrete reinforcement

KEY BENEFITS• Tensile strength increased by up to 30%• Maximum working temperature increased by up to 15% • Lightweight and non-corrosive material


4 COMPOSITES APPLICATION = GFRC tanks & pipes


COMPANYIdentity covered by NDA, Europe

PRODUCT• GFRC tanks made with 0.5wt% MATRIX 204 instead of 15wt% CB• GFRC pipes made with 0.2wt% MATRIX 301 instead of 4wt% CB

APPLICATIONAnti-static tanks & pipes for storage/transport of flammable/dangerous goods

KEY BENEFITS• Volume resistivity of both tanks & pipes < 106 Ω·cm• Permanent, stable & homogenous anti-static properties without “hot spots”• Resistivity is independent of humidity• Clean manufacturing process without carbon black powder or dust• Pipes hydrostatic pressure increased by up to 15%


4 COMPOSITES APPLICATION = Honeycomb structures


COMPANYIdentity covered by NDA, Asia

PRODUCTConductive honeycomb made with 10wt% MATRIX 205instead of iron-oxide Ferrite

APPLICATIONEMI shielding of airplanes structures

KEY BENEFITS• Cost reduction• Wave absorption improved• Lowest point frequency ≤ 4GHZ


4 COMPOSITES APPLICATION = FRP cable trays


COMPANYIdentity covered by NDA, Asia

PRODUCTFRP cable trays made with 0.1wt% MATRIX 201instead of 5wt% conductive carbon black tape

APPLICATIONAnti-static trays for electric & data cables in ATEX environment

KEY BENEFITS• Surface resistivity < 10⁸ Ω/sq• Permanent, stable & homogenous anti-static properties without “hot spots”• Various colours are possible• No negative effect on mechanical properties or surface quality


4 APPLICATIONS = Overview

• TUBALLTM production is certified ISO 9001 : 2015Certificate n°31100940 QM15 available since December 2017

• TUBALLTM production is certified ISO 14001 : 2015Certificate n°31100940 UM15 available since December 2017


5 EHS & QUALITY = ISO & OHSAS certifications

• TUBALLTM production is certified BS OHSAS 18001 : 2007Certificate n°31100940 BSOH available since December 2017

Anastasiya Zagoruyko / Quality Assurance Manager / +7 913 956 10 10 / [email protected]

Quality-related issues

• TUBALLtm is REACH-registered for sales up to 10 tons

Registration n°01-2120130006-75-0000

• TUBALLtm REACH-registration for sales up to 100 tons started in 2017

Registration awaited in 2019


5 EHS & QUALITY = REACH registration

Gunther Van Kerckhove / H&S lead Manager / +352 661 183 429 / [email protected]

EHS-related issues

• BAUA will start in Q1/2018 a new R&D program to develop criteria for assessing the toxicological impact of carbon fibrous material

• OCSiAl will cooperate with the BAUA (Federal Institute for Occupational Safety & Health9 in the field of toxicological investigations and dustiness tests on TUBALLTM


5 EHS & Quality = Compliance & cooperation

• TUBALLtm passed the mandatory nanomaterial registers in France & BelgiumFrance declaration number: XS969-2016-07617722

• OCSiAl also co-operated with the Belgium authorities on a range of issues, including estimating types, quantities, applications of nanomaterials, as well as managing the risks associated with the substances

• Registered nanomaterials are given a single identification number that follows them all the way through the supply chain.

• OCSiAl submitted the EPA a pre-manufacture notice (PMN) in Q1/2017 to be registered on the TSCA inventory in S1/2018 Submission number: P-17-0257

• PMN submissions require all available data on:Chemical identityProduction volumeByproductsUseEnvironmental releaseDisposal practicesHuman exposureExisting available test data…


5 EHS & Quality = TSCA registration

Presentation and contents are intellectual property of OCSiAl. Copy or transmission withoutOCSiAl authorization forbidden.

THANK YOU!

OCSiAl Europe S.à r.l. 1, rue de la Poudrerie3364 Leudelange, Luxembourgwww.ocsial.com

[email protected]+352 661 184 008

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