Lighter, Stronger, Better: Composites and Graphene …...• GFRC tanks made with 0.5wt% MATRIX 204...
Transcript of 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
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2.0
50
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2019-22 20XX
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1.0
10
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10 t
60 t
310 t
TUBALLTM SWCNT I Overview l OCSiAl 2018
1 t
1 OCSiAl = Production Capacity
Novosibirsk
Columbus
Moscow
Tel-Aviv
India
Seoul
Hong Kong
China
Sales Office
Luxembourg Manufacturing (2019-22)
Luxembourg
Headquarters
TUBALLTM SWCNT I Overview l OCSiAl 2018
Novosibirsk Manufacturing
1 OCSiAl = Locations
TUBALLTM 3D network
SEM
im
ages
SW
CN
T in p
ow
der
form
TUBALLTM SWCNT I Overview l OCSiAl 2018
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
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
INCREASED CREEP RESISTANCE
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
INCREASED CREEP RESISTANCE
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.
TUBALLTM SWCNT I Overview l OCSiAl 2018
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
4 COMPOSITES APPLICATION = GFRC rebars
More applications available in the PDF “Success Stories”
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
4 COMPOSITES APPLICATION = GFRC tanks & pipes
More applications available in the PDF “Success Stories”
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%
TUBALLTM SWCNT I Overview l OCSiAl 2018
4 COMPOSITES APPLICATION = Honeycomb structures
More applications available in the PDF “Success Stories”
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
4 COMPOSITES APPLICATION = FRP cable trays
More applications available in the PDF “Success Stories”
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
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
TUBALLTM SWCNT I Overview l OCSiAl 2018
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…
TUBALLTM SWCNT I Overview l OCSiAl 2018
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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