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TUBALL™ SINGLE WALL CARBON NANOTUBES IN SILICONE APPLICATION
OCSIAL 2018
INTRODUCTION
1.Electrically conductive fillers for silicones can lead to a number of negativetrade-offs in flexibility and elasticity, resulting in hardening and a reduced lifecycle for the final products
2. Single wall carbon nanotube (SWCNT) additives have been shown tosignificantly improve mechanical and conductive properties in elastomers inextremely low concentrations
3. Previous work has incorporated SWCNT using various approaches in mixingand compounding
1. Mixing: ultrasonication, calendering, ball milling, shear mixing, and extrusion
2. Compounding: solution mixing, melt blending, in situ polymerization, latextechnology
4.However, these approaches are not scalable. This presentation highlights aninvestigation of SWCNT into LSR, RTV compounds using a new nanotubeconcentrate based on SWCNT and commonly used plasticizers.
SINGLE WALL CNT
~ 4 µm
~ 2 nm
LENGTH
DIAMETER
GRAPHENEGRAPHENENANOTUBE
TUBALLTM
SINGLE WALL CARBON NANOTUBES
Length – 5-10 μm, >5000 length to width ratio, more than for any other material
Remarkable mechanical properties
SWCNTs form electrically conductive 3D network in media at extremely low concentrations as <0.2%. This is the reason to use SWCNT as conductive agent.
Example: percolation threshold in elastomers (for electrical conductivity)
SWCNT PROPERTIES
METAL FILLERS 15-35%
CARBON BLACK 10-40%
MWCNT 1-6%
SWCNT 0.01-0.5%
CARBON FIBERS 3-12%
DISPERSION VISUALIZATIONBY PARTICLE TYPE
ONLY SWCNT FORMS THEIR OWN CONDUCTIVE 3D NETWORK AT ULTRA-LOW CONCENTRATIONS
The same concentration of particles (~0.1%)in the samevolume
MICROPARTICLES CARBON FIBERS SWCNT
200 nm
SWCNT USED IN THIS STUDY CHARACTERISTICS
Property TUBALL™ SWCNT Measurement
Carbon content, wt. % > 85
CNT content, wt % > 80
Number of layers CNT 1
Outer mean diameter, nm 1.6 ± 0.4
Length of CNT, µm > 5
Metal impurities, wt % < 15
CONDUCTIVE SILICONE ELASTOMERS(HCR, LSR and RTV)
TESTING A NEW NANOTUBE CONCENTRATEVS. CURRENT CONDUCTIVE ADDITIVES
1.Carbon black, carbon fiber, graphite, MWCNT based solutions causes dramatically degradation of mechanical properties, coloration and compounding issues due to high loading
2.New Approach tested a pre-dispersed concentrate of SWCNT
1.Result of $80 million investment into R&D by OCSiAl
2.Using the #1 SWCNT brand, 10 ton production capacity (80% of global)
3. Additional 50 ton reactor in development for future-proofing
SWCNT CONCENTRATES FOR SILICONESTESTED IN THIS STUDY
Carrier: polydimethylsiloxane and vinyl-terminated oil
For LSR and RTV siliconesSize of particles 30-40 μm
Neat0.01%
TUBALLTM
• ASTM D991Electrical conductivity
• ASTM D2240Hardness
• ASTM D412Tensile Strength
• ASTM D412Elongation
• ISO-34:2015, die A
Tear Strength
• ASTM D991Electrical Conductivity
• ASTM D412Tensile Strength
• ASTM D412Elongation
• ASTM D412Modulus
LSR Test:“Compound A”
PDMS
RTV Test:“Compound B”
PDMS
SWCNT concentrate in LSR & RTV
2 TESTS IN LSR AND RTV
MECHANICAL AND CONDUCTIVE PROPERTIES
TESTING PROTOCOLCHARACTERIZATION SEM
CONDUCTIVITY & HIGH MECHANICAL PROPERTIES
TEST #1
COMPOUND ALSR 6360 AND TUBALLTM MATRIX 601
TESTING PROTOCOLMIXING AND CURING
MIXING STAGE 1: MASTERBATCH PREBLENDING
Recipe LSR 6360 (Elkem Xinghuo Silicones, Shore A 60) + TUBALL™ MATRIX 601 4wt.%
Equipment 3-Roll Mill Type Sower-150. Separate mixing for part A and B with MATRIX 601
Process Gap 80/40 μm , <3> Passes
MIXING STAGE 2: MASTERBATCH PREBLENDING
Recipe Part A (mixed with MATRIX 601) + Part B (mixed with MATRIX 601)
Process Step 1 3-Roll Mill Type Sower-150. Mixing part A and B
Process Step 2 Gap 80/40 μm , <3> Passes
CURING PROTOCOL
Process Vulcanizing Press: 200 kgf/cm2, 177°C, 7 minPost curing 200°C, 4 hours
PHYSICAL PROPERTIES OF CONDUCTIVE LSR WITH 4% TUBALLTM MATRIX 601
Customer functional test
* Tested in LSR 6360 (Bluestar Silicones)
2,12,4
М50, MPa
520
Tensile strength,MPa
490510
10
18
Elongation at break,%
+14%
-6%+80%
8,4 8,0
Tear strength, kN/m
-5%
60 59
Hardness, Shore A
Volume resistivity
LSR 6360 1014 Ω∙cm
LSR 6360 + 4% TUBALL™ MATRIX 601
80 Ω∙cm
MECHANICAL & ELECTRICAL PROPERTIES
TEST #2
COMPOUND BSWCNT VS CONDUCTIVE CARBON BLACK IN RTV
MIXING STAGE 1: MASTERBATCH PREBLENDING
Recipe RTV Neukasil RTV 230, Neukasil crosslinker A149 (Altropol) + TUBALL™ MATRIX 601 3wt.%, Conductive carbon black VULCAN® VXC72R
Equipment Overhead stirrer
Process Dispersing of MATRIX 601 in part A - 2000 rpm, 30 minutes; Mixing with part B - 1000 rpm, 20 minutes
MIXING STAGE 2: CARBON BLACK DISPERSING
Recipe Part A (mixed with VULCAN® VXC72R ) + Part B (mixed with VULCAN® VXC72R )
Process Step 1 Overhead stirrer
Process Step 2 Dispersing of carbon black in part A and B separate - 500 rpm, 20 minutes; Mixing with part B - 1000 rpm, 20 minutes
CURING PROTOCOL
Process Vacuumed for 1–2 minutesRoom temperature 24 hours
TESTING PROTOCOLMIXING AND CURING
PHYSICAL PROPERTIES OF RTV WITH 3% TUBALLTM MATRIX 601 IN COMPARISON WITH 15% CONDUCTIVE CARBON BLACK
Customer functional test
0,53
0,69 0,82
М100, MPa
5
0,9
Tensile strength,MPa
4510
420
100
Elongation at break,%
+30% +55% -20% -82%-18% -80%
2,4
2,6
М300, MPa
+8%
* Tested in two component RTV. Study was conducted with conductive carbon black VULCAN® XC72R by Cabot
RTV base
15% Conductive carbon black*
3% TUBALL™ MATRIX 601
Volume resistivity 100-200 Ω∙cm
Контроль
2.6%
TUBALLTM MATRIX 604
ELECTRICAL PROPERTIES
OF RTV WITH
TUBALLTM MATRIX 601
IN COMPARISON WITH
CONDUCTIVE CARBON
BLACK
R&D И IP
* Tested in two component RTV. Study was conducted with conductive carbon black VULCAN® XC72R by Cabot
SWCNT IN LSR AND RTV-BASED COMPOUNDS
TESTING SUMMARY
MAJOR INCREASE OF TEAR AND MAINTAINING TENSILE STRENGTH WITHOUT TRADE-OFF ON FLEXIBILITY QUALITIES (HARDNESS, ELONGATION) FOR CONDUCTIVE APPLICATIONS
TUBALL™ MATRIXFEATURES
• For anti-static, static dissipative and conductive
applications
• Extremely low loadings of TUBALL™ that
preserve properties
• Retain mechanical properties including softness
• Maintain rheology of the uncured compound
• Standard processing and mixing equipment
• Enables colored ESD compounds TUBALL™ MATRIX 601 for LSR & RTVTUBALL™ MATRIX 602 for HCR & LSRTUBALL™ MATRIX 605 for HCR
REACH certification is Registration, Evaluation, Authorisation and Restriction of Chemicals
First and only SWCNT completed
TUBALL™ is registered under the number 01-2120130006-75-0000
Allows to commercialize up to 10 tonnes in EU
REACH CERTIFIED (EU)
EPA is United States Environmental Protection Agency
Allows to commercialize up to 25 tonnes in US
Wide range of applications
Reasonable regulations of safety, transportation and disposal
EPA CONSENTED (USA)
TUBALL™ FOR SILICONE: COMPOSITION & MANUFACTURING
LSR HCR
Production steps:• premixing with a SpeedMixer• 3-roll mill or Planetary mixer • Homogenization
Production steps (2-roll mill):• Introduction directly to mills,
pre-dispersion• Homogenization
COLORED ANTI-STATICSILICONE RUBBER
Volume resistivity103-1011 Ω•cm
TUBALLTM 0.2-0.01 wt.%
COLORED ANTI-STATIC SILICONE RUBBER
Coating forcleanroom factories0.1%
Printing rollers0.06%
Watchband for smart watch0.04%
Cable jacketing0.01%
*
TUBALLTM, wt.%
Tested in two component RTVor HCR based compounds. Measurements conducted according to ASTM D991 standard.
0.1 0.2 0.3
CABLE CONNECTORS OUTER CONDUCTIVE LAYER
REQUIREMENTS
Outer layer — surface resistivity 5000 Ω/sq
R&D И IP
MECHANICAL PERFORMANCE• Longer cycle life• Good quality of surface
TURNING POINT• Graphite dispersion in toluene
(25% solid) replaced with 5% TUBALL™ MATRIX 601
• Easier processing vs. Graphite dispersion
• Cost effective spray technology in comparison with molding
Cable connectors / Application case
T-connectors
Cold shrink connectors CONDUCTIVE PERFORMANCE• 5000 Ω/sq• Stable and consistent for expanded parts
CONNECTING CABLE SLEEVE
Elastomers / Application case
REQUIREMENTSVolume resistivity < 100 Ω×cm
YIELD• 20-50% Carbon black replaced with 5% TUBALL™ MATRIX 605 for HCR or 5% TUBALL™ MATRIX 601 in LSR• Easier processing vs. high carbon black loading
MECHANICAL PERFORMANCE• Reduced the required loading of conductive filler• Longer cycle life, due to better mechanical properties
CONDUCTIVE PERFORMANCE• Stable electrical resistivity < 100 Ω×cm
Inner layer connecting cable sleeve
PRINTING ROLLERS PLATES
PRODUCTPrinting rollers, plates, anti dusting colorful coating for electronics and consumer goods
R&D И IP
MECHANICAL PERFORMANCE• Maintaining mechanical
properties• Longer cycle life• Enabling coloration
TURNING POINT• Stable conductivity with 1-2% TUBALL™ MATRIX
Elastomers / Application case
SUCCESS MARKET APPROACH:• Korea, China,Taiwan
CONDUCTIVE SILICONE GREASE
Main Properties: • Stable conductivity below 100 Ohm with 10% of TUBALL™
MATRIX • Optimal viscosity in combination with high conductivity• Cost effective and not cost sensitive • Compatible with flame retardant and other additives
Application: Industrial machinery, Electronics, Electric cars
PARTNERS PRODUCTS COLORED MASTERBATCH FOR HCR
Designed for use in a variety of molded and extruded goods for electrical conductive and anti-static goods (colorable) such as OA roller, Sheet, Pad, Gasket, Hose, Cable
ANTI-STATIC COATING & PSA
FLEXIBLE DISPLAYS ANTI-STATIC FILMS ANTI-STATIC TAPES
ANTI-STATIC LABELS
SILICONE RELEASE FILM AND TAPE
• Excellent compound ability with water and solvent
• Low dosage, high level high transparency• Stable surface resistance, not degradation with
time, temperature and moisture • Easy to use, one time coating technology, reduce
customer’s coating process
TUBALL™ FOR CONDUCTIVE APPLICATION
Dispersion Process via high speed mixer• Silicon Gum＋ TUBALL™ MATRIX 601 • Add 80% Toluene• No Surfactant
OCSiAl RESULTS
0.4 wt.% TUBALL™ MATRIX 601 in Silicon based PSA 20% Solid
PRESSURE-SENSITIVE ADHESIVE FILM
Elastomers / Application case
REQUIREMENTSSurface resistivity 107 Ω/sq
YIELD• 2 layer conductive system replaced with a single conductive silicone containing 0.4% TUBALL™ MATRIX 601• Excellent wet-out performance
MECHANICAL PERFORMANCE• High adhesive force• Low curing temperature
CONDUCTIVE PERFORMANCE• 107 Ω/sq• Stable and consistent
PRODUCTPSA anti-static film for protect screen, flexible display, labels & tapes
CONTACT INFORMATION
OCSiAl ASIA PACIFIC CO., LTD.
Office 208, Pilot Plant Bldg., Incheon Technopark12, Gaetbeol-ro, Yeonsu-gu, Incheon 406-840 Korea
+82 32 260 [email protected]
OCSiAl LLC
500 S Front St, Suite 860, Columbus, OH 43215
+1 415 [email protected]
OCSiAl Private Limited
A504 Universal Business Park, Ansa Industrial Estate, Chandivali Andheri East, Mumbai 400072, MH India
+91 22 [email protected]
OCSIAL Europe Sàrl
1, rue de la PoudrerieL 3364 LeudelangeLuxembourg
+352 [email protected]
