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Polymer Applications

C4IR Conference Series 2017

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Applications of NanoDiamond in
Thermally Conductive / Electrically Nonconductive
Polymers
15th Anniversary HVM 2017 & 4th Graphene New Materials Conference
2-3 November 2017 Cambridge, UK
www.cir-strategy.com/events
Gavin Farmer – Carbodeon / Business Development
Carbodeon in Brief
•  uDiamond® NanoDiamonds
•  >12 M€ investment in NanoDiamond production and application
technologies
•  Offering
•  For Engineering polymers
–  20-200% improvement in thermal conductivity
–  Tailored glass transition temperature
–  Significant improvements in compound mechanical properties
•  For Wear and corrosion resistant metal coatings
–  >200% improvement in electroless nickel coating wear
resistance, without impairing friction or corrosion properties
•  For Industrial polymer coatings
–  Fluoropolymer coatings with doubled wear resistance,
improved corrosion resistance and tailored friction properties.
–  Transparent coatings with improved wear and corrosion
resistance, without impairment of optical properties
•  USP’s
•  High performance with very low NanodDiamond loadings, easy to use
and implement to current production processes, cost efficient
•  Industrially applied
•  IP
•  Both product line and key applications are IP protected
w HQ in Finland, Helsinki Region
w Established 2006
w 10 employees
w Sales on 4 continents
Carbodeon in Brief
Artwork: Nancy Farmer / www.nancyfarmer.gallery
Nanodiamond Material
Nanodiamonds - Snapshot
Sp3 Diamond Core
With functional groups
Extreme Hardness
Graphitic facets
Electrically Insulating
Extreme Thermal Conductivity
Optical properties
Competitors
w  Detonation produced 4-6 nm
particles
w  Base technology invented
1963 – not “getting there”
w  Carbodeon disruptive
technologies realizing the
industrial potential
w  Able to manufacture and
utilize the primary particles
w  “Less is More”
Application Dependent Surface Chemistry and Morphology
Powder	grades	 Surface	 Zeta	poten3al	 Solid	content**	
Molto	 Mul3-func3onalized	 Slightly	nega3ve	 100	wt.%	
Vox	P	 Carboxylated	 Highly	nega3ve	 100	wt.%	
Hydrogen	P	 Hydrogen	terminated	 Highly	posi3ve	 100	wt.%	
Amine	P	 Amine-fucn3onalized	 Highly	posi3ve	 100	wt.%	
Dispersion	grades	 Surface	 Zeta	poten3al	 Solid	content	
Vox	D,	in	water	 Carboxylated	 Highly	nega3ve	 5	wt.%	
Vox	D,	in	NMP	 Carboxylated	 Highly	nega3ve	 2	wt.%	
Vox	D,	in	DMA	 Carboxylated	 Highly	nega3ve	 2	wt.%	
Hydrogen	D,	in	water	 Hydrogen	terminated	 Highly	posi3ve	 2.5	wt.%	
Hydrogen	D,	in	ethyl	glycol	 Hydrogen	terminated	 Highly	posi3ve	 4	wt.%	
Hydrogen	D,	in	GBL	 Hydrogen	terminated	 Highly	posi3ve	 3	wt.%	
Hydrogen	D,	in	NMP	 Hydrogen	terminated	 Highly	posi3ve	 3	wt.%	
Hydrogen	D,	in	NEP	 Hydrogen	terminated	 Highly	posi3ve	 2	wt.%	
Hydrogen	D,	in	DMA	 Hydrogen	terminated	 Highly	posi3ve	 3	wt.%	
Amine	D,	in	water	 Amine-func3onalized	 Highly	posi3ve	 0.5	wt.%	
Amine	D,	in	NMP	 Amine-func3onalized	 Highly	posi3ve	 3.0	wt.%	
Amine	D,	in	ethyl	glycol	 Amine-func3onalized	 Highly	posi3ve	 3.0	wt.%	
Amine	D,	in	GBL	 Amine-func3onalized	 Highly	posi3ve	 3.0	wt.%	
Amine	D,	in	DMA	 Amine-func3onalized	 Highly	posi3ve	 2.0	wt.%	
COOH
H
NH2
Specialty	Addi3ve	Grades	 Surface	 Zeta	poten3al	 Solid	content	
Pla3ng	Addi3ve	 Proprietary,	in	water	 Highly	posi+ve	 2	wt.%	
Fluoropolymer	coa3ng	addi3ve	 Proprietary,	in	GBL	 Highly	posi+ve	 0.5	wt.%
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Polymer Applications

  • 1. Applications of NanoDiamond in Thermally Conductive / Electrically Nonconductive Polymers 15th Anniversary HVM 2017 & 4th Graphene New Materials Conference 2-3 November 2017 Cambridge, UK www.cir-strategy.com/events Gavin Farmer – Carbodeon / Business Development
  • 2. Carbodeon in Brief •  uDiamond® NanoDiamonds •  >12 M€ investment in NanoDiamond production and application technologies •  Offering •  For Engineering polymers –  20-200% improvement in thermal conductivity –  Tailored glass transition temperature –  Significant improvements in compound mechanical properties •  For Wear and corrosion resistant metal coatings –  >200% improvement in electroless nickel coating wear resistance, without impairing friction or corrosion properties •  For Industrial polymer coatings –  Fluoropolymer coatings with doubled wear resistance, improved corrosion resistance and tailored friction properties. –  Transparent coatings with improved wear and corrosion resistance, without impairment of optical properties •  USP’s •  High performance with very low NanodDiamond loadings, easy to use and implement to current production processes, cost efficient •  Industrially applied •  IP •  Both product line and key applications are IP protected w HQ in Finland, Helsinki Region w Established 2006 w 10 employees w Sales on 4 continents
  • 3. Carbodeon in Brief Artwork: Nancy Farmer / www.nancyfarmer.gallery
  • 5. Nanodiamonds - Snapshot Sp3 Diamond Core With functional groups Extreme Hardness Graphitic facets Electrically Insulating Extreme Thermal Conductivity Optical properties Competitors w  Detonation produced 4-6 nm particles w  Base technology invented 1963 – not “getting there” w  Carbodeon disruptive technologies realizing the industrial potential w  Able to manufacture and utilize the primary particles w  “Less is More”
  • 6. Application Dependent Surface Chemistry and Morphology Powder grades Surface Zeta poten3al Solid content** Molto Mul3-func3onalized Slightly nega3ve 100 wt.% Vox P Carboxylated Highly nega3ve 100 wt.% Hydrogen P Hydrogen terminated Highly posi3ve 100 wt.% Amine P Amine-fucn3onalized Highly posi3ve 100 wt.% Dispersion grades Surface Zeta poten3al Solid content Vox D, in water Carboxylated Highly nega3ve 5 wt.% Vox D, in NMP Carboxylated Highly nega3ve 2 wt.% Vox D, in DMA Carboxylated Highly nega3ve 2 wt.% Hydrogen D, in water Hydrogen terminated Highly posi3ve 2.5 wt.% Hydrogen D, in ethyl glycol Hydrogen terminated Highly posi3ve 4 wt.% Hydrogen D, in GBL Hydrogen terminated Highly posi3ve 3 wt.% Hydrogen D, in NMP Hydrogen terminated Highly posi3ve 3 wt.% Hydrogen D, in NEP Hydrogen terminated Highly posi3ve 2 wt.% Hydrogen D, in DMA Hydrogen terminated Highly posi3ve 3 wt.% Amine D, in water Amine-func3onalized Highly posi3ve 0.5 wt.% Amine D, in NMP Amine-func3onalized Highly posi3ve 3.0 wt.% Amine D, in ethyl glycol Amine-func3onalized Highly posi3ve 3.0 wt.% Amine D, in GBL Amine-func3onalized Highly posi3ve 3.0 wt.% Amine D, in DMA Amine-func3onalized Highly posi3ve 2.0 wt.% COOH H NH2 Specialty Addi3ve Grades Surface Zeta poten3al Solid content Pla3ng Addi3ve Proprietary, in water Highly posi+ve 2 wt.% Fluoropolymer coa3ng addi3ve Proprietary, in GBL Highly posi+ve 0.5 wt.%
  • 7. Patent Finland PCT EPO USA Japan Korea China Russia India Products& production Blend Purification method     P P P   P     Carboxylated SDND G   P P P P P P   Hydrogenated SDND G   P P P P P P   Amine SDND G  P    P   P     Applications Thermoplastic ND containing thermal compounds G   G G P P P   P Polymer ND containing thermal compounds P   P P         Mechanically enhanced Fluoro-polymer Coatings, 1st application G   P G P P P     Metal coating, with SDND’s P  X    P           Mechanically enhanced Fluoro-polymer Coatings, 2nd application P                 7 P = Pending / P = Pending (posi+ve Official Ac+on( No+ce of Allowance G = Granted Carbodeon invested heavily in the IP protection of its developments over the entire supply chain •  The uDiamond® trademark is worldwide* registered •  The IPR are based upon a combination of 3 pillars: 1) Product 2) Production 3) Application * Worldwide: Finland, EPO, USA, Norway, India, Canada, Russia, Japan, China, South Korea Intellectual Property
  • 8. Nanodiamond Additives Within Polymer Materials for Thermal Management
  • 9. Nanodiamond – Advanced Thermal Additive for Polymers w  Optimized control of interaction between the filler, resin and other fillers (when present) •  Reduced thermal resistance •  High wettability w  Isotropic filler, with size fitting between the polymer chains Diamond H-BN Al2O3 SiO2 AlN ZnO Thermal Properties Thermal conductivity, (W/m K) 2000 300+ 30 1.4 260 54 Theoretical Density, g/cm3 3.1-3.2 3.9 3.98 2.2 3.26 5.64 Electrical Properties Dielectric constant 3.4 3.9 9.7 3.8 8.8 9.8 Electrical Resistivity, ΩŸcm 1013 1015 1014 1014 1014 107 Surface properties, for coupling effect Chemical Functionalization Yes No No No No No
  • 10. Nanodiamond Thermal Management Milestones w  Silicone based thermal interface materials •  Nanodiamond+aluminium oxide filled silicone interface material in mass production for use in OEM consumer electronics devices since 2012 . Carbodeon supplies nanodiamond and nanodiamond filler mixes mainly to formulators. w  Thermally conductive thermoplastic materials •  In house developments on PA and PP since 2012 – Nanodiamond + boron nitride, Nanodiamond + graphite filler combinations •  Production on the way - validated since 2016 – consumer electronics devices – Carbodeon supplies nanodiamonds and nanodiamond filler mixes at various levels in the supply chain •  Patent granted on nanodiamond thermoplastic compounds 2015 WO 2014049212 w  Epoxy materials •  Customer validations 2017 in both coatings and thermal management applications for electronics – Carbodeon supplies nanodiamonds and nanodiamond filler mixes at various levels in the supply chain. w  Nanodiamond containing thermal compounds •  Patent granted 2017, new invention encompassing both thermoplastic and thermoset materials US 9598558
  • 11. Case Example: Nylon-66 Thermal Compounds w  Materials: •  PA-66: Zytel 135F •  Boron Nitride: ESK Boronid® thermal filler, 15 µm •  Nanodiamond: Carbodeon mono-functionalized ND’s w  Processing: •  Compounding: Xplore15 micro-compounder •  Injection molding: Thermo-Haake Minijet, 25*25*3 mm mold w  Thermal analyses: •  Laser flash method (ISO 18755; LFA 447, Netzsch GmbH)
  • 12. PA-66 Thermal Compound, 20 wt.% Overall Filler Loading w  References: •  Neat PA-66 •  Compound with 20 wt.% BN loading w  ND-containing compounds: 18.5 wt.% BN + 1.5 wt.% ND w  Performance (W/m . K) •  Powder grade: > 22% improvement in average thermal conductivity •  Dispersion grade: •  132% improvement within in-plane thermal conductivity •  105% improvement within average thermal conductivity w  Highlights the importance of the preparation method 0 0.5 1 1.5 2 2.5 3 PA-66 20 wt.% BN 18.5 wt.% BN + 1.5 wt.% ND Powder 18.5 wt.% BN + 1.5 wt.% SDND in-plane (x/y) Average (x/y/z) wt% Nd powder wt% Nd dispersion
  • 13. PA-66 Thermal Compound, 45 wt.% Overall Loading w  References: •  neat PA-66 •  compound with 45 wt.% BN loading w  Processing: •  Carbodeon proprietary w  Performance (W/m . K): •  0.05 wt.% •  36.3% improvement within in- plane thermal conductivity •  29.4% improvement within average thermal conductivity •  0.1 wt.% •  51.4% improvement within in- plane thermal conductivity •  38.2% improvement within average thermal conductivity w  Works at very low nanodiamond concentrations 0 1 2 3 4 5 6 PA-66 Ref45 0.05+44.95 0.1+44.9 in-plane (x/y) average (x/y/z) 44.9+0.1 Nanodiamond49.95 + 0.05
  • 14. PA-66 Electrically Conducting Thermal Compound, 50 wt.% Overall Loading w  References: •  neat PA-66 •  compound with 50 wt.% graphite loading •  Graphite filler material, TIMCAL TIMREX® KS5-75TT Primary Synthetic Graphite w  Performance: •  0.5 wt.% •  46.3% improvement within in-plane thermal conductivity •  40.7% improvement within average thermal conductivity w  Works with a wide variety of filler materials 0 2 4 6 8 10 12 PA-66 Ref50 0.5+49.5 in-plane (x/y) average (x/y/z) 49.5 + 0.5 Nanodiamond
  • 15. PP Electrically Insulating Thermal Compound w  45 wt.% overall filler loading w  References: •  neat PP; Moplen RP340N •  compound with 45 wt.% BN loading •  ESK Boronid® thermal filler, 15 µm w  Performance: •  0.1 wt.% •  63% improvement within in-plane thermal conductivity •  58% improvement within average thermal conductivity w  Works with a wide variety of thermoplastic polymers 0 0.5 1 1.5 2 2.5 3 Moplen RP340N 45% BN 44.9% BN + 0.1% SDND in-plane (x,y) average (x,y,z) Nanodiamond
  • 16. Verifying the Coupling Concept w  Diamonds retain their adhesion to h-BN during compounding and injection molding FIB-STEM on a ready PA-66/BN/ND compound
  • 17. Ongoing Activities With NanoDiamond Combined Fillers w  Thermoplastics •  Main application area is in electronics and LED applications. w  Thermosets •  Main application has been in thermal interface materials to date, but materials such as coatings of wires for electrical coils/ machinery could be a viable application. w  In house filler mixes •  So far, about 90% of the developments involve nanodiamond supply only, with in-house filler mixing (in sample form) accounting for around 10%, but there is growing interest in this. •  Ready preparations of nanodiamond and boron nitride, aluminium oxide or other materials will be easier to disperse into customer polymers. w  Supply Chain •  Attacking mainly at component/ system level, formulators include both Carbodeon preferred partners and customer’s existing suppliers
  • 18. Industry Targets w  Consumer Electronics w  High Powered LED w  E-Mobility (New Focus) •  Power electronics at device and assembly level - vehicles and charging systems •  Coatings and insulating pieces for electrical machine coils •  Nanodiamond electrolytes to control dendrite growth in Lithium batteries •  Low friction/ wear resistant materials and coatings in driveline
  • 19. Nanodiamond USP within Polymer Thermal Management w  Technical performance •  NanoDiamonds exhibit very high thermal conductivity and are electrically insulating •  NanoDiamond surface functionalization allows efficient coupling to applied polymers and other thermal filler materials •  Nanodiamond dispersions allow the improvements with very low nanodiamond concentrations w  Processing •  Nanodiamonds can be applied within existing production processes & supply chains w  Cost •  By using low concentrations, impact on material cost starts from approximately €1 per kg of the compounds. Most applications are in the range €2-10 w  Commercial stage •  NanoDiamonds are already applied in industrial solutions
  • 20. Contact: Carbodeon Vesa Mayllymaki, CTO, CEO vesa.myllymaki@carbodeon.com +358 50 5678828 Gavin Farmer, Business Development gavin.farmer@carbodeon.com +44 7768 587105 +44 1953 850011 www.carbodeon.com @carbodeon, @fightingtorque Carbodeon Ltd Oy