The document discusses Tyco Electronics' collaboration with academic researchers to develop new technologies. It provides examples of how Tyco has taken inventions from universities and applied them commercially through innovation. Specifically, it describes how Tyco worked with UC Berkeley to radiation crosslink self-assembled block copolymers for applications in areas like shape memory polymers and optical materials. It also discusses Tyco's collaboration with UC Davis to develop a catalytically crosslinkable and decrosslinkable polymer system using olefin metathesis, enabling recyclability. Finally, it outlines Tyco's research on graphene preparation and potential applications of graphene in areas like lightweight conductors.

1. From Invention to Innovation:
Practical Examples of Academic
Discovery Leading to Commercial
Viability
Mark W. Ellsworth
Senior Director
January 4, 2011

2. A brief history of Tyco Electronics
Radiation chemistry
applied to polymers Launch Day
Raychem July 11th
1957 1999 2007
1932 •Tyco International 2007
AMP acquires AMP, 1998 Tyco International announces
Wire crimping •Tyco International break-up plan
acquires Raychem, 1999 • Tyco International
technology
• Tyco Electronics
• Tyco Healthcare (Covidien)
A Start-Up Company with $12B in Worldwide Sales, 75 years of innovation,
and 90,000 employees in 125 countries

3. TE At A Glance:
A World Leader Enabling Smart Connectivity
Serving Large Attractive Markets
Consumer Industrial and Infrastructure
Transportation Consumer Communications Energy Industrial Aerospace Healthcare
Products Equipment & Defense
A Broad Range of Connectivity Products and Technology
Connectors Fiber Optics Touch Systems Circuit Sealing & Wireless Precision
Protection Protection Wiring
Extensive Global Resources
100
7,000 Engineers 5,000 Salespeople 125 Countries Manufacturing Sites
Close to our Customers Advising our Customers Served Serving Every Region
No competitor serves the range of industries breadth our breadth of products and resources

4. Product Capabilities for
Automotive Market
Alternative
High Speed Data
Power Systems
Networking
Sensor
Technology
Mechatronics
Inductive
Systems Relays &
Switching
Cable Assembly Modules
Terminals &
Systems
Connectors

5. Product Capabilities for
Computer & Consumer Electronics Markets
Antenna Products Sockets Coax
Active Optical Cables Fine Pitch SFP+ & QSFP
B-to-B Connectors I/O Products

6. Product Capabilities for
Energy Networks
Surge Arresters
Insulation Enhancement
Cable Accessories Insulators
New Products for Solar and Wind Energy
Power Measurement
& Control
Switching and
Protection

7. Product Capabilities for
Communication Service Providers
Copper Networks Fiber Networks Intelligent Broadband Connectivity

8. Product Capabilities for
Medical Markets
Medical Connectors Cable Assemblies Cable Assemblies
(Surgical) (Ultrasound)
Micro-miniature Coax Precision Stamping Medical Grade Tubing

9. Product Capabilities for
Touch Systems
Medical Retail Restaurant Entertainment
Office
Automation Government
Industrial
Military
Self-Service/
Informational Kiosks

10. We have a Treasure of Technology . . .
Undersea Telecommunications Energy Networks
Performance leader in fiber Large scale connectors sealed for 30
optic communications. years. High energy circuit protection.
Telecom Networks Communications
Copper and fiber connectors. High density copper
Sealed and protected for 30 years. and fiber interconnects.
$500M+ of annual
R&D investment
Transportation 14,000+ patents Touch Systems
Copper and fiber connectors. Advanced materials to
issued or pending create touch screens.
Rugged housings, sensors.
Products introduced in
last 3 years accounted
Circuit Protection
Healthcare for 36% of sales
Ultra fine cable manufacturing Advanced materials technology
and connection. Highly regulated. to create protection for commercial
& consumer devices.
Computer & Industrial Aerospace & Defense
High density copper and fiber High density metals and fiber connectors.
interconnects, high performance. High performance wire.

11. Key Market Trends
• Electronic feature growth in all industries
• Miniaturization and weight reduction
• Higher data-speed requirements
• Broadband proliferation
• Growth of wireless technologies
• Upgrade of global energy networks
• Environmental and Social responsibility
• Increasing demand for all industries in emerging markets

12. Invention and Innovation

13. Invention and Innovation
• Invention: n an original creation
• Innovation: n an introduction of something new

14. Invention and Innovation
• Invention: n an original creation
• Innovation: n an introduction of something new

15. Invention and Innovation
• Invention: n an original creation
• Innovation: n an introduction of something new

16. Invention and Innovation
Invention: the light bulb Innovation: power distribution
• Vacuum sealed glass bulb • Power generators
• Carbon filament • Cables
• Junction boxes

17. Finding the Right Inventions
• Important criteria for inventions to be potentially useful:
– Published and/or patented
– Tested, demonstrated, and proven in several laboratories
– Potential to be applied to a number of different applications
– Commercialization interests

18. Finding the Right Inventions
• Important criteria for inventions to be useful:
– Published and/or patented
– Tested, demonstrated, and proven in several laboratories
– Potential to be applied to a number of different application
– Commercialization interests
• Other criteria that help…
– Nobel Prize winning technology
– UC Davis alums working on the innovation

19. Open Innovation
Internal
Technology Technology New
Inputs
Spin-offs Markets
Current
Markets
Technology New
External Licensing Revenues
Technology
Inputs

20. Academic – Industrial Collaborations at TE
• Connecting technologies and capabilities:
– Self-assembled block copolymers and electron beam crosslinking
• New technologies applied to existing capabilities:
– Olefin metathesis crosslinking of polymers
• Catching an early commercialization wave:
– CNT’s and graphene for light weight composite materials
• Establishing a new capability:
– Core-shell nanoparticles via atomic layer deposition

21. Radiation crosslinking of self-assembled
block copolymers
Collaboration with Prof. Nitash Balsara, University of California,
Berkeley Department of Chemical Engineering
January 4, 2011

22. Radiation crosslinking of polymers
Invention Innovation
• Discovery of polonium and • Large scale particle accelerators
radium • Crosslinking of polyethylene by GE
• Isolation, purification, researchers
concentration • Engineered commercial
• Chemical effects of radiation manufacturing by Raychem Corp.

23. How it works
How an electron beam works
Polyethylene is composed of
hydrogen atoms (red) and
HIGH VOLTAGE carbon atoms (black)
TERMINAL
ELECTRON
GUN
When the polymer chains are
BEAM TUBE exposed to the electron beam,
hydrogen atoms are dislodged,
forming reactive sites on the
polymer chains
SCAN MAGNETS
The reactive sites on
neighboring chains bond,
SCAN creating a crosslinked
WINDOW
polymer
(Ti METAL)

24. The statistics of self-assembly
A B A
• Self assembled structures calculations
and experiments:
– Ratio of A to B segments
– Length of A and B segments and
length distribution
– Molecular motion within the segments
– Strength of interaction amongst the
segments
• Experimental variables:
– Thermal treatment and history Matsen and Bates, Macromolecules, 1996, 7641-7644
– Mechanical forces

25. Collaborative research: block-copolymer
nanocomposites
Highly ordered block copolymer nanostructures are prepared by
engineers at University of California, Berkeley and the structures
are “locked” into place using Tyco Electronics’ electron beam
crosslinking capabilities.

26. Radiation crosslinking in the ordered state
Peroxide crosslinking Radiation crosslinking
After radiation crosslinking, ordered structures are
maintained above the melting point of the copolymer

27. Potential applications
Shape memory polymers
Optical materials
Energy storage

28. Reversible crosslinking via olefin
metathesis
Stefanie Gravano
UC Davis, PhD Chemistry 2006
January 4, 2011

29. Invention and Innovation:
olefin metathesis and polymer crosslinking
A X A X
M
B Y B Y

30. Invention and Innovation:
olefin metathesis and polymer crosslinking
A X A X
M
B Y B Y

31. Invention and Innovation:
olefin metathesis and polymer crosslinking
A X A X
M
B Y B Y

32. Concept: Catalytic Crosslinking
Catalyst
– CH2CH2 (g)

33. Property Enhancement from Crosslinking
• Shape Memory Nylon 6 after lead free solder reflow (260 ºC)
– Heat Shrink Capability WITHOUT Cross-linking
• Temperature Stability
– Improved higher and lower use temps
• Chemical Resistance
Nylon 6 after lead free soldering (260 ºC)
WITH Cross-linking

34. Crosslinking is useful……..
But crosslinking renders the polymer intractable
How can we recycle these polymers?
…..by a decrosslinking reaction

35. Concept: Catalytic Crosslinking and
Decrosslinking
Catalyst Catalyst
+CH2CH2 (g) – CH2CH2 (g)

36. Concept: Catalytic Crosslinking and
Decrosslinking
Catalyst Catalyst
CH2CH2 (g) – CH2CH2 (g)
Goal: Develop a catalytically Applicable to multiple polymer types
crosslinkable and decrosslinkable • Poly(ethylenes) •Fluoropolymers
system applicable to current crosslinked • Poly(esters)
materials and other materials that are •Acrylics
– Hytrel™
crosslink adverse • Rubbers
The alkene (C=C) is the key! – EPDM

37. Crosslinking and Decrosslinking System
Variables

38. Variable 1: Alkyl Chain Length
O O O O
n
C Monomer Polymer X-Link De-X-Link
3 No / Red → Brown N/A
4 (Gel) No / Red → Blue → Brown N/A
5
6
11

39. Variable 2: % of Olefin Content
x y
O O O O
9
x y Mn (g/mol) Ru Crosslink/gel Decrosslink
1% olefin 3 310 31,719 Yes Yes
10% olefin 38 338 42,791 Yes Yes

40. Variable 3: Polymer Backbone
Olefin Olefin Crosslin
Polymer Crosslinked Decrosslinked Polymer Decrosslinked
content content ked
5
10 % No N/A
O O 5%
1 Yes (67%) Yes
(n = 9)
n 6
10 % No N/A
O O 10 % 7
2 Yes (74%) Yes (71%)
(n = 9) 55 % Yes N/A
n
O O
20 %
3 Yes (76%) Yes
(n = 9)
n
x y
4 O O O O 50 % Yes (100%) Yes (54%)
9

41. Melt Processed Olefin modified PE-co-PAA
Catalytic Crosslinking and Electron Beaming
• Two-roll-mill
Beamed Additive (by
Sample Polymer Catalyst M-100 (psi)
(MRads) wt)
1 Modified PE 5 MRads 1% TAIC None 18
2 Modified PE 10 MRads 1% TAIC None 72
3 Modified PE None None 0.3 mol % 254
4 Modified PE None 1% TAIC 0.3 mol% 309
• Catalytic Crosslinking yields 3 x the strength of a 10 MRad beam dose
• Cat Crosslinking & TAIC yields 4 x the strength of a 10 MRad beam
dose
TAIC

42. Decrosslinking Reaction Conditions
Decrosslinking Reaction of PE using
Grubbs G1 Ru Catalysis
Crosslinked Decrosslinked
29% 71% C=C Modified PE
Decrosslinking Reaction of PE using
Ozonolysis Crosslinked Material
Crosslinked Decrosslinked
HC=O Modified PE
35% 65%

43. Designed for Recycling
Typical plastics recycling Materials designed for recycling
Properties degrade when Chemically and structurally
material is recycled created to return to the original
form upon recycling

44. Graphene
January 4, 2011

46. The World of Nanocarbon

47. Comparison of Nanocarbon Technologies
Carbon Nanofiber Carbon Nanotube
Graphene
(CNF) (CNT)
Physical Cylinder Cylinder Platelet
Structure ∼ 20 nm × 100 µm ∼ 1 nm × 100 nm ∼ 1 nm × 100 nm
Tensile Modulus 0.25 – 0.5 TPa 1.0 – 1.7 TPa ∼ 1.0 TPa
Electrical 5 – 100 × 10-3 Ω⋅cm ∼ 50 × 10-6 Ω⋅cm ∼ 50 × 10-6 Ω⋅cm ¦
Resistivity ∼ 1 Ω⋅cm -
Thermal 20 – 3000 W/m K 3000 W/m k ∼ 3000 W/m K ¦
Conductivity ∼ 6 W/m K -
Cost $ 50-100 /lb $ 500 – 50,000 /lb < $10 /lb*

48. Light weight conductors
• Copper • Carbon Nanotubes
– Resistivity = 17 x 10-6 ohm-cm – Resistivity = 50 x 10-6 ohm-cm
– Density = 8.9 g/cc – Density = 1.4 g/cc
CNT conductor cable could be 1/4 of the weight of the copper conductor cable

49. Light weight conductors
• Copper • Carbon Nanotubes
– Resistivity = 17 x 10-6 ohm-cm – Resistivity = 50 x 10-6 ohm-cm
– Density = 8.9 g/cc – Density = 1.4 g/cc
CNT conductor cable could be 1/4 of the weight of the copper conductor cable

50. Light weight conductors
• Copper • Carbon Nanotubes
– Resistivity = 17 x 10-6 ohm-cm – Resistivity = 50 x 10-6 ohm-cm
– Density = 8.9 g/cc – Density = 1.4 g/cc
CNT conductor cable could be 1/4 of the weight of the copper conductor cable
• Lifetime operating cost savings as
a function of weight
– Satellite = $10,000/kg
– Airplane = $1,000/kg
– Automobile = $100/kg

51. Comparison of Nanocarbon Technologies
Carbon Nanofiber Carbon Nanotube
Graphene
(CNF) (CNT)
Physical Cylinder Cylinder Platelet
Structure ∼ 20 nm × 100 µm ∼ 1 nm × 100 nm ∼ 1 nm × 100 nm
Tensile Modulus 0.25 – 0.5 TPa 1.0 – 1.7 TPa ∼ 1.0 TPa
Electrical 5 – 100 × 10-3 Ω⋅cm ∼ 50 × 10-6 Ω⋅cm ∼ 50 × 10-6 Ω⋅cm ¦
Resistivity ∼ 1 Ω⋅cm -
Thermal 20 – 3000 W/m K 3000 W/m k ∼ 3000 W/m K ¦
Conductivity ∼ 6 W/m K -
Cost $ 50-100 /lb $ 500 – 50,000 /lb < $10 /lb*

52. Graphene Preparation in Large Quantities
O OH
OH O
O
O
OH
HO
OH
OH OH O
Graphite Graphite Oxide (GO) Exfoliated Graphite Oxide
GO/water
tion dispersion
on ica
ras
NaNO3 + H2SO4 Ult
+ KMnO4 Graphene/
Chemical reduction
water/PSS
Th e dispersion
r mal
e xfol
i atio
Graphite Flakes n
“Dried” Graphite oxide Graphene
powder

53. Graphene Aerogels
Synthesis of Exfoliation of
Graphene Oxide Graphene Oxide
from Graphite in Water
Graphitic Oxide
GO Dispersion

54. High Strength Composite Foam
Compression Test of GO/PVA Aerogel
25
Aerogel pillars: Ø 0.7 inch; height 0.5 inch;
weight 44 mg
Compressive Strength (kPa)
20
15
1 kg
10
5
Graphene oxide aerogel/polymer 0
composite foam 0 5 10 15 20 25 30
Weight = 128 mg Compressive strain (%)
Compressive Modulus = 0.1 MPa

55. Thermal treatment of graphene oxide
1.00E+07
1.00E+06
resistivity (ohm-cm)
1.00E+05
1.00E+04
1.00E+03
1.00E+02
1.00E+01
1.00E+00
GO 120C 200C 300C 500C 800C
conversion temperature

56. Electrical Properties of Graphene Aerogels
1.00E+12
1.00E+11 graphene oxide aerogel
1.00E+10 graphene aerogel
1.00E+09
resistivity (ohm-cm)
1.00E+08
1.00E+07
1.00E+06
1.00E+05
1.00E+04
1.00E+03
1.00E+02
1.00E+01
1.00E+00
0 0.005 0.01 0.015 0.02 0.025 0.03
graphene content (g/cc)

57. Graphene Aerogel as Electrode Material for
Supercapacitor
4.0 1
Mass of the electrode: 1 mg
3.0
0.8
Potential (V vs. Ag/AgCl)
2.0
0.6
Current (mA)
1.0
0.4
0.0 1st
0.2
-1.0
-2.0 0
-3.0 -0.2
1 M H2SO4, 20 mV/s 1 mA
-4.0 -0.4
-0.2 0.0 0.2 0.4 0.6 0.8 0 400 800 1200 1600 2000
Potential (V vs. Ag/AgCl) Time (s)
• Specific Capacitance: 70- 150 F/g.
• Affecting factors: PVA, thermal treatment temperature,
pore size, electrolyte pore accessibility, etc.

58. CNT and Graphene research
• Light weight conductors
• Structural composites
• Field Effect Transistors
• Sensors
• Transparent Electrodes
• Thermal Substrates
• Environmental Health and Safety Issues

59. Core-Shell Nanoparticles via ALD
Aaron Holm
UC Davis, PhD Chemistry 2002
January 4, 2011

60. The Big D’s (Deposition)
• Physical Vapor Deposition • Chemical Vapor Deposition (CVD)
– Cathodic arc deposition – APCVD – atmospheric pressure CVD
– Electron beam deposition – LPCVD – low pressure CVD
– Evaporative deposition – UHVCVD – ultra high vacuum CVD
– Pulsed laser deposition – AACVD - aerosol assisted CVD
– Sputter deposition – DLICVD – direct liquid injection CVD
– PECVD – plasma enhanced CVD
– MPCVD – microwave plasma assisted CVD
– MOCVD - metalorganic CVD
– HPCVD – hybrid physical CVD
– RTCVD – rapid thermal CVD
– CCVD – combustion CVD

61. Atomic Layer Deposition (ALD)
conformal metal
oxide coating
reactant
(water)
Step 2:
reaction
byproducts
• ALD is a variation of CVD
• Literature reports dating back to
mid 1960’s
• Current commercial uses in IC and precursor
other wafer processing Step 1:
substrate
deposition

62. Multiple Cycles of ALD
• Key aspects of ALD conformal metal
oxide coating
– Two step process
– Precursor reacts with the
substrate surface reactant
– Precursor does not react (water)
Step 2:
with itself during the
reaction
deposition step
– Reactions are self-limiting byproducts
– Multiple layers achieved by
repeated cycles
• Can this be applied to precursor
particles? Step 1:
substrate
deposition

63. ALD on Particles
• First demonstrated at University
of Colorado, Boulder (George,
Weimer, Ferguson)
ALDN coating
• Conventional fluidized bed reactor (new process)
coupled to ALD precursor delivery
system
• Allows for coating a wide variety of
particles CVD coating
– Anything that can be fluidized (incumbent process)
– Coats porous and nonporous
particles
Reactants

64. Commercialization of Particle ALD
Technology

65. Commercialization of Particle ALD
Technology

66. Commercialization of Particle ALD
Technology
News Release
For Immediate Release – Wednesday, Feb 10, 2010
ALD NanoSolutions, Inc. and Tyco
Electronics Announce Collaboration Agreement
ALD NanoSolutions’ Particle ALD™ coating platform to
be used to develop advanced electronic materials and
applications.

67. Laser marking pigment and fading:
nanoparticle titanium dioxide
UV laser
TiO2 TiO
Heat aging
TiO2

68. Permanent laser marking pigment:
core-shell nanoparticles
phenylsilicone Graphite-like char
UV laser
TiO2 TiO
Graphite-like char
Heat aging
TiO2

69. Solution reaction
- -
-
NH4OH -
Create surface charges on particles by TiO2 TiO2
-
removing H from surface OH groups H2O - -
- -
OCH3
Surface charges repel particles and initiate PhSi(OCH3)3
Ti O Si + CH3OH
hydrolysis and condensation reactions of H 2O
PhTMOS on TiO2 OCH3
OH
Catalyst continues the cycle of hydrolysis and NH4OH
Ti O Si + CH3OH
condensation of PhTMOS with those grafted H 2O
O -
to the TiO2 surface
O-
PhSi(OCH3)3
Ti O Si + CH3OH
An insoluble network structure of PPSQ H2O
forms around the particle O
H3CO Si OCH3

70. Coated titanium dioxide particles
As-received 25 w/w% PPSQ

71. Laser marking and aging results
90
80
mark contrast (%)
70
60
standard
50
pigment
40
ELMS pigment Original Mark
30
20
10
0
initial aged
Mark Aged 70 hrs. @ 260°
C

72. Applications for ALD on particles
• Pigments
• Filler compatibilization
• Particle encapsulation
• Varistors

73. Academic – Industrial Collaborations at TE
• Connecting technologies and capabilities:
– Self-assembled block copolymers and electron beam crosslinking
• New technologies applied to existing capabilities:
– Olefin metathesis crosslinking of polymers
• Catching an early commercialization wave:
– CNT’s and graphene for light weight composite materials
• Establishing a new capability:
– Core-shell nanoparticles via atomic layer deposition

74. Three Things…
• Innovation is the conversion of an invention into something practical
• Inventions and Innovations are everywhere, waiting to be discovered,
so keep asking “what can I do with this?”
• Your innovations may not finish where you thought they would, but
you can always go back to where you started.

75. Acknowledgements
Prof. Winston Ko • The Polymers, Ceramics, and
Prof. Gang-Yu Liu Technical Services Group at Tyco
Prof. Timothy Patten Electronics
and all the faculty and staff for the
invitation and arrangements – Stefanie Gravano
– Aaron Holm
• Prof. Nitash Balsara (UC Berkeley) – Jian Wang
and the Balsara Group – Len Radzilowski
– Mark Wartenberg
• Karen Buechler, Chris Gump and – Henry Cervantes
Jeff Lints at ALD Nanosolutions – Frances Peralta