© SRI Consulting PEP Report 51D

Abstract Process Economics Program Report 51D

POLYMER NANOCOMPOSITES (September 2010)

This report is an update of our earlier PEP report (PEP Report 51C) on polymer nanocomposites which was published in 2002. Development in polymer nanocomposites was at a relatively early stage with only a few commercial products by 2002. Most of the efforts were focused on clay-based nanoparticles. Since then the field of polymer nanocomposites has grown greatly. The progress in polymer nanocomposites has been wide and encompassed many different industries. New types of nanoparticles or nanofillers have been developed. Applications range from automotive, biological implants, packaging, aircraft components, etc. However, commercialization of many applications has taken longer than anticipated. There are still technological challenges to be overcome before there is widespread commercialization of polymer nanocomposites. The main barriers to overcome include cost and dispersion of the nanoparticles with the polymer matrix.

In this report, we will review the current state of polymer nanocomposites in terms of patent literature, other scientific literature and commercialization activities. Nanofillers and polymer nanocomposites encompass a wide subject area. The report will focus on nanoparticles and polymer nanocomposites that are already commercialized or have a commercialization potential. The commercial status, potential markets, and producers of polymer nanocomposites are discussed. Technological developments in nanoparticles and polymer nanocomposites production will be reviewed. Nanoparticles or nanofillers reviewed in this report include clay-based nanoparticles such as montmorillonite and halloysite, carbon-based nanoparticles such as carbon nanotubes and graphene sheets, and other nanofillers such as nanosilica, metal oxide nanoparticles, polymeric nanoparticles and cellulose nanofibers.

POLYMER NANOCOMPOSITES

Report No. 51D

by Susan Bell

September 2010

Menlo Park, California 94025

Process Economics Program

A private report by the

SRIC agrees to assign professionally qualified personnel to the preparation of the Process Economics Program’s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither SRIC nor its employees will assume any liability for the special or consequential damages arising from the Client’s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client’s use of the reports or other deliverables produced by SRIC pursuant to this agreement.

For detailed marketing data and information, the reader is referred to one of the SRI Consulting programs specializing in marketing research. THE CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS PROGRAM covers major hydrocarbons and their derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico.

CONTENTS

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GLOSSARY........................................................................................................................ xiii

1 INTRODUCTION ........................................................................................................1-1

2 SUMMARY ................................................................................................................. 2-1

INTRODUCTION ........................................................................................................ 2-1

COMMERCIALIZATION OF POLYMER NANOCOMPOSITES................................. 2-2

TECHNOLOGICAL ASPECTS...................................................................................2-3

Nanoparticles..............................................................................................................2-3

Polymer Nanocomposites........................................................................................... 2-5

Polymer/Clay-Based Nanocomposites.................................................................. 2-6

Polymer/Carbon-Based Nanocomposites ............................................................. 2-6

Polymer/Other Nanocomposites ........................................................................... 2-7

3 STATUS OF POLYMER NANOCOMPOSITES......................................................... 3-1

INTRODUCTION ........................................................................................................ 3-1

PATENT ACTIVITIES................................................................................................. 3-1

NANOPARTICLE SUPPLIERS .................................................................................. 3-6

Clay-Based Nanoparticles.......................................................................................... 3-6

Applied Minerals Inc. ............................................................................................. 3-6

Nanocor Inc. ..........................................................................................................3-7

Southern Clay Products......................................................................................... 3-7

Elementis Specialties ............................................................................................ 3-7

Laviosa Chimica Mineraria .................................................................................... 3-7

NaturalNano Research, Inc. .................................................................................. 3-7

NanoClay and Technologies, Inc. .........................................................................3-7

Carbon-Based Nanoparticles ..................................................................................... 3-8

Asbury Carbon.......................................................................................................3-9

Bayer MaterialScience AG .................................................................................... 3-9

Cheap Tubes, Inc. .................................................................................................3-10

CONTENTS (Continued)

© SRI Consulting iv PEP Report 51D

CNano.................................................................................................................... 3-10

GrafTech International........................................................................................... 3-10

Hyperion Catalysis International............................................................................3-10

Materials & Electrochemical Research (MER) ...................................................... 3-11

Nano Carbon Technologies (NCT)........................................................................ 3-11

Nanocyl.................................................................................................................. 3-11

Pyrograf® Products, Inc. (PPI) .............................................................................. 3-11

Showa Denko K.K. (SDK)...................................................................................... 3-11

Vorbeck Materials.................................................................................................. 3-12

Unidym Inc.............................................................................................................3-12

XG Sciences..........................................................................................................3-12

Other Nanoparticles....................................................................................................3-13

Aspen Aerogel .......................................................................................................3-14

Bayer MaterialScience AG .................................................................................... 3-14

Cabot Corporation ................................................................................................. 3-14

Hybrid Plastics.......................................................................................................3-14

Lanxess AG ........................................................................................................... 3-14

Minerals Technologies Inc..................................................................................... 3-15

Nanophase ............................................................................................................ 3-15

Nanotek ................................................................................................................. 3-15

Prices.......................................................................................................................... 3-15

COMMERCIAL POLYMER NANOCOMPOSITE APPLICATIONS............................ 3-17

Polymer/Clay Nanocomposites ..................................................................................3-18

Polymer/Oxides Nanocomposites ..............................................................................3-19

Polymer/POSS Nanocomposites ............................................................................... 3-20

Polymer/Polymer Nanocomposites ............................................................................3-20

Polymer/Aerogel Nanocomposites .............................................................................3-20

Polymer/CNT Nanocomposites .................................................................................. 3-20

SAFETY, HEALTH AND ENVIRONMENTAL ASPECTS OF POLYMER NANOCOMPOSITES ................................................................................................. 3-21

CONTENTS (Continued)

© SRI Consulting v PEP Report 51D

4 NANOPARTICLES.....................................................................................................4-1

INTRODUCTION ........................................................................................................ 4-1

CLAY-BASED NANOPARTICLES ............................................................................. 4-1

Nanoclay..................................................................................................................... 4-2

Montmorillonite—Layered Structure...................................................................... 4-2

Sepiolite—Fibrous Structure ................................................................................. 4-3

Halloysite—Tubular Structure ............................................................................... 4-3

Kaolin—Layered Structure .................................................................................... 4-3

Talc—Layered Structure ....................................................................................... 4-4

Layered Double Hydroxides (LDHs) ..................................................................... 4-4

Organoclay ................................................................................................................. 4-4

CARBON-BASED NANOPARTICLES ....................................................................... 4-7

Carbon Black .............................................................................................................. 4-7

Carbon Nanotubes .....................................................................................................4-8

Properties .............................................................................................................. 4-8

Carbon Nanotube Production................................................................................ 4-9

Expandable Graphite.................................................................................................. 4-10

Graphene Sheets or Nanoplatelets ............................................................................ 4-11

Properties .............................................................................................................. 4-11

Graphene Sheet Production.................................................................................. 4-11

OTHER NANOPARTICLES........................................................................................ 4-14

Calcium Carbonate.....................................................................................................4-14

Silicon Oxide Nanoparticles........................................................................................ 4-14

Metal Nanoparticles....................................................................................................4-14

Metal Oxides Nanoparticles........................................................................................ 4-14

Polymeric Nanoparticles............................................................................................. 4-15

Aerogels...................................................................................................................... 4-16

Properties .............................................................................................................. 4-16

CONTENTS (Continued)

© SRI Consulting vi PEP Report 51D

Aerogel Production ................................................................................................ 4-17

Polyhedral Oligomeric Silsesquioxanes (POSS)........................................................ 4-19

Properties .............................................................................................................. 4-19

POSS Production .................................................................................................. 4-20

Cellulose Nanofibers .................................................................................................. 4-21

Properties .............................................................................................................. 4-21

Cellulose Nanofiber Production.............................................................................4-22

5 POLYMER/CLAY NANOCOMPOSITES ................................................................... 5-1

INTRODUCTION ........................................................................................................ 5-1

EXFOLIATION OF ORGANOCLAY OR NANOCLAY TO FORM POLYMER NANOCOMPOSITES ................................................................................................. 5-1

IN-SITU POLYMERIZATION PROCESS ................................................................... 5-2

MELT INTERCALATION PROCESS ......................................................................... 5-4

SOLUTION INDUCED INTERCALATION PROCESS............................................... 5-7

LATEX PROCESS...................................................................................................... 5-8

PRODUCTION OF POLYAMIDE/CLAY NANOCOMPOSITES ................................. 5-9

PRODUCTION OF POLYOLEFIN/CLAY NANOCOMPOSITES................................ 5-9

PRODUCTION OF EVA COPOLYMERS/CLAY NANOCOMPOSITES .................... 5-11

PRODUCTION OF POLYESTER/CLAY NANOCOMPOSITES................................. 5-11

PRODUCTION OF PVC/CLAY NANOCOMPOSITES............................................... 5-12

PRODUCTION OF POLYSTYRENE/CLAY NANOCOMPOSITES ........................... 5-12

PRODUCTION OF POLYCARBONATE/CLAY NANOCOMPOSITES ...................... 5-13

PRODUCTION OF ELASTOMER/CLAY NANOCOMPOSITES................................ 5-13

Styrene-Butadiene-Rubber (SBR) Elastomers...........................................................5-13

Halobutyl Elastomers.................................................................................................. 5-14

Thermoplastic Elastomers .......................................................................................... 5-15

PRODUCTION OF ACRYLIC LATEX POLYMER/CLAY NANOCOMPOSITES ....... 5-16

CONTENTS (Continued)

© SRI Consulting vii PEP Report 51D

PRODUCTION FLUOROPOLYMER/CLAY NANOCOMPOSITES ........................... 5-16

POLYMER NANOCOMPOSITE PROPERTIES......................................................... 5-16

Mechanical Properties ................................................................................................ 5-16

Barrier Properties .......................................................................................................5-22

Flame Retardancy ......................................................................................................5-25

Other Properties .........................................................................................................5-27

CASE STUDY: POLYMER/CLAY-BASED NANOCOMPOSITES FOR AUTOMOTIVE APPLICATIONS................................................................................. 5-29

6 POLYMER NANOCOMPOSITES WITH CARBON-BASED NANOPARTICLES..... 6-1

INTRODUCTION ........................................................................................................ 6-1

POLYMER/CARBON NANOTUBE NANOCOMPOSITES......................................... 6-1

In-Situ Polymerization for Polymer/CNT Nanocomposite Production ........................ 6-2

Solution Processing for Polymer/CNT Nanocomposite Production ........................... 6-3

Melt Mixing for Polymer/CNT Nanocomposite Production ......................................... 6-5

Properties of Polymer/CNT Nanocomposites ............................................................ 6-6

POLYMER/GRAPHENE NANOCOMPOSITES ......................................................... 6-8

7 POLYMER NANOCOMPOSITES WITH OTHER NANOPARTICLES...................... 7-1

INTRODUCTION ........................................................................................................ 7-1

CALCIUM CARBONATE NANOPARTICLES ............................................................ 7-1

SILICON OXIDE NANOPARTICLES ......................................................................... 7-1

METAL OXIDE NANOPARTICLES............................................................................ 7-4

POLYMERIC NANOPARTICLES............................................................................... 7-7

METAL NANOPARTICLES OR NANOMETAL .......................................................... 7-10

AEROGELS................................................................................................................ 7-12

POLYHEDRAL OLIGOMERIC SILSESQUIOXANES (POSS)................................... 7-13

CELLULOSE NANOFIBERS...................................................................................... 7-15

CONTENTS (Concluded)

© SRI Consulting viii PEP Report 51D

APPENDIX A PATENT SUMMARY TABLES................................................................A-1

APPENDIX B DESIGN AND COST BASES ..................................................................B-1

APPENDIX C CITED REFERENCES .............................................................................C-1

APPENDIX D PATENT REFERENCES BY COMPANY................................................D-1

APPENDIX E PRODUCT INFORMATION .....................................................................E-1

FIGURES

© SRI Consulting ix PEP Report 51D

1.1 Polymer Nanocomposite Patent Activity ............................................................... 1-2

3.1 Polymer Nanocomposite Patent Activity ............................................................... 3-2

3.2 Polymer Nanocomposite Patent Activity Based on Nanoparticles........................ 3-3

3.3 Polymer Nanocomposite Patents Issued by Country or Region ........................... 3-3

4.1 Graphene Nanoplatelet Production.......................................................................4-12

4.2 Aerogel Production ................................................................................................ 4-19

4.3 POSS Structure ..................................................................................................... 4-20

4.4 Cellulose Nanowhisker Production from Wheat Straw ......................................... 4-23

5.1 Schematic of Shear Mixing and Extensional Flow ................................................ 5-7

5.2 Predicted Young’s Modulus of a Polymer Composite Based on the Halpin-Tsai Model..................................................................................................5-17

5.3 Flexural Impact at Low Temperatures for TPO/Clay Nanocomposites................. 5-30

TABLES

© SRI Consulting x PEP Report 51D

2.1 Different Clay-Based Nanoparticles ......................................................................2-3

2.2 Different Carbon-Based Nanoparticles .................................................................2-4

2.3 Other Nanoparticles............................................................................................... 2-4

2.4 Properties of Nanoparticles for Mechanical Enhancement ................................... 2-5

2.5 Methods to Produce Polymer Nanocomposites .................................................... 2-6

3.1 Polymer Nanocomposite Patent Activities (Year 2002–2009): Companies ............................................................................................................ 3-4

3.2 Polymer Nanocomposite Patent Activities (Year 2002–2009): Research Institutes and Universities .....................................................................3-5

3.3 Commercial Nanoclay and Organoclay Suppliers.................................................3-6

3.4 Commercial Carbon-Based Nanoparticle Suppliers ............................................. 3-8

3.5 Commercial Suppliers: Other Nanoparticles .........................................................3-13

3.6 Nanoparticle Prices ............................................................................................... 3-16

3.7 Commercial Applications of Polymer Nanocomposites ........................................ 3-17

4.1 Organic Compounds Used for Organoclay ........................................................... 4-6

4.2 Typical Mechanical Properties of Carbon Nanotubes........................................... 4-9

4.3 Typical Properties of Cabot Nanogel™ Silica Aerogels........................................ 4-17

5.1 Mechanical Properties of Different Clay-Based PA-6 Nanocomposites ............... 5-18

5.2 Mechanical Properties of Different Clay-Based PP Nanocomposites .................. 5-19

5.3 Mechanical Properties of SBR/Clay Polymer Nanocomposites Formed by a Latex Process........................................................................................................5-20

5.4 Mechanical Properties of Nylon Nanocomposites with Halloysite Clay Nanotubes .................................................................................... 5-21

5.5 Mechanical Properties of Polypropylene Nanocomposite with Halloysite Clay Nanotubes .................................................................................... 5-21

5.6 Multi-Layer PET Bottle Containing MXD6 Nylon/Clay Nanocomposites............... 5-23

5.7 Oxygen Barrier Properties Enhancement Using Nanocomposite Barrier Coatings................................................................................................................. 5-24

5.8 Polyethylene Nanocomposite Pipes......................................................................5-24

5.9 Barrier Properties of HDPE/Clay Nanocomposites ............................................... 5-25

TABLES (Continued)

© SRI Consulting xi PEP Report 51D

5.10 Flame Retardancy of Clay-Based Polymer ........................................................... 5-26

5.11 Nanoclay/Conventional FR Systems for Polypropylene........................................ 5-27

5.12 Cost of Polypropylene Composites .......................................................................5-30

5.13 Typical Class A SMC Formulation.........................................................................5-31

5.14 “Tough Low-Mass” Class A SMC Formulation...................................................... 5-32

5.15 Comparison of Weight and Estimated Costs of “Tough Low-Mass” SMC and Conventional Materials .......................................................................................... 5-33

6.1 Comparison of Electrical Conductivity of PC/ABS Resins with Different Additives ................................................................................................................ 6-7

6.2 Comparison of Ductility of PC/ABS Resins with Different Additives ..................... 6-8

6.3 Comparison of Properties of Polymer/FGS and Polymer/Clay Nanocomposites .6-11

7.1 Potential Coating Property Improvement with Metal Oxide Nanoparticles ........... 7-4

7.2 Effect of Microgels on Rubber Composite Properties ........................................... 7-7

7.3 Properties of TPE Containing Microgels ...............................................................7-8

7.4 Effect of Bridgestone’s Polymeric Nanoparticles on Rubber Composite Properties ............................................................................... 7-10

7.5 Yield Strength of Various Nickel Particles............................................................. 7-12

7.6 Properties of Polypropylene/POSS Composites ................................................... 7-13

7.7 Mechanical Properties Polyimide/POSS Composites ........................................... 7-14

7.8 Permeability of Nylon 6 with POSS .......................................................................7-14

7.9 Mechanical Properties of Neat PLA and PLC/Cellulose Nanofibers Composites ......................................................................................... 7-16

A.1 Nanoparticles Patent Summary....................................................................................................A-3

A.2 Polymer/Clay Nanocomposites Patent Summary....................................................................................................A-17

A.3 Polymer Nanocomposites with Carbon-Based Nanoparticles Patent Summary....................................................................................................A-45

A.4 Polymers Nanocomposites with Other Nanoparticles Patent Summary....................................................................................................A-56

E.1 Nanocor Clay Nanomer® Fillers for Nylon Nanocomposites................................E-3

TABLES (Concluded)

© SRI Consulting xii PEP Report 51D

E.2 Nanocor Imperm® Nanocomposites .....................................................................E-3

E.3 Nanocor Clay Nanomer® Fillers............................................................................E-4

E.4 Nanocor Clay Nanomer® Fillers for Epoxy Resins ...............................................E-4

E.5 Laviosa Chimica Mineraria Dellite® Grades .........................................................E-5

E.6 Southern Clay Cloisite® and Nanofil® Fillers........................................................E-5

E.7 Hyperion Catalysis Fibril® Nanotube-Based Masterbatches................................E-6

E.8 Hyperion Catalysis Fibril® Nanotube-Based Ready-to-Mold Compounds ...........E-7

E.9 XG Sciences xGnP™ Graphene Nanoplatelets....................................................E-8

E.10 Lanxess Nanoprene™ Nanoadditive ....................................................................E-8