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product commercialization one nanostep at a time

FF Conference-1998.

paul
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product commercialization one nanostep at a time

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    1. Product Commercialization One Nanostep at a Time Karl Kamena Southern Clay Products

    3. Murphy’s Corollary #1 “Nothing ever gets built on schedule or within budget.”

    4. FF Conference-2002 “Timing-wise, I believe we’re still a few years away from a robust market…yes, I do believe there will be a nano in your future.”

    5. Murphy’s Corollary #2 “To spot the expert, pick the one who predicts the job will take the longest and cost the most.”

    6. FF Conference-2004 Developing products and technologies from concept to the production floor Evolving nanocomposite products and applications Commercialization timelines

    7. SOUTHERN CLAY PRODUCTS A Global Leader in Functional, Specialty Natural and Synthetic Smectite Clays”

    8. SCP’s Rheological Additives

    11. Nanocomposites at SCP Began early 90’s with resin suppliers SCP clay experts (knowledge) Partner with resin suppliers expertise (knowledge) Provide clays to nanocomposite technology developers Partner with other interested parties

    12. Nanocomposites Concept The incorporation of single-digit percentages of high surface-area nanoclays into host polymer systems improves the performance of the specific polymer matrix without significant deterioration of properties.

    13. Nanocomposite Benefits Lower Density Reinforcement Increased Dimensional Stability Increased HDT Improved Barrier Properties Synergistic Flame Retardant Approach Increased melt strength Thermoplastic Recyclable

    14. Clay Terminology Bentonite A rock A mixture of several minerals (one is smectite) Billions of tons worldwide Smectite Component of bentonite Known as a 2:1 layered clay Clays in the smectite family Montmorillonite (di-octahedral) Hectorite (tri-octahedral) Others

    18. Smectite Aggregate

    19. Key Properties of Montmorillonite Shape: Platelet Size: 1nm thick, 75-150 nm across Charge: unit cell 0.5-0.75 charge 92 meq/100g clay Surface Area: >750 m2/g High Modulus: ~170 GPa Particle: robust under shear, not abrasive

    20. Smectite Clay Chemistry Smectite (dioctahedral) 2-dimensional arrays of silicon-oxygen tetrahedra and 2-dimensional arrays of aluminum- or magnesium-oxygen-hydroxyl octahedra

    21. Organoclay Chemistry

    22. Quat Ion Exchanged Montmorillonite

    25. Cloisite® 93A (90 MER)

    29. The dispersed phase MMT is mixed with the resin by melt blending or extruding. Four separate or combinations of mixtures can result: - Tactoid: polymer encapsulates stacks of MMT platelets. - Intercalate: polymer chains enter between MMT parallel platelets. - Disordered intercalate: the MMT platelets are not parallel. - Delaminated or Exfoliated: MMT platlets separated and dispersed in the resin. The dispersed phase MMT is mixed with the resin by melt blending or extruding. Four separate or combinations of mixtures can result: - Tactoid: polymer encapsulates stacks of MMT platelets. - Intercalate: polymer chains enter between MMT parallel platelets. - Disordered intercalate: the MMT platelets are not parallel. - Delaminated or Exfoliated: MMT platlets separated and dispersed in the resin.

    31. Murphy’s Corollary #3 If it works in theory, it won’t work in practice. If it works in practice, it won’t work in theory.

    33. The Processing Challenge SCP provides Cloisite as a powder with a mean of about 8?m particle size. Extrusion is used to melt blend the powder with the resin. In each particle of powder there are more than 3000 platelets. The processing challenge is to disperse not only the powder particles but also the platelets. Dispersion to individual platelets is needed to take advantage of the high aspect ratio (>50) and high surface area (>750m2/gm) of MMT. SCP provides Cloisite as a powder with a mean of about 8?m particle size. Extrusion is used to melt blend the powder with the resin. In each particle of powder there are more than 3000 platelets. The processing challenge is to disperse not only the powder particles but also the platelets. Dispersion to individual platelets is needed to take advantage of the high aspect ratio (>50) and high surface area (>750m2/gm) of MMT.

    34. Nanocomposite Exfoliation

    35. This figure proposes a mechanism for nanocomposite formation based upon a combination of chemical compatibility and processing. Not all comments are based on this study. Case 1, Compatible Clay Treatment and Resin Chemistry: - Most any processing condition (except a single screw extruder will yield delamination and dispersion. - The platelets almost explode to come apart. - Example is PA6 and Cloisite 30B. Case 3, Clay Treatment Not Compatible with Resin Chemistry: - Process changes can help reduce the size of the intercalant, but condition changes (to date) do not led to delamination and dispersion. - Example is PP and standard organoclays. Case 2, Partially Compatible Clay Treatment and Resin Chemistry: - Varying extruder conditions and screw design can improve delamination and dispersion. - Examples are PA6 and Cloisite 15A and PP and Cloisite 15A with maleated PP. This figure proposes a mechanism for nanocomposite formation based upon a combination of chemical compatibility and processing. Not all comments are based on this study. Case 1, Compatible Clay Treatment and Resin Chemistry: - Most any processing condition (except a single screw extruder will yield delamination and dispersion. - The platelets almost explode to come apart. - Example is PA6 and Cloisite 30B. Case 3, Clay Treatment Not Compatible with Resin Chemistry: - Process changes can help reduce the size of the intercalant, but condition changes (to date) do not led to delamination and dispersion. - Example is PP and standard organoclays. Case 2, Partially Compatible Clay Treatment and Resin Chemistry: - Varying extruder conditions and screw design can improve delamination and dispersion. - Examples are PA6 and Cloisite 15A and PP and Cloisite 15A with maleated PP.

    36. Dispersion Mechanism This figure continues the proposed mechanism. Particles of organoclay, with >3000 platelets, fracture to ribbons of intercalants or tactoids. It is proposed this is a results of shearing stacks of platelets apart to make shorter stacks of platelets. Ribbons reach a size where shearing no longer reduces the ribbon size (the number of platelets in a stack). Platelets in the ribbons delaminate by peeling apart. This happens after more polymer chains enter the clay galleries and push the platelets further apart. At either some polymer concentration or some platelet separation distance, the platelets peel away from the ribbon to be dispersed as individual platelets. This figure continues the proposed mechanism. Particles of organoclay, with >3000 platelets, fracture to ribbons of intercalants or tactoids. It is proposed this is a results of shearing stacks of platelets apart to make shorter stacks of platelets. Ribbons reach a size where shearing no longer reduces the ribbon size (the number of platelets in a stack). Platelets in the ribbons delaminate by peeling apart. This happens after more polymer chains enter the clay galleries and push the platelets further apart. At either some polymer concentration or some platelet separation distance, the platelets peel away from the ribbon to be dispersed as individual platelets.

    37. A number of TEMs have been examined during this and other nanocomposite studies at SCP. The small picture in the figure shows the result of particles being sheared to ribbons, stacks of many platelets more than 100nm thick. The ribbons seen in this TEM are common for Case 3 Nanocomposites. TEM evidence of platelets peeling apart is not common, but has been seen multiple times with a representative TEM shown in the larger picture in the figure.. One of the regions where the platelets are peeling apart from the ribbon is outlined in the TEM. A number of TEMs have been examined during this and other nanocomposite studies at SCP. The small picture in the figure shows the result of particles being sheared to ribbons, stacks of many platelets more than 100nm thick. The ribbons seen in this TEM are common for Case 3 Nanocomposites. TEM evidence of platelets peeling apart is not common, but has been seen multiple times with a representative TEM shown in the larger picture in the figure.. One of the regions where the platelets are peeling apart from the ribbon is outlined in the TEM.

    38. XRD Examples: 15A/PA6 Delamination dispersion is monitored by X-Ray Diffraction (XRD) and by Transmission Electron Microscopy (TEM). Four sample XRD are shown in the figure. MMT with its ordered platy morphology causes x-rays to diffract indicating the distance from the top of one platelet to the top of the next platelet (Basal Spacing or D001 Spacing). The organoclay Cloisite 15A has a d-spacing of about 32Ĺ. When Cloisite15A is compounded with PA6 in a single screw extruder, the peak intensity decreases, the peak shape broadens but the peak position remains at about 32Ĺ. Co Rotating Low Shear and Medium Shear samples further decrease in size and show the platelets mover further apart, 34Ĺ and 38Ĺ, respectively. The sample made in the Tangential Medium Shear extruder showed no XRD peak. The lack of XRD peak suggests either an exfoliated or an intercalated disordered nanocomposite. TEM is required to see what the platelet distribution looks like. Delamination dispersion is monitored by X-Ray Diffraction (XRD) and by Transmission Electron Microscopy (TEM). Four sample XRD are shown in the figure. MMT with its ordered platy morphology causes x-rays to diffract indicating the distance from the top of one platelet to the top of the next platelet (Basal Spacing or D001 Spacing). The organoclay Cloisite 15A has a d-spacing of about 32Ĺ. When Cloisite15A is compounded with PA6 in a single screw extruder, the peak intensity decreases, the peak shape broadens but the peak position remains at about 32Ĺ. Co Rotating Low Shear and Medium Shear samples further decrease in size and show the platelets mover further apart, 34Ĺ and 38Ĺ, respectively. The sample made in the Tangential Medium Shear extruder showed no XRD peak. The lack of XRD peak suggests either an exfoliated or an intercalated disordered nanocomposite. TEM is required to see what the platelet distribution looks like.

    39. The TEM of the sample from the Single Screw extruder shows big ribbons that are of stacks of intercalated platelets. The samples from the Co Rotating extruder show increasing dispersion as the ribbons get smaller and some single platelets can be seen, particularly in the sample from the Medium Shear extruder. The sample from the Tangential Medium Shear extruder shows excellent delamination and dispersion. The TEM of the sample from the Single Screw extruder shows big ribbons that are of stacks of intercalated platelets. The samples from the Co Rotating extruder show increasing dispersion as the ribbons get smaller and some single platelets can be seen, particularly in the sample from the Medium Shear extruder. The sample from the Tangential Medium Shear extruder shows excellent delamination and dispersion.

    41. Exfoliation in nylon and PP

    42. Evolving Nanocomposite Products Polyamides Polyolefins Styrenics Epoxies UPR TPU PLA EVA Rubbers Synergistic FR additive Others

    43. Evolving Application Areas Reinforcement Thermal Barrier Synergistic Flame Retardant

    44. Partnering Relationships-General Motors & Basell GM Research-go nano TPO nanocomposites Ran first experiment late ’97 JDA with SCP in ’98 1st generation technology & products Compete with talc-filled TPO

    45. Partnering Relationships-General Motors & Basell Commercial applications M-Van Step Assist, 08/01 Impala side moldings, 02/04 Hummer H2 SUT trim, panels (05/04)

    46. Impala side moldings

    47. General Motors-Technical Challenges and Roadmap Different shrinkage rate Different part thickness Coloring recipe revisions Developed and qualified new nanocomposite to meet requirements

    48. General Motors/Basell/SCP-Critical Issue Surface defects Painting problems 8 micron CLOISITE nanoclay 100-200 micron clay clumps Causes? Solutions?

    49. General Motors/Basell/SCP-Critical Issue Clay agglomeration caused by processing conditions Clay feed position Screw design/speed Temperature Pressure

    50. General Motors/Basell/SCP-Critical Issue Clay agglomeration resolved by processing conditions Clay feed position Screw design/speed Temperature Pressure

    51. Murphy’s Corollary #4 New systems generate new problems

    52. General Motors-more to come Additional applications Exterior trim, range of models Announcements not news Second generation nanoproducts & developments

    53. Commercialization Timelines “Wise men talk because they have something to say; fools talk because they have to say something.” Plato (427-347 BC)

    54. Others-more to come Additional products Additional applications Some nano announcements Second generation nanoproducts & developments

    55. SPE Plastics Engineering, May 2004 “Nanocomposites”; “Microscopic Reinforcements Boost Polymer Performance”, “Nanocomposites Market Starts To Pick Up Steam”, “The long-awaited potential of nanocomposites is being realized”.

    56. Plastic in Packaging, June 2004 “Nanocomposites: a world of opportunity?” “Nanocomposite technologies are still in their infancy…there are promising opportunities for nanomaterials, which have the potential to offer flexible and rigid packaging producers improved properties at lower costs.”

    57. Modern Plastics, August 2004 “Promise of compounds containing nanoclays becoming reality?” “Nanocomposites have been the Next Big Thing in the plastics industry for several years now. What has been lacking in all that time is the killer application to prove out the hype.” “What has happened instead is a slow trickle of relatively modest applications.”

    58. Commercialization Timelines Nano is happening now One nanostep at a time Part of the polymer system Cost, performance, value

    59. Commercialization Strategies Pay attention Get started (restarted) Do something nano One nanostep at a time Multiple nanosteps

    60. Karl’s Corollary Do it right the last time, over and over again.

    61. THANK YOU Karl Kamena Visit us at www.nanoclay.com

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