Applied Colloid Technology: How Do I Apply the Principle of Colloid Chemistry in Industrial R&D

(Applied Colloid Technology)

October 19, 2008

C. Chachi Ou ()

Visiting Professor, Department of Chemical and Materials Engineering, National Kaohsiung University

Outline of this Talk

PLS (Polymer-Layered Silicate) Nanotechnology - Past and PresentWhat is PLS NanotechnologyWhy PLS?Structure and Chemistry of LS (Clay) ChemistryVermiculite vs. MontmorilloniteMicroLite the First Commercialized NanoclayPolymer-Vermiculite/MicroLite Nanocomposite Research at National Kaohsiung UniversalityFuture

Polymer/ Layer Silicate Nanocomposite

Also called: Clay Nanocomposites, PLSWhat is PLS?Why PLSMarket:75 millions USD currently250 millions by 2010

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.

Nanocomposite Language

*

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 focus of this study was delamination and dispersion. A few mechanical properties were also measured. This figure shows the tensile modulus increases as TEM Dispersion increases.A big increase in tensile modulus occurs by reinforcing the PA6 with ribbons of clay tactoids or intercalants.Mod vs Elong3.33.33.53.53.73.73.73.73.63.63.43.43.63.6443.63.6%E-2%E-0.2Tensile ModulusElongationTen Mode Vs Elongation26372347351434516832183502003244173960200TM Pl vs E Pl13.213.224.524.559.259.229.629.650.450.4343439.639.61081087272E2/#PlatE0.2/#PlatMod*PlateletsElong/#PlateletsTM*Pl vs E/Pl6.59.253.28571428576.71428571432.18758.93755.625212.285714285713.07142857145202.909090909140.62962962961.4444444444310disp vs d spacing44272777161688141410101111202013133535D-Spacing, 15AD-Spacing, 30BTEM DispersionD-SpacingDispersion vs D-Spacing32.236.237.734.43837.934.737.930.9dis vs res time good44272777161688141410101111202013133535Time, 15ATime, 30BTEM DispersionMean Residence TimeDispersion vs. Mean Residence Time1411626716247102117108136141102dis vs XRD Area44272777161688141410101111202013133535XRD Area, 15AXRD Area, 30BTEM DispersionXRD AreaDispersion vs. XRD Area82503821462631061645812771200disp vs PW1-2H44272777161688141410101111202013133535XRD PW1/2H, 15AXRD PW1/2H, 30BTEM DispersionXRD PW1/2HDispersion vs. XRD PW1/2H1705.33.511.84.85.915.76.41.80mod vs disp000444777161616888141414101010111111272727202020353535131313Nylon30B15ATEM DispersionTensile Modulus, GPaModulus vs Dispersion2.73.33.53.73.73.63.43.643.64.33.7Sheet1E-ScrewClayTen ModeTen Stre%E-2%E-0.2# PlateletsTM*#PlatTS*#PlatE2/#PlatE0.2/#PlatSS15A3.3772637413.23086.59.3CoR-L15A3.5782347724.55463.36.7CoR-H15A3.781351431659.212962.28.9CnRI-L15A3.77745168829.66165.621.0CnRI-M15A3.675321831450.410502.313.1CnRI-H15A3.4695020010346905.020.0CnRNI-L15A3.67832441139.68582.94.0CnRNI-M15A48517392710822950.61.4CnRNI-H15A3.68060200207216003.010.0ModulusYieldElongation 2%Elongation 0.2%ModulusElongation 2%ModulusYieldElongation 2%Elongation 0.2%NylonNylonNylonNylon30B30B15A15A15A15A02.7644020043.377263773.5782347163.7813514383.77745168143.67532183103.46950200113.6783244274851739203.68060200354.310133.78Extruder and Screw TypeXRDXRDTEMExtruderBasalBasalXRDArea Under CurvePlatelets orMean ResidenceSpacing,Spacing,Peak ( W H)IntercalatesTimeper sq. in.Sec.Single Screw ExtruderBasalXRD AreaTEMTime30B30.9XRD PW1/2H1201314115A32.21.88254141Twin Screw Extruder17Co-RotatingIntermeshingLow Shear 15A36.2382767Medium Shear 15A37.75.314616162Counter-Rotating3.5IntermeshingLow Shear 15A34.4263847Medium Shear 15A3811.810614102Medium Shear 30B04.8035102High Shear 15A37.9016410117Counter-Rotating5.9Non-IntermeshingLow Shear 15A34.758111108Medium Shear 15A015.7027162High Shear 15A37.9027720136TEM, 15A6.4Time, 30BD-Spacing, 15AD-Spacing, 30BXRD Area, 15A4Time, 15A32.2825XRD Area, 30BXRD PW1/2H, 15AXRD PW1/2H, 30BXRD Area, 15AXRD Area, 30B1411782527012016200736.2382166737.71465.33821623.5146834.426314473810611.82631024.81061037.91641175.91134.75812010837.927715.75811366.42771314130.9351021201.8120000Sheet1000000000000000000Nylon15ANumber of PlateletsTensile ModulusModulus vs Dispersion000000000000000000Sheet2000000000000000000Nylon15ANumber of PlateletsElongationElongation vs Dispersion000000000000000000Sheet3000000000000000000000000000000000Nylon30B15ANumber of PlateletsTensile ModulusModulus vs. Dispersion000000000000000000000000000000000000000000000000000000000000000000Nylon30B15ANumber of PlatletsElongation, 2"/minElongation vs Dispersion000000000000000000000000000000000Extruder and Screw TypeXRDXRDXRDTEMExtruderBasalPeak ( W H)AreaPlatelets orMean ResidenceSpacing,UnderIntercalatesTimeCurveper sq. in.Sec.Single Screw Extruder30B30.91.81201314115A32.2178254141Twin Screw ExtruderCo-RotatingIntermeshingLow Shear 15A36.25.3382767Medium Shear 15A37.73.514616162Counter-RotatingIntermeshingLow Shear 15A34.411.8263847Medium Shear 15A384.810614102Medium Shear 30B00035102High Shear 15A37.95.916410117Counter-RotatingNon-IntermeshingLow Shear 15A34.715.758111108Medium Shear 15A00027162High Shear 15A37.96.427720136

Evolving Nanocomposite Products

PolyamidesPolyolefinsStyrenicsEpoxiesUPRTPUPLAEVARubbersSynergistic FR additiveOthers

*

Journal Articles

Use Web of Science Search for the Number of Recent ArticlesClay Nanocomposite: 1641Montmorillonite Nanocomposite: 989Vermiculite: 13

Dispersion:
Particles Shear Apart
Platelets Peel Apart

Platelets Peel Apart

Particles Shear Apart

*

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.

Source: M. Kato and A. Usuki, Ch.5, Edited by Pinnavaia, et.al.: Polymer-Clay nanocomposites, Wiley (2000)

MicroLite Vermiculite Dispersions

Elastomeric Gas Barrier Applications

MicroLite 963 has demonstrated technical success as a nanoclay in elastomeric coatings to improve gas retention. The best examples are Double Core Tennis balls through Inmat and Michelins tire efforts.

Inmat Air D-Fense

Inmat Air D-Fense Butyl Rubber Latex/MicroLite 963 system is used in Wilson Double Core tennis balls; Inmat is also developing other Bladder and barrier applicationsRecent investments in Inmat by DSM and Nextgen Partners focus on tires

Michelin Tire

Michelin and Hoechst developed elastomeric coatings to improve air retention in tires using MicroLite 963. Patent applications indicate significant Butyl Rubber savings (PCT WO 98/56598)

Impala side moldings

2.bin

Structure of Montmorillonite/ Vermiculite

Isomorphous Substitution

Al3+ Fe2+, Mg2+

Si4+ Al3+

2: 1 Layered Silicate

Montmorillonite

1 micron

SEM Bentonite Rock TEM Montmorillonite

Source: Southern Clay Products

10 microns

*

A nanocomposite is a resin containing a nano sized dispersed phase. Nanocomposites in this study are based on the clay mineral montmorillonite (MMT). Smectite is the mineral group. The clay mineral MMT a species in the the smectite group. MMT has a platy morphology seen both in the Bentonite rock and refined MMT. The TEM of MMT shows a cluster of platelets, 1nm thick and 50 - 500nm laterally.

Factors to Achieve Performance

Intercalation (Surfactant & Polymer)Interfacial Adhesion or WettingExfoliation (Dispersion and Delamination)

*

Dispersion Mechanism

8 m Particle

> 3000 Platelets

Chemistry Chemistry/Processing Processing

Dispersion

Dispersion

Tactoids/

Intercalants

Partial

Dispersion

Tactoids/

Intercalants

Tactoids/

Intercalants

Tactoids/

Intercalants

Source: Southern Clay Products

*

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.

N

C18

CH2CH2OH

HOCH2CH2

Methyl, Tallow, bis-2-Hydroxyethyl, Quaternary Ammonium X

CH3

+

*

Cloisite 30B

90 meq/100g

N

C18

C18

H

CH3

Methyl, Dihydrogenatedtallow, Ternary Ammonium X

+

Cloisite 93A (90 MER)

N

C18

CH2

CH3

Dimethyl, Hydrogenated tallow, Benzyl, Quaternary Ammonium X

CH3

+

*

Cloisite 10A

125 meq/100g

N

C18

CH2CH(CH2)3CH3

CH3

Dimethyl, Hydrogenated tallow, 2-Ethylhexyl, Quaternary Ammonium X

CH3

C2H5

+

*

Cloisite 25A

125 meq/100g

N

C18

C18

CH3

CH3

Dimethyl, Dihydrogenated tallow, Quaternary Ammonium X

+

*

Cloisite 15A

125 meq/100g

Cloisite 20A

95 meq/100g

SCP CLOISITE Products

*

( ( ( ( ( (

Increasing polymer/monomer hydrophobicity

( ( ( ( ( (

( ( ( ( ( (

Increasing surface hydrophobicity

Cloisite 15A

Cloisite 20A

Cloisite 25A

Cloisite 10A

Cloisite

93A

Cloisite 30B

Cloisite Na+

(Aqueous Systems)

Leistritz Counter Rotating Intermeshing

High Shear

Medium Shear

Low Shear

*

The Counter Rotating Intermeshing Low Shear screw is an open flighted pump. The Counter Rotating Intermeshing Medium Shear screw is a close flighted pump. The Counter Rotating Intermeshing High Shear screw is close flighted with shearing and turbine (slit stowing) elements added.8.bin9.bin10.bin

10 microns

2 mm = 2000 microns

Journal Articles

Use Web of Science Search for the Number of Recent ArticlesClay Nanocomposite: 1641Montmorillonite Nanocomposite: 989Vermiculite: 13

What is Vermiculite?

Vermiculite is a mined silicate mineral with trapped water between the

silicate layers. This water turns to steam when heated (exfoliated)

forcing the silicate layers apart. This produces a lightweight, inorganic,

highly absorbent material that Grace sells as Zonolite vermiculite.

In addition, rather than thermally exfoliating the mined vermiculite

concentrate (VCX), the mineral can be chemically delaminated to produce

very high aspect ratio platelets that carry a surface charge. This product,

MicroLite, forms thin film coatings that have the same properties (inorganic, anisotropic heat shield, vapor and oxygen barrier) as exfoliated vermiculite.

*

X -- Enoree, SC

Pompano Beach, FL -----X

X ------ Ajax, Ont.

Phoenix, AZ ---- X

X ---- Winnipeg, Man.

X ---- Edmonton, Alb.

Specialty Vermiculite Manufacturing Locations

MicroLite Vermiculite Dispersions

Introduction to Specialty Vermiculite

Grace operates 5 expansion facilities to further process vermiculite mined at Enoree.

Vermiculite Business

2002 Sales over $20MMEmploys 120 at 6 sites60,000 tons of vermiculite sold annually. Largest producer in North America. Second largest global producer. 10 years of proven reserves, an additional 10 years probable reserves

MicroLite Business

At Enoree, SC siteSeparate downstream process

Vermiculite Mine

Expansion Processing

*

Vermiculite Crystal,
Swollen Vermiculite and MicroLite

Product Overview

Chemically exfoliated vermiculiteUnique patented processCharacteristicsComposed of inorganic vermiculite plateletsClear film formerHigh aspect ratio (up to 20,000:1)Molecular level smooth surfaceCationic exchange capability Stable dispersion and sprayed dried formatsApplicationsHeat and fire resistance Abrasion resistanceInorganic gasketing material Gas barriers

MicroLite Vermiculite Dispersions

Introduction to MicroLite

MicroLite is used as a water-based coating to provide fire resistance/protection, lubricity, or gas barrier properties.

SEM of MicroLite Powder

Avg particle size 20 microns

MicroLite Film

Nine commercially available products - aqueous colloidal dispersions and a dry powderOne ultra refined product (963++) available for limited samplingProduct RangeUnformulated Products: 100% inorganic dispersions with a range of solid contents903, HTS, 923, 963 and 963++Formulated Products: Includes organic binders for a range of applicationsHTSXE, HTSXE20, HTS SE, MicroWhiteMicroLite Powder: Spray-dried material used to upgrade heat or barrier properties

MicroLite Vermiculite Dispersions

MicroLite Product line

MicroLite Product mix covers a breadth of particle size and is offered with/out organic binder or in dry format.

(A) Target and Typical Results

903

HTS

923

963

963++

HTS XE

HTS EX20

HTS SE

MicroWhite

% Solids (A)

7.5

15

7.5

7.5

7.5

15.5

17.5

15

15

%Solids Spec ranges

7.5-8.0

15.0-16.0

7.5-8.0

7.5-8.0

7.5-8.0

15.5-16.0

17.0-18.0

15.0-16.0

15.0-16.0

Viscosity (cps) (A)

700

6600

250

550

>500

5100

4500

4500

2500

Viscosity Spec ranges (cps)

200-1000

4000-9000

200-1000

200-1000

200-1000

2000-7000

2000-7000

2000-7000

2000-7000

Tensile Strength (psi)

6000

5000

8000

10,000

Not Available

5500

6500

5000

2500

% OSP

MicroLite Vermiculite Dispersions

Current Commercial Applications

Key end uses of MicroLite is in safety fabrics, gaskets and brakes, packaging film and construction. We have seen steady growth in gasket applications.

Fire Protection

Coatings to fiberglass woven and non-woven textiles to increase thermal resistance (competes with silica glass). Good NA coverage, continued growth possible in Europe, gaining in Asia

Construction

Wall coverings and room partitions for public spaces

Gaskets and Friction Coatings (Brakes)

MicroLite improves thermal resistance, improved flexibility and sealing characteristics. Sales doubling for automotive applications between 2000 and 2002.

Others

Barrier Packaging Film (Microlite only). New efforts expected to result in increased sales in 2004Elastomeric gas bladder applications (see next page)

MicroLite Results by Segment

Chart12000 ($1.5MM)2000 ($1.5MM)2000 ($1.5MM)2000 ($1.5MM)2001 ($1.8MM)2001 ($1.8MM)2001 ($1.8MM)2001 ($1.8MM)2002 ($1.6MM)2002 ($1.6MM)2002 ($1.6MM)2002 ($1.6MM)2003 ($1.7MM Proj)2003 ($1.7MM Proj)2003 ($1.7MM Proj)2003 ($1.7MM Proj)Safety FabricConstructionGasketsMicro OthersYearMicrolite Markets870097.3171258270544.19312195.841169366.1630668382221.84232465.98873180.0164944427806.2257765.181008136.416168854.4287364.376246647.056InmatBusiness areaGrace Construction PrPlantEnoree - Verm DispersBill-to partyINMAT LLCNo. of Period: 25PeriodGrs Sls less RgGrs Sls less Rg-PYGross MarginGrs.Margin - PYNet Invoice QtyInvoiced qty - PYCGrpTotal60,054.50USD30,145.50USD46,873.25USD23,365.03USD4,180.00GAL2,090.00GALPeriodGrs Sls less RgAug-00770USD0USD580.43USD0USD55GAL0GALD2Sep-001,540.00USD0USD1,160.87USD0USD110GAL0GALD2Oct-002,310.00USD0USD1,741.30USD0USD165GAL0GALD2Nov-004,620.00USD0USD3,482.61USD0USD330GAL0GALD2Dec-002,310.00USD0USD1,790.11USD0USD165GAL0GALD2Jan-012,425.50USD0USD1,905.62USD0USD165GAL0GALD2Feb-012,425.50USD0USD1,905.61USD0USD165GAL0GALD2Mar-012,425.50USD0USD1,905.61USD0USD165GAL0GALD2Apr-013,234.00USD0USD2,540.82USD0USD220GAL0GALD2May-013,234.00USD770USD2,540.82USD580.43USD220GAL55GALD2Jun-010USD1,540.00USD0USD1,160.87USD0GAL110GALD2Jul-012,425.50USD2,310.00USD1,905.62USD1,741.30USD165GAL165GALD2Aug-012,425.50USD4,620.00USD1,905.61USD3,482.61USD165GAL330GALD2Sep-010USD2,310.00USD0USD1,790.11USD0GAL165GALD2Oct-010USD2,425.50USD0USD1,905.62USD0GAL165GALD2Nov-012,112.00USD0USD1,623.42USD0USD165GAL0GALD2Dec-012,508.00USD2,425.50USD1,998.22USD1,905.61USD165GAL165GALD2Jan-026,688.00USD0USD5,328.60USD0USD440GAL0GALD2Feb-023,344.00USD2,425.50USD2,664.30USD1,905.61USD220GAL165GALD2Mar-023,344.00USD3,234.00USD2,664.30USD2,540.82USD220GAL220GALD2Apr-023,025.00USD3,234.00USD2,345.30USD2,540.82USD220GAL220GALD2May-023,344.00USD0USD2,664.30USD0USD220GAL0GALD2Jun-022,268.75USD2,425.50USD1,758.98USD1,905.62USD165GAL165GALD2Jul-022,519.00USD2,425.50USD1,881.69USD1,905.61USD220GAL165GALD2Aug-02756.25USD0USD579.11USD0USD55GAL0GAL7.353FT30FT3Sep-020USD0USD0USD0USD0GAL0GAL0FT30FT3Oct-023,940.75USD2,112.00USD3,055.06USD1,623.42USD275GAL165GAL36.765FT322.059FT3Nov-020USD2,508.00USD0USD1,998.22USD0GAL165GAL0FT322.059FT3Dec-023,025.00USD6,688.00USD2,321.13USD5,328.60USD220GAL440GAL29.412FT358.824FT3Jan-033,025.00USD3,344.00USD2,321.14USD2,664.30USD220GAL220GAL29.412FT329.412FT32260.4596774194Inmat367393673936770367703680036800368313683136861368613689236892369233692336951369513698236982370123701237043370433707337073371043710437135371353716537165371963719637226372263725737257372883728837316373163734737347373773737737408374083743837438374693746937500375003753037530375613756137591375913762237622Grs Sls less RgMonthsSales $Inmat Monthly Sales $77015402310462023102425.52425.52425.53234323402425.52425.50021122508668833443344302533442268.752519756.2503940.750302530252003 MayYTD MktDivisionVermiculitePlantEnoree - Verm DispersNo. of Customer group: 9Customer groupGrsSlsLesRgGrsSlsLesRg PrYrSlsGrsMrgnSlsGrsMrgn PrYrNet Qty SkNet Qty Sk PrYrVolumeVolume PrYrMayYTDTotal704,583.75USD712,924.75USD479,441.67USD474,621.69USD74,387.87***81,411.16***10,430.83FT311,686.17FT3Regular0USD250.81USD0USD216.12USD0GAL10.04GAL0FT31.342FT3Friction2,232.73USD1,116.33USD1,615.03USD818.87USD220GAL110GAL29.412FT314.706FT3Gaskets22,704.00USD29,700.00USD14,945.80USD20,231.69USD2,640.00GAL3,300.00GAL352.94FT3441.175FT3Auto Others274.5USD366USD212.5USD286.23USD30GAL40GAL4.01FT35.347FT3Safety Fabric420,056.84USD389,339.55USD293,637.01USD266,914.47USD44,856.66***47,762.52***6,004.85FT36,385.37FT3Packaging Films10,554.50USD11,308.00USD7,972.83USD8,950.24USD825GAL770GAL110.295FT3102.942FT3Construction70,356.00USD27,060.00USD45,158.24USD17,486.07USD8,580.00GAL3,300.00GAL1,147.06FT3441.176FT3SV-Gaskets86,464.74USD166,123.35USD49,270.87USD95,936.40USD8,348.62***16,654.72***1,591.42FT33,028.89FT3Micro Others91,940.44USD87,660.71USD66,629.39USD63,781.60USD8,887.60***9,463.89***1,190.84FT31,265.23FT32003 AnnualizedRegular00SV-Friction5358.5523876.072SV-Gaskets54489.635869.92SV-Auto Others658.8510SV-Safety Fabric1008136.416704728.824SV-Packaging Films25330.819134.792SV-Construction168854.4108379.776SV-Gaskets207515.376118250.088SV-Micro Others220657.056159910.536Total16910011150660.0082002 MktBusiness areaGrace Construction PrPlantEnoree - Verm DispersNo. of Customer group: 11Customer groupGrs Sls less RgGrs Sls less Rg-PYGross MarginGrs.Margin - PYNet Invoice QtyInvoiced qty - PYCGrpTotal1,623,695.39***1,815,102.98***1,088,303.71***1,198,071.39***181,315.20***202,858.43***0USD335.25USD0USD280.64USD0GAL15GALRegular2,352.31USD791.61USD1,878.51USD598.63USD145.04GAL64.994GAL1Friction3,537.60CAD2,535.52CAD2,595.06CAD1,825.19CAD220GAL165GALA1Gaskets69,696.00USD74,745.00USD47,009.03USD51,391.44USD7,920.00GAL7,920.00GALA3Auto Others640.5USD498USD500.91USD399.95USD70GAL40GALA4Safety Fabric873,180.01USD1,169,366.16USD602,915.00USD791,936.37USD103,588.47***136,413.86***D1Packaging Films29,152.75USD20,905.50USD22,929.11USD16,399.82USD2,035.00GAL1,430.00GALD2Construction64,944.00USD30,668.00USD42,151.43USD19,639.93USD7,920.00GAL3,740.00GALD3Gaskets354,572.60USD304,941.32USD204,806.25USD169,327.50USD35,397.67***29,666.38***D4Micro Others225,619.62***210,270.87***163,518.41***146,236.44***24,019.02***23,398.21***D5SV-Independent Exp0USD45.75USD0USD35.48USD0GAL5GALI72001 MktBusiness areaGrace Construction PrPlantEnoree - Verm DispersNo. of Customer group: 13Customer groupGrs Sls less RgGrs Sls less Rg-PYGross MarginGrs.Margin - PYNet Invoice QtyInvoiced qty - PYCGrpTotal1,815,102.98***1,524,389.84***1,198,071.39***1,004,264.31***202,858.43***173,329.78***335.25USD0USD280.64USD0USD15GAL0GALRegular791.61USD46,972.73USD598.63USD36,798.18USD64.994***3,278.10***1SV-Friction2,535.52CAD0CAD1,825.19CAD0CAD165GAL0GALA1SV-Gaskets74,745.00USD62,634.00USD51,391.44USD42,668.67USD7,920.00***6,702.36***A3SV-Auto Others498USD449.25USD399.95USD358.82USD40***31.609***A4SV-Safety Fabric1,169,366.16USD870,097.31USD791,936.37USD565,753.27USD136,413.86***115,521.29***D1SV-Packaging Films20,905.50USD135,507.98USD16,399.82USD102,915.59USD1,430.00***7,936.30***D2SV-Construction30,668.00USD71,258.00USD19,639.93USD44,971.38USD3,740.00***9,064.33***D3SV-Gaskets304,941.32USD207,910.19USD169,327.50USD120,156.78USD29,666.38***19,223.72***D4SV-Micro Others210,270.87***129,265.88***146,236.44***90,399.07***23,398.21***11,557.07***D5SV-Independent Exp45.75USD0USD35.48USD0USD5GAL0GALI7SV-Indust Others0USD0USD0USD0USD0LB0LBI8SV-Waste Others0USD294.5USD0USD242.55USD0GAL15GALW42000 MktBusiness areaGrace Construction PrPlantEnoree - Verm DispersNo. of Customer group: 10Customer groupGrs Sls less RgGrs Sls less Rg-PYGross MarginGrs.Margin - PYNet Invoice QtyInvoiced qty - PYCGrpTotal1,524,389.84USD1,680,033.99USD1,004,264.31USD1,179,907.35USD173,329.78***184,063.98***Regular46,972.73USD10,761.34USD36,798.18USD7,825.84USD3,278.10***1,175.13***1SV-Gaskets62,634.00USD11,111.10USD42,668.67USD7,858.37USD6,702.36***1,543.27***A3SV-Auto Others449.25USD366USD358.82USD201.56USD31.609***26.435***A4SV-Safety Fabric870,097.31USD863,760.03USD565,753.27USD587,625.37USD115,521.29***105,737.69***D1SV-Packaging Films135,507.98USD324,458.52USD102,915.59USD253,037.19USD7,936.30***15,849.59***D2SV-Construction71,258.00USD54,543.50USD44,971.38USD37,654.90USD9,064.33***8,359.03***D3SV-Gaskets207,910.19USD297,553.33USD120,156.78USD206,895.89USD19,223.72***34,855.04***D4SV-Micro Others129,265.88USD117,388.67USD90,399.07USD78,757.84USD11,557.07***16,511.19***D5SV-Refractory0USD91.5USD0USD50.39USD0LB6.609LBI3SV-Waste Others294.5USD0USD242.55USD0USD15GAL0GALW4microliteBusiness RegionNorth AmericaPlantEnoree - Verm DispersNo. of Period: 36PeriodGrsSlsLesRgGrsSlsLesRg PrYrSlsGrsMrgnSlsGrsMrgn PrYrVolumeVolume PrYrTotal4,958,199.70USD3,336,170.73USD3,287,072.73USD2,199,978.80USD78,966.23FT352,975.34FT3Jan-0067,660.33USD0USD44,300.39USD0USD1,355.34FT30FT3Feb-00131,487.27USD0USD93,341.39USD0USD1,646.45FT30FT3Mar-00172,629.79USD0USD119,556.56USD0USD2,509.67FT30FT3Apr-00135,744.50USD0USD84,363.38USD0USD2,808.76FT30FT3May-00154,677.06USD0USD99,145.85USD0USD2,696.22FT30FT3Jun-00143,560.59USD0USD92,180.46USD0USD2,211.08FT30FT3Jul-00130,336.16USD0USD93,486.72USD0USD1,545.23FT30FT3Aug-00153,752.06USD0USD99,360.26USD0USD2,640.23FT30FT3Sep-0093,671.43USD0USD60,638.49USD0USD1,437.56FT30FT3Oct-00131,984.22USD0USD85,250.60USD0USD2,324.53FT30FT3Nov-0089,769.45USD0USD61,134.59USD0USD1,170.91FT30FT31,524,389.84Dec-00119,116.98USD0USD71,505.62USD0USD2,040.45FT30FT3Jan-01180,837.01USD67,660.33USD118,327.36USD44,300.39USD2,707.65FT31,355.34FT3Feb-01137,547.13USD131,487.27USD83,281.33USD93,341.39USD2,160.89FT31,646.45FT3Mar-01169,184.58USD172,629.79USD118,358.73USD119,556.56USD2,258.94FT32,509.67FT3Apr-0170,858.29USD135,744.50USD46,486.66USD84,363.38USD1,205.36FT32,808.76FT3May-01149,606.46USD154,677.06USD101,901.41USD99,145.85USD2,489.88FT32,696.22FT3Jun-01228,232.75USD143,560.59USD148,573.26USD92,180.46USD3,625.17FT32,211.08FT3Jul-0186,394.34USD130,336.16USD58,277.52USD93,486.72USD1,273.56FT31,545.23FT3Aug-01149,515.15USD153,752.06USD92,254.71USD99,360.26USD2,796.28FT32,640.23FT3Sep-01142,459.73USD93,671.43USD98,079.23USD60,638.49USD2,039.65FT31,437.56FT3Oct-01200,214.69USD131,984.22USD135,578.60USD85,250.60USD3,201.70FT32,324.53FT3Nov-01110,132.26USD89,769.45USD65,796.06USD61,134.59USD2,056.44FT31,170.91FT31,811,780.89Dec-01186,798.50USD119,116.98USD128,799.62USD71,505.62USD2,773.40FT32,040.45FT3Jan-02132,187.19USD180,837.01USD86,558.39USD118,327.36USD2,449.91FT32,707.65FT3Feb-02149,178.07USD137,547.13USD95,328.24USD83,281.33USD2,602.97FT32,160.89FT3Mar-0288,319.27USD169,184.58USD57,777.31USD118,358.73USD1,503.53FT32,258.94FT3Apr-02168,806.94USD70,858.29USD112,349.53USD46,486.66USD2,614.27FT31,205.36FT3May-02174,433.28USD149,606.46USD122,608.22USD101,901.41USD2,515.49FT32,489.88FT3Jun-02146,403.42USD228,232.75USD95,031.93USD148,573.26USD2,429.74FT33,625.17FT3Jul-0277,257.41USD86,394.34USD54,240.33USD58,277.52USD1,012.30FT31,273.56FT3Aug-02189,624.81USD149,515.15USD127,613.66USD92,254.71USD2,985.13FT32,796.28FT3Sep-02126,121.88USD142,459.73USD85,857.82USD98,079.23USD1,995.88FT32,039.65FT3Oct-0284,802.25USD200,214.69USD54,540.21USD135,578.60USD1,523.42FT33,201.70FT3Nov-02110,236.90USD110,132.26USD72,094.63USD65,796.06USD1,858.67FT32,056.44FT31,622,028.97Dec-02174,657.55USD186,798.50USD123,093.66USD128,799.62USD2,499.59FT32,773.40FT3Avg Gross Margins67.0%MicroLite SalesYearSales $2000$1,5242001$1,8122002$1,6222003 Annualized$1,691microlite0000Year$MM SalesMicroLite SalesMktsMicrolite Markets (2000 - 2003)2003 Projected200220012000Avg GrowthCustomer groupGrsSlsLesRgSlsGrsMrgnMargin %GrsSlsLesRgSlsGrsMrgnMargin %GrsSlsLesRgSlsGrsMrgnMargin %GrsSlsLesRgSlsGrsMrgnMargin %Regular$ -$ -0%2,352.311,878.5180%791.61598.6376%46,972.7336,798.1878%SV-Friction$ 5,359$ 3,87672%3,537.602,595.0673%2,535.521,825.1972%000%SV-Gaskets$ 54,490$ 35,87066%69,696.0047,009.0367%74,745.0051,391.4469%62,634.0042,668.6768%SV-Auto Others$ 659$ 51077%640.5500.9178%498399.9580%449.25358.8280%SV-Safety Fabric$ 1,008,136$ 704,72970%873,180.01602,915.0069%1,169,366.16791,936.3768%870,097.31565,753.2765%SV-Packaging Films$ 25,331$ 19,13576%29,152.7522,929.1179%20,905.5016,399.8278%135,507.98102,915.5976%SV-Construction$ 168,854$ 108,38064%64,944.0042,151.4365%30,668.0019,639.9364%71,258.0044,971.3863%SV-Gaskets$ 207,515$ 118,25057%354,572.60204,806.2558%304,941.32169,327.5056%207,910.19120,156.7858%SV-Micro Others$ 220,657$ 159,91172%225,619.62163,518.4172%210,270.87146,236.4470%129,265.8890,399.0770%TOTAL$ 1,691,001$ 1,150,66068%$ 1,623,695$ 1,088,30467%$ 1,814,722$ 1,197,75566%$ 1,524,095$ 1,004,02266%Graph dataCustomer group2000 ($1.5MM)2001 ($1.8MM)2002 ($1.6MM)2003 ($1.7MM Proj)Safety Fabric870,097.311,169,366.16873,180.01$ 1,008,136Construction71,258.0030,668.0064,944.00$ 168,854Gaskets270,544.19382,221.84427,806.20$ 287,364Micro Others312,195.84232,465.98257,765.18$ 246,647TOTAL$ 1,524,095$ 1,814,722$ 1,623,695$ 1,711,002Mkts0000000000000000Safety FabricConstructionGasketsMicro OthersYearMicroLite Markets

US 4,655,842 (EP0212930B1) and US 4,780,147 use of Li citrate ion in manufacturing (current process)US5,102,464 (EP0366417B1) - use of an anionic chelating agent in manufacturing process (not in use)US 5,326,500 (No Euro) details optimal grade selection of vermiculite US 5,330,843 and US 5,336,348 covers the treatment of MicroLite to enable water resistivityTrade Secrets Manufacturing Concentration dispersion process (used in all products) Homogenation Dispersion 963 and 963 ++Low and moisture-free product

MicroLite Vermiculite Dispersions

Intellectual Property

MicroLites patents cover current and improved manufacturing processes, Vermiculite selection and application processes. Product development and manufacturing trade secrets are significant.

Primary manufacturing patents expire October 2005 in the US (August 2006 in Europe and Japan).More efficient process under 464. If used, protection till 09. Higher levels of exfoliation than current process.Vermiculite selection patent 500 maximize selectionApplication patents pertaining to a practical approach to water resistance. Currently used by some customers. Coverage till 2011. Significant trade secrets provide barriers to entryTechniques were developed to make MicroLite hydrophobic

MicroLite IP

Nanocomposite Benefits

Lower DensityReinforcementIncreased Dimensional StabilityIncreased HDTImproved Barrier PropertiesSynergistic Flame Retardant ApproachIncreased melt strengthThermoplastic Recyclable

*

Evolving Application Areas

ReinforcementThermalBarrierSynergistic Flame Retardant

*

From concept to production

Concepts lead to new technologies and products, but its all academic until you bring it to and through the production floor.

Commercialization Timelines

Nano is happening nowOne nanostep at a timeCost, performance, valueCompeting materials

Source: Southern Clay Products

The critical pieces are now in place to broadly move the concept forward to commercial applications.Timing-wise, I believe were still a few years away from a robust marketyes, I do believe there will be a nano in your future.

/(OVMT)
Preparation and Characterization of Epoxy Organic-Vermiculite (OVMT) Hybrid Nanocomposites

(Organic VermiculiteOVMT)

/(PLS)

11

Pristine VMT

Organic VMT

Intercalation

Exfoliation

d001

d001

Epoxy Resin/OVMT nanocomposite

Hexadecyltrimethylammoniun bromideHDTMABMw=284.54g/mole Cetylpyridium chloride monohydrateCPCMw=304.53g/mole N-DodecylamineDDAMw=186.35g/mole 14.cdx15.cdx16.cdx

Epoxy Resin, Hardener, and Accelerant

Diglycidyl ether of bisphenol ADGEBAEpoxy Equivalent weightEEW=176-184 g/eq4-Methylhexanhydrophthalic anhydrideMHHPAweight(AEW)=160-170 g/eq , Mw=168.2g/mole N-benzyldimethylamineBDMA17.cdx18.cdx19.cdx

1. VMTOVMT

WAXD

FTIR

TGA

DSC

TEM

(aq) + Vermiculite

8024

100 24

Organic Vermiculite

AgNO3

2. Epoxy/VMT nanocomposite

Epoxy Resin + MHHPA + Organic Vermiculite + Acetone

24

Epoxy blends 5012

BDMA 1.5phr

WAXDFTIRTGADSCTEM

d001=4.09nm

d001=1.2nm

d001=4.55nm

d001=3.81nm

WAXD patterns of

(a)pure VMT

(b)VMT/CPC OVMT

(c)VMT/DDA OVMT

(d)VMT/HDTMAB OVMT

WAXD patterns of

(a)pure VMT

(b)VMT/CPC OVMT

(c)140mesh VMT/HDTMAB OVMT

(d)60 mesh VMT/HDTMAB OVMT

(e)VMT/DDA OVMT

(f)nanoVMT/HDTMAB OVMT

20.bin

Refecence

Tsay SY, Chen BK, Chen CP. JOURNAL OF APPLIED POLYMER SCIENCE 99 (6): 2966-2972 MAR 15 2006

Uyanik N, Erdem AR, Can MF, Celik MS. POLYMER ENGINEERING AND SCIENCE 46 (8): 1104-1110 AUG 2006

2d sin=nn=1 , =1.541838VMTMMT2d0012d001pure VMT7.381.2nmpure MMT(Nanofil 757)6.501.36nmnano VMT+HDTMAB case12.164.09nmorganoclay with n-dodecylamine3.602.45nmnano VMT+HDTMAB case22.204.02nmorganoclay with HDTMAB3.002.94nmVMT+n-dodecylamine1.944.55nmorganoclay with dodecylamine4.082.16nmVMT+cetylpyridinium chloride2.323.81nm60mesh VMT+HDTMAB 1.924.6nm140mesh VMT+HDTMAB 2.084.25nm

Perkin Elmer spectrum GX

FTIR patterns of

(a)pure VMT

(b)HDTMAB

(c)VMT/HDTMAB OVMT

21.bin

Perkin Elmer spectrum GX

FTIR patterns of

(a)pure VMT

(b)CPC

(c)VMT/CPC OVMT

22.bin

TGA of Quats-VMT

23.unknown

Conclusion

1.FTIRWAXDVMT2.WAXD3DDA 4.55nm3.TGAneat epoxy4.TGA

NUK

24.unknown

Modulus vs Dispersion

0

0.5

1

1.5

2

2.5

3

3.5

4

4.5

5

0510152025303540

TEM Dispersion

Tensile Modulus, GPa

Nylon

30B

15A

Cloisite 30B 90 meq/100g

Cloisite 10A 125 meq/100g

Cloisite 25A 125 meq/100g

Cloisite 15A 125 meq/100g

Cloisite 20A 95 meq/100g

Increasing polymer/monomer

hydrophobicity

Cloisite

15A

Cloisite

20A

Cloisite

25A

Cloisite

10A

Cloisite

93A

Cloisite

30B

Increasing surface hydrophobicity

Cloisite

Na+

(Aqueous Systems)

Microlite Markets

$-

$400,000

$800,000

$1,200,000

$1,600,000

$2,000,000

2000

($1.5MM)

2001

($1.8MM)

2002

($1.6MM)

2003

($1.7MM

Proj)

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Micro Others

Gaskets

Construction

Safety Fabric

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