applied colloid technology: how do i apply the principle of colloid chemistry in industrial r&d...
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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
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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.
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*
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*
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Journal Articles
Use Web of Science Search for the Number of Recent ArticlesClay Nanocomposite: 1641Montmorillonite Nanocomposite: 989Vermiculite: 13 -
Dispersion:
Particles Shear Apart
Platelets Peel ApartPlatelets Peel Apart
Particles Shear Apart
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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)
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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 tiresMichelin 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+
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2: 1 Layered Silicate
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Montmorillonite
1 micron
SEM Bentonite Rock TEM Montmorillonite
Source: Southern Clay Products
10 microns
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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)*
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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
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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.
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N
C18
CH2CH2OH
HOCH2CH2
Methyl, Tallow, bis-2-Hydroxyethyl, Quaternary Ammonium X
CH3
+
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Cloisite 30B
90 meq/100g
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N
C18
C18
H
CH3
Methyl, Dihydrogenatedtallow, Ternary Ammonium X
+
Cloisite 93A (90 MER)
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N
C18
CH2
CH3
Dimethyl, Hydrogenated tallow, Benzyl, Quaternary Ammonium X
CH3
+
*
Cloisite 10A
125 meq/100g
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N
C18
CH2CH(CH2)3CH3
CH3
Dimethyl, Hydrogenated tallow, 2-Ethylhexyl, Quaternary Ammonium X
CH3
C2H5
+
*
Cloisite 25A
125 meq/100g
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N
C18
C18
CH3
CH3
Dimethyl, Dihydrogenated tallow, Quaternary Ammonium X
+
*
Cloisite 15A
125 meq/100g
Cloisite 20A
95 meq/100g
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SCP CLOISITE Products
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( ( ( ( ( (
Increasing polymer/monomer hydrophobicity( ( ( ( ( (
( ( ( ( ( (
Increasing surface hydrophobicity
Cloisite 15A
Cloisite 20A
Cloisite 25A
Cloisite 10A
Cloisite
93A
Cloisite 30B
Cloisite Na+
(Aqueous Systems)
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Leistritz Counter Rotating IntermeshingHigh Shear
Medium Shear
Low Shear
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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
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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.
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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 reservesMicroLite Business
At Enoree, SC siteSeparate downstream processVermiculite Mine
Expansion Processing
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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 barriersMicroLite 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
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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
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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 AsiaConstruction
Wall coverings and room partitions for public spacesGaskets 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 hydrophobicMicroLite 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. VMTOVMTWAXD
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)
Year
Micro Others
Gaskets
Construction
Safety Fabric
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MELT
BLENDING
Polymer
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Delaminated
or
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Intercalated
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+
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