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New Understanding of Clay Minerals

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New Understanding of Clay Minerals NewNew UnderstandingUnderstanding ofof ClayClay MineralsMinerals Sang-Mo Koh Geology and Geoinformation Division, KIGAM 2006. 11. 27 ClayClay && ClayClay MineralsMinerals Introduction ContentsContents Definition of clay and clay minerals Classification of clay minerals Structure of clay minerals Properties of clay minerals Utiliz New field of clay minerals ation of clay minerals Organo-clay : Modified clay Nano-composite clay Introduction FieldField ofof ClayClay MineralogyMineralogy Quantitative chemistry Crystallography Geology Clay Mineralogy Soil science Mineralogy Physical chemistry WhatWhat isis clayclay ?? Definition Size terminology Ceramics A very fine grained soil that is plastic when moist but hard when fired. Civil Decomposed fine materials with the size less than 5μm engineering in weathered rocks and soils Geology Sediments with the size less than 1/256mm (4μm) Pedology All the materials with size less than 2μm in soils (ISSS) ISSS: International Society of Soil Science WhatWhat isis clayclay mineralmineral ?? Definition in Clay Mineralogy (Bailey, 1980) Clay minerals belong to the family of phyllosilicates and contain continuous two-dimensional tetrahedral sheets of composition T2O5 (T=Si, Al, Be etc.) with tetrahedral linked by sharing three corners of each, and with the four corners pointing in any direction. The tetrahedral sheets are linked in the unit structure to octahedral sheets, or to groups of coordinating cations, or individual cations ClassificationClassification ofof clayclay mineralsminerals Group Layer (x=charge per Subgroup Species type Definition in Clayformula Mineralogyunit) (Bailey, 1980) Kaolin~ Kaolin Kaolinite, dickite, halloysite, nacrite 1:1 serpentine x=0 Serpentine Chrysotile, lizardite, amesite Pyrophyllite~ Pyrophyllite Pyrophyllite talc x=0 Talc Talc Montmorillonite Montmorillonite, beidellite, nontronite Smectite (dioctaheral smectite) x=0.2-0.6 Saponite Saponite, hectorite, (trioctahedral smectite) Vermiculite Dioctaheral vermiculite Dioctaheral vermiculite x=0.6-0.9 Trioctaheral vermiculite Trioctaheral vermiculite Dioctaheral mica Muscovite, illite, glauconite, paragonite 2:1 Mica x=0.5-1.0 Trioctaheral mica Phlogopite, biotite, lepidolite Brittle mica Dioctaheral brittle mica Margarite x=2.0 Trioctaheral brittle mica Clintonite, anandite Dioctaheral chlorite donbassite Chlorite Di,trioctaheral chlorite Cookeite, sudoite x=variable Trioctaheral chlorite Chlinochlore, chamosite, nimite Palygorskite~ Sepiolite Sepiolite sepiolite x=variable Palygorskite palygorskite StructureStructure ofof clayclay mineralsminerals Tetrahedron structure Definition in Clay Mineralogy (Bailey, 1980) StructureStructure ofof clayclay mineralsminerals DefinitionThree ways in Clay of tetrahedralMineralogy sheet(Bailey, 1980) StructureStructure ofof clayclay mineralsminerals Octahedron structure Definition in Clay Mineralogy (Bailey, 1980) StructureStructure ofof clayclay mineralsminerals Trioctahedral & dioctahedral sheet Octahedral sheet Six coordination number Divalent cations (Mg2+) : Three of every octahedral sites are occupied : Trioctahedral Trivalent cations (Al3+) : Two of every octahedral sites are occupied : Dioctahedral StructureStructure ofof 1:11:1 typetype clayclay mineralsminerals 1:1 layer structure consists of a unit made up of one octahedral& one tetrahedral sheet, with the apical O2- ions of the tetrahedral sheets being shared with the octahedral sheet. Kaolin and serpentine group StructureStructure ofof 2:12:1 typetype clayclay mineralsminerals 2:1 layer structure consists of two tetrahedral sheet with one bound to each side of an octahedral sheet. Octahedral sheet Smectite, micas, pyrophyllite, and vermiculite etc. EquipmentEquipment forfor researchresearch ofof clayclay mineralsminerals X-ray Diffractometer SEM Thermal TEM Analyser FTIR EPM A Qualitative and quantitative analysis of clay minerals Study on the crystal structure Study on the mineral chemistry Study for the utilization of clay minerals PropertiesProperties ofof clayclay mineralsminerals Permanent negative charge ( 2:1 clay minerals) - By isomorphic substitution in octahedral and tetrahedral site [ octahedral site: Al 3+ (Fe 3+)→Fe 2+, Ca 2+, Mg 2+ ] [ tertrahedral site: Si 4+ → Al 3+ , Fe 3+ ] pH dependent charge or edge charge (1:1 clay minerals) - Broken, structural defect (terraces, kinks, holes) - react with water molecules to form surface hydroxyl group aluminol and silanol functional group PropertiesProperties ofof clayclay mineralsminerals Negative Charge : Cation Exchange Capacity (CEC) : High Adsorption Capacity of Heavy Metals & Cationic nuclides Mineral type CEC (cmol/kg) Kaolinite 3-15 Halloysite 5-10 (2H2O) Halloysite 40-50 (4H2O) Zeolite 100-300 Diocahedral vermiculite 10-150 Trioctahedral vermiculite 100-200 Chlorite 10-40 Biotite 10-40 Smectite 80-150 PropertiesProperties ofof clayclay mineralsminerals High Surface Area : high adsorption capacity Mineral type Surface area(cm2/g) EGME BET EGME Ethylene Glycol Montmorillonite 35 ~ 48 810 Monoethyl Ether Kaolinite 5 ~ 9 48 Halloysite 76-173 Atapulgite 50 ~ 83 Illite 89 ~ 112 193 Talc 2.4 ~ 5.8 7 Vermiculite 350 Hectorite 461 High Refractoriness : SK PropertiesProperties ofof clayclay mineralsminerals High Viscosity Mineral type Viscosity (cP) : 10% solution Bentonite 10-30 Pyrophyllite 1-1.5 Kaolin 1-1.2 Sericite 1-1.2 High Expansion & Swelling Colloidal property Hydrophyllic property : well dispersed in the water solution Very easily hydrated and dehydrated High plastic property : important property of ceramic materials ClassicClassic UtilizationUtilization Ceramics : pottery, sanitary ware, refractory brick, tile etc. : kaolin, pyrophyllite, illite(sericite) Refractory Plastic Materials Flux Mateerialrial Materials Mixing, Molding, Drying, Sintering ClassicClassic UtilizationUtilization Filler : paper, plastic and rubber (kaolinite, pyrophyllite) Cosmetics : kaolinite, smectite, illite, talc Glass fiber : pyrophyllite, dickite Agricultural fertilizer : pyrophyllite, kaolinite etc. Civil engineering (water barrier & stablizer) : bentonite (smectite) Foundry : bentonite (smectite) Environmental barrier : backfill material of waste disposal site : artificial barrier of nuclear disposal site ClassicClassic UtilizationUtilization BestBest ClayClay MineralsMinerals ?? for Environmental Remediation or Treatment BentoniteBentonite Industrial ore composed of smectite (mainly montmorillonite) Montmorillonite + R 0.33 (Al1.67Mg0.33)Si4O10(OH)2 Expandable interlayer Exchangeable cations in interlayer high adsorption capacity Waste water purification - precipitation of phosphates - sorption of heavy metals - purification of sewage plants : nitrogen and ammonium gases Pre-purification Post-purification BentoniteBentonite Liner of Waste Disposal Site ( Prevention of leachate) BentoniteBentonite Nuclear Waste Disposal Site Radionuclide transport barrier : adsorption of nuclides New Field of Clay Minerals RecentRecent NewNew FieldField ofof ClayClay MineralsMinerals ?? Modification of Clay Minerals OrganoclayPillared Clay Organo-modified clay Organic ---- substances + + + + Na+ -- - - OH Na OH OH OH Ca OH OH Ca OH OH - - OH Na OH H2O - - H2O -+ --+ + Purified clay Preparation of (Ca-type clay) Nano-composite WhatWhat isis OrganoclayOrganoclay ? ? ModificationOrganic chemicals of Claycan be Minerals adsorbed on the clay surface and interlayer. Compound of clay mineral and organic chemicals Pillared Clay It is manufactured by the reaction between clay and chemicals. OrganoclayOrganoclay ModificationCommonly of used Clay clay Minerals mineral : smectite Expandable Interlayer & high charge Organo-modified minerals Organo-sericite Organo-zeolite Organo-montmorillonite Different mineral types Different surfactants (chemicals) Characteristics of organo-modified minerals manufactured by different minerals and chemicals Organo-modifiedOrgano-modified mineralmineral Three minerals Three Chemicals S 8000 S : Sericite C : Clinoptilolite M : Mordenite S Mo : Montmorillonite 10.05 (001) CT : Opal-CT R S Hyamine 1622 6000 5.03(002) S S S S S S S S S S C C C 4000 C C C C M M C M C M C M M Intensity (counts /Intensity second) Mo Mo Benzyldimethyltetradecylammonium (BDTDA) 2000 (005) 12.5(001) Mo (020) Mo (006) CT Mo (002) 0 212223242 2 Theta Benzyltrimethylammonium (BTMA) 5 Å Organo-montmorilloniteOrgano-montmorillonite HYAMINE BDTDA BTMA 300 BDTDA (Benzyldimethyltetradecylammonium) -MONTMORILLONITE -MONTMORILLONITE -MONTMORILLONITE N 27.9 14.1 30.84 16.27 14.9 20000 250 239% 262% 200 27.5 30.68 97% Hyamine 16000 O 14.0 16.02 O N 213% 238% 96% 150 29.51 12000 27.3 93% 15.94 14.1 100 89% BTMA (Benzyltrimethylammonium) 191% 199% N 50 8000 19.19 78% 22.9 Actual exchanged amount compared to CEC (%) CEC to compared amount exchanged Actual INTENSITY (COUNTS / SECOND) / (COUNTS INTENSITY 103% 60% 103% 0 40% 4000 0 50 100 150 200 250 300 350 400 450 12.5 Exchanging amount compared to CEC (%) Non-treated Na-montmorillonite Non-treated 0 2 4 6 810 2 4 6 810 2 4 6 810 2 THETA XRD pattern of Hyamine-. BDTDA, and BTMA-montmrorillonite with increasing chemicals : the interlayer(d001) is gradually expanded to 27.9, 30.8 and 14.9Å. Adsorption capacity of three chemicals into montmorillonite BDTDA and Hyamine show the strong interlayer expansion and the excellent adsorption into montmorillonite. AdsorptionAdsorption behaviorsbehaviors 25 BDTDA-MONT BDTDA 20 -Zeolite BTMA -Zeolite HYAMINE-MONT 15 Hyamine -Zeolite 10 BDTDA -Sericite Amount adsorbedAmount cmol ( kg ) / BTMA-MONT kg) / (cmol adsorbed
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