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New Understanding of Clay MineralsNew Understanding of Clay Minerals
Sang-Mo KohGeology and Geoinformation Division, KIGAM
2006. 11. 27
-
Clay & Clay MineralsClay & Clay Minerals
-
ContentsContents
Introduction Definition of clay and clay minerals
Classification of clay minerals
Structure of clay minerals
Properties of clay minerals
Utilization of clay minerals
New field of clay minerals
Organo-c
lay : Mod
ified
clay
Nano-com
posite cl
ay
-
Introduction
-
Field of Clay Mineralogy Field of Clay Mineralogy
Clay Mineralogy
Mineralogy
Crystallography
Quantitative chemistry
Geology
Soil science
Physical chemistry
-
All the materials with size less than 2m in soils (ISSS)
ISSS: International Society of Soil Science
What is clay ? What is clay ?
Ceramics
Definition
A very fine grained soil that is plastic when moist but
hard when fired.
Civil engineering
Decomposed fine materials with the size less than 5m
in weathered rocks and soils
Geology Sediments with the size less than 1/256mm (4m)
Pedology
Size terminologySize terminology
-
What is clay mineral ? What is clay mineral ?
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
-
Classification of clay minerals Classification of clay minerals
Definition in Clay Mineralogy (Bailey, 1980)
Layertype
Group(x=charge per formula unit)
Subgroup Species
Kaolin Kaolinite, dickite, halloysite, nacrite
Serpentine Chrysotile, lizardite, amesite
Pyrophyllite Pyrophyllite
Talc Talc
Montmorillonite(dioctaheral smectite) Montmorillonite, beidellite, nontronite
Saponite(trioctahedral smectite) Saponite, hectorite,
Dioctaheral vermiculite Dioctaheral vermiculite
Trioctaheral vermiculite Trioctaheral vermiculite
Dioctaheral mica Muscovite, illite, glauconite, paragonite
Trioctaheral mica Phlogopite, biotite, lepidolite
Dioctaheral brittle mica Margarite
Trioctaheral brittle mica Clintonite, anandite
Dioctaheral chlorite donbassite
Di,trioctaheral chlorite Cookeite, sudoite
Trioctaheral chlorite Chlinochlore, chamosite, nimite
Sepiolite Sepiolite
Palygorskite palygorskite
Palygorskite~sepiolite
x=variable
Chloritex=variable
Brittle micax=2.0
Micax=0.5-1.0
Vermiculitex=0.6-0.9
Smectitex=0.2-0.6
Pyrophyllite~talcx=0
2:1
1:1Kaolin~
serpentinex=0
-
Structure of clay minerals Structure of clay minerals
Definition in Clay Mineralogy (Bailey, 1980)
Tetrahedron structure
-
Structure of clay minerals Structure of clay minerals
Definition in Clay Mineralogy (Bailey, 1980)
Three ways of tetrahedral sheet
-
Structure of clay minerals Structure of clay minerals
Definition in Clay Mineralogy (Bailey, 1980)
Octahedron structure
-
Structure of clay minerals Structure of clay minerals
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
Trioctahedral & dioctahedral sheet
-
Structure of 1:1 type clay minerals Structure of 1:1 type clay minerals
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
-
Structure of 2:1 type clay minerals Structure of 2:1 type clay minerals
Octahedral sheet
2:1 layer structure consists of two tetrahedral sheet with one bound to
each side of an octahedral sheet.
Smectite, micas, pyrophyllite, and vermiculite etc.
-
Equipment for research of clay mineralsEquipment for research of clay minerals
X-ray Diffractometer
Thermal Analyser
FTIR
SEM
TEM
EPMA
Qualitative and quantitative analysis of clay minerals
Study on the crystal structure
Study on the mineral chemistry
Study for the utilization of clay minerals
-
Properties of clay mineralsProperties of clay minerals
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
-
Properties of clay mineralsProperties of clay minerals
Negative Charge : Cation Exchange Capacity (CEC)
: High Adsorption Capacity of Heavy Metals
& Cationic nuclides
Mineral type CEC (cmol/kg)
Kaolinite 3-15 Halloysite (2H2O)
5-10
Halloysite (4H2O)
40-50
Zeolite 100-300 Diocahedral vermiculite 10-150 Trioctahedral vermiculite 100-200 Chlorite 10-40 Biotite 10-40 Smectite 80-150
-
Properties of clay mineralsProperties of clay minerals
High Surface Area : high adsorption capacity
Surface area(cm2/g) Mineral type BET EGME
Montmorillonite 35 ~ 48 810 Kaolinite 5 ~ 9 48 Halloysite 76-173 Atapulgite 50 ~ 83 Illite 89 ~ 112 193 Talc 2.4 ~ 5.8 7 Vermiculite 350 Hectorite 461
EGME
Ethylene Glycol
Monoethyl Ether
High Refractoriness : SK
-
Properties of clay mineralsProperties of clay minerals
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
-
Classic UtilizationClassic Utilization
Ceramics : pottery, sanitary ware, refractory brick, tile etc.
: kaolin, pyrophyllite, illite(sericite)
PlasticPlasticMaterialsMaterials
RefractoryRefractoryMaterialsMaterials Flux MaterialFlux Material
Mixing, Mixing, Molding,Molding,Drying, SinteringDrying, Sintering
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Classic UtilizationClassic Utilization
Filler : paper, plastic and rubber (kaolinite, pyrophyllite)
Cosmetics : kaolinite, smectite, illite, talc
Glass fiber : pyrophyllite, dickite
Civil engineering (water barrier & stablizer) : bentonite
(smectite)Foundry : bentonite (smectite)
Agricultural fertilizer : pyrophyllite, kaolinite etc.
Environmental barrier : backfill material of waste disposal site
: artificial barrier of nuclear disposal site
-
Classic UtilizationClassic Utilization
Best Clay MineralsBest Clay Minerals ? ? for Environmental Remediation or Treatment for Environmental Remediation or Treatment
-
BentoniteBentonite
Industrial ore composed of smectite (mainly montmorillonite)
MontmorilloniteR+0.33 (Al1.67Mg0.33)Si4O10(OH)2Expandable interlayer Exchangeable cations in interlayer high adsorption capacity
Pre-purification Post-purification
Waste water purification
- precipitation of phosphates- sorption of heavy metals- purification of sewage plants: nitrogen and ammonium
gases
-
BentoniteBentonite
Liner of Waste Disposal Site ( Prevention of leachate)
-
BentoniteBentonite
Nuclear Waste Disposal Site
Radionuclide transport barrier : adsorption of nuclides
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New Field of Clay Minerals
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Recent New Field of Clay Minerals ?Recent New Field of Clay Minerals ?
Modification of Clay Minerals
Pillared ClayOrganoclay
Organo-modified clay
Purified clay(Ca-type clay)
+ + ++
+ + +
- - - -
- - -
H2O
Na+Organic
substances
H2O
CaOH OH
-
CaOH OH
-
--Na
Na
OH
OHOH
OH
OH
OH
-
--
-
Preparation ofNano-composite
-
What is Organoclay ?What is Organoclay ?
Modification of Clay Minerals
Pillared Clay
Organic chemicals can be adsorbed on the clay
surface and interlayer.
Compound of clay mineral and organic chemicals
It is manufactured by the reaction between clay and chemicals.
-
OrganoclayOrganoclay
Modification of Clay Minerals Commonly used clay mineral : smectite
Expandable Interlayer & high charge
-
Organo-modified mineralsOrgano-sericiteOrgano-zeolite
Organo-montmorillonite
Different mineral types
Different surfactants (chemicals)
Characteristics of organo-modified minerals manufactured by different minerals and chemicals
-
Organo-modified mineralOrgano-modified mineral
2 12 22 32 42
2 Theta
0
2000
4000
6000
8000
Inte
nsity
(cou
nts
/ sec
ond)
S10.05 (001)
S5.03(002)
M
M M M
M M
Mo12.5(001)
S : Sericite C : Clinoptilolite M : Mordenite Mo : MontmorilloniteCT : Opal-CT
C
Mo(002)
Mo(020)
CT
Mo(005)
Mo(006)
S S
S
S
S S
S S
S
S S
C
C
C
C C C C C
C
Hyamine 1622R
Benzyldimethyltetradecylammonium (BDTDA)
Benzyltrimethylammonium (BTMA)
5
Three minerals Three
Chemicals
-
Organo-montmorilloniteOrgano-montmorillonite
Hyamine
NO
O
N
N
BDTDA (Benzyldimethyltetradecylammonium)
BTMA (Benzyltrimethylammonium)
0 50 100 150 200 250 300 350 400 450
Exchanging amount compared to CEC (%)
0
50
100
150
200
250
300
Actu
al e
xcha
nged
am
ount
com
pare
d to
CEC
(%)
12.5
22.9
103%
27.314.1
27.5
14.0
14.1
191%
213%
239%
2 2 4 6 8 4 6 8 2 4 6 8 10
Na-montmorillonite
10 10
27.9
19.19
15.9429.51
16.02
30.68
16.27 14.9
HYAMINE-MONTMORILLONITE
BDTDA-MONTMORILLONITE
BTMA-MONTMORILLONITE
199%
238%
262%
40%
60%
78%
89%
93%
96%
97%
Non-treated
103%
Non-treated
30.84
2 THETA
0
4000
8000
12000
16000
20000
INTE
NSI
TY (C
OU
NTS
/ S
ECO
ND
)
XRD pattern of Hyamine-. BDTDA, and BTMA-montmrorillonite with increasing chemicals : the interlayer(d001) is gradually expanded to 27.9, 30.8 and 14.9.
Adsorption capacity of three chemicals into montmorilloniteBDTDA and Hyamine show the strong interlayer expansion and the excellent
adsorption into montmorillonite.
-
Adsorption behaviors Adsorption behaviors
BDTDA-MONT
HYAMINE-MONT
BTMA-MONT
mmol Surfactant / L
Am
ount
ads
orbe
d (
cmol
/ kg
)
BDTDA-Zeolite
BDTDA -Sericite
Hyamine-Zeolite
Hyamine-Sericite
BTMA-Zeolite
BTMA-Sericite
0.0 0.5 1.0 1.5 2.0 2.5
Equilibrium concentration (mmol / L)
0
5
10
15
20
25
Amou
nt a
dsor
bed
(cm
ol /
kg)
Adsorption isotherm curves of several organomodified minerals Of them, BDTDA and Hyamine-montmorillonite show the strong and stable adsorption into montmorilloniteSo, montmorillonite is the best mineral & BDTDA is the one of the best chemicals for the manufacturing the organo-minerals.
-
Organo-modified montmorillonite
Most economic chemicals
BDTDA (160 US$ / 50g)
HDTMA (286 US$ / 50g)
CP (77 US$ / 500g)
To investigate the adsorption capacity and
behavior of CP exchanged smectite
-
Organic chemicals Organic chemicals
Modification of Clay Minerals Organic cations : Quaternary ammonium cations
II . N a m e A b b rev ia tion S tru ctu re M r (ch lo r id e sa lt)
H ex ad ecy l- tr im eth y l-
am m on iu m H D T M A +
3 2 0 .0 1
C ety lp y r i- d in iu m (H ex ad ecy lp -r id in iu m )
C P +
3 5 8 .0 1
B en zy ld im et-h y lte tra d ecy l- am m o n iu m
B D T D A +
3 6 8 .0 5
CP is firstly studied in my research
Journal of Clay Minerals (2005)
-
0 4 8 12 16 20
mmol CP / l
0
50
100
150
200
250
300C
P ( c
mol
/ kg
)
0 4 8 12 16 20
mmol CP / l
0
50
100
150
200
250
300
CP
( cm
ol /
kg )
CP Na smectite CP Ca smectite
Adsorption isotherm curves of CP-smectite.CP shows the excellent adsorption into smectite like HDTMA
and BDTDA-smectite : L type isotherm
Adsorption BehaviorAdsorption Behavior
-
HDTMA - Ca smectite
2 4 6 8 10
2Theta (degree)
0
2000
4000
6000
8000In
tens
ity (c
ount
s/se
cond
)
20%40%60%80%
100%150%200%
250%300%350%
400%
Non-treated15.02
16.2915.25
21.42
22.4622.46
31.64 20.06
37.09 19.66
38.38 19.75
38.5419.70
12.93
19.57
20.06
13.06
12.78
38.88
39.58
20%
40%
60%
Non-treated
80%100%150%200%250%
300%
350%400%
19.7919.93
13.20
40.12
2 4 6 8 10
2Theta (degree)
0
4000
8000
12000
16000
Inte
nsity
(cou
nts
/ sec
ond)
HDTMA - Na smectite
39.06
19.79
19.79
12.76
13.40
12.74
15.5416.94
20.8223.11
29.52 20.11 12.51
38.14
12.85
38.38
12.95
19.97
39.40
XRD patterns of HDTMA-smectite exchanged with different HDTMA concentration to check the change of smectite interlayer.
With increasing of HDTMA amount, the interlayer is expanded to39-40 . Excellent adsorption and sequential adsorption in the smectite interlayer
d(001) d(002) d(003)..
Interlayer expansion of HDTMA-smectiteInterlayer expansion of HDTMA-smectite
-
2 4 6 8 102 Theta ( degree )
0
4000
8000
12000
16000
Inte
nsity
( co
unts
/ se
cond
)
Nontreated
20%(18.8%)
40%(39.2%)
60%(58.6%)
80%(79.9%)100%(99.7%)140%(138.3%)
189%(170.2%)220%(183.9%)260%(194.7%)300%(198.3%)
340%(202.4%)
380%(216.5%)
420%(222.2%)
12.7
15.3
16.1
16.122.422.6
23.221.940.4
40.521
40.721
40.7
40.7
40.7
40.9
40.9
20.7
20.7
20.6
20.820.8
CP-Na smectite
2 4 6 8 102 Theta (degree)
0
2000
4000
6000
8000
Inte
nsity
(cou
nts
/ sec
ond)
Nontreated 20%(18.8%)
40%(39.2%)
60%(58.6%)
80%(79.9%)
100%(99.7%)
140%(138.3%)
180%(170.2%)220%(183.9%) 260%(194.7%)
300%(198.3%)
340%(202.4%)380%(216.5%)
420%(222.2%)
15.02
16.08
15.40
21.12
22.1822.21
20.8240.30
20.5839.76
39.7639.09
40.6739.58
40.6740.15
20.29
20.75
20.29
20.67
20.2820.48
CP - Ca smectite
Interlayer expansion of CP-smectiteInterlayer expansion of CP-smectite
XRD patterns of CP-smectite exchanged with different CP concentration. It shows the strong interlayer expansion and adsorption like HDTMA.
So CP can be used for the economic organosmectite.
-
Whats property ?Whats property ?
Modification of Clay Minerals
Pillared Clay
Hydrophyllic surface is changed to organophyllic nature
Hardness
Viscosity
Flocculation (dispersion behavior)
Sorption capacity
Structure (Interlayer expansion)
-
Smectite (Bentonite) Organo-smectite
0
2
4
6
8
10
12
pHHDTMA-bentonite
BDTDA-bentonite
CP-bentonite
0
2
4
6
8
10
12
pH
Na-be. Ca-be.Non-treated
pHpH
-
Volume expansion caused by bonding between interlayer of montmorillonite and water molecules.
0
5
10
15
20
25
30Sw
ellin
g (m
l/2g)
Na-be. Ca-be.Non-treated0
5
10
15
20
25
30
Swel
ling
(ml/2
g)
HDTMA-bentonite
BDTDA-bentonite
CP-bentonite
SwellingSwelling
-
0
2
4
6
8
10
12
visc
osity
( m
Pa
s )
HDTMA-bentonite
BDTDA-bentonite
CP-bentonite
0
2
4
6
8
10
12
Visc
osity
(mPa
s)
Na-be. Ca-be.Non-treated
ViscosityViscosity
-
Turbidity measurement Na-smectite : steady Ca-smectite : flocculatoin Organo-smectite : fast and strong flocculation
Time (Minutes)
400
600
800
1000
1200
1400
1600
1800Tu
rbid
ity (N
TU)
L E G E N D Non - treated Na - bentoniteCa - bentonite
0 1 5 10
0 10 20 30 40 50 60Time (min.)
0
200
400
600
800
1000
1200
Turb
idity
(NTU
)
LEGENDHDTMABDTDACP
Flocculation and dispersion behaviorFlocculation and dispersion behavior
-
Intercalation model of large molecules exchanged smectitesuch as HDTMA-, BDTDA, and CP-smectite.
40 (10+15+15)
Adsorption Model Adsorption Model
It is explained by the total length of expanded interlayer Double layered paraffin structure
-
5 10 15 20 25 30 35 40 45
2Theta (degree)
0
400
800
1200
1600
2000
Inte
nsity
(cou
nts
/ sec
ond)
2
No heating
90 C Heating
250 C Heating
400 C Heating
600 C Heating
890 C HeatingHDTMA - smectite
HDTMA-smectite 250 C > : HDTMA begins to decompose. 400 C : HDTMA is completely decomposed. 600 C > : smectite structure begins to decompose. 890 C : complete decomposition of smectite structue
19.4
13.8
12.8
12.6
0 500 1000
Temp.( C)
-20
0
20
40
60
20
24
28
32
DTAuv
TGAmgHDTMA - smectite
10.34mg34.4%
93.13 C268.84 C
889.36 C
606.94 C
403.60 C
Thermal stability of HDTMA-smectiteThermal stability of HDTMA-smectite
-
BDTDA-smectite 250 C > : BDTDA begin to decompose. 400 C : BDTDA is completely decomposed. 550 C > : smectite structure begins to decompose.
5 10 15 20 25 30 35 40 45
2Theta (degree)
0
400
800
1200
1600
2000
Inte
nsity
(cou
nts
/ sec
ond)
2
No heating
90 C Heating
250 C Heating
400 C Heating
600 C Heating
890 C Heating
BDTDA - smectite
24.6
14.0
12.5
10.9
0 500 1000
Temp.( C)
-20
0
20
40
60
20
24
28
32
DTAuv
TGAmg
11.154mg35.59%
89.87 C248.74 C
402.98 C
BDTDA - smectite
554.57 C
Thermal stability of BDTDA-smectiteThermal stability of BDTDA-smectite
-
Thermal stability of CP-smectite
CP-smectite 250 C > : BDTDA decomposed 430 C : completely decomposed 600 C > : smectite structure
decomposed 5 10 15 20 25 30 35 40 45
2Theta (degree)
0
400
800
1200
1600
2000
Inte
nsity
(cou
nts
/ sec
ond)
2
No heating
90 C Heating
250 C Heating
400 C Heating
600 C Heating
890 C HeatingCP-smectite
19.4
14.0
12.7
10.9
0 500 1000
Temp.( C)
-20
0
20
40
60
16
20
24
28
32
DTAuv
TGAmgCP - smectite
10.78 mg36%
434.5 C
90.65 C
262.3 C
609.73 C
896.13 C
-
Thermal stability of BDTDA-smectiteThermal stability of BDTDA-smectite
Generally HDTMAGenerally HDTMA--, BDTDA, BDTDA--, and CP, and CP--smectitesmectite, , their thermal decomposition begins at 250 their thermal decomposition begins at 250 CCand ends at around 400 and ends at around 400 C. C.
-
Utilization of organoclayUtilization of organoclay
- 1950 ~ : soil amendment, paint, paper, lubricant, grease, flocculant, adsorbent, cosmetics, medicines etc.
- Recent (G. R. Alther, 1998) : Removal of organic contaminantsM ortland
(1970) G. Alther (1998)Rem ovedpollutants
Lubricants M anufacturing process w ater Oil and grease
Paper Degreasing operation Oil and grease
Cosmetics Electroplating Heavy metals
Paint M etal casting Dye penetrate
Soil amendment Ground w ater and drinkingw ater
Oil and greaseHeavy metals
BTEX
Pentachlorophenol
Wood treating Creosote
Pigment production Organic pigments
Dry cleaning Perchloroethylene
-
Utilization of organoclay ? Utilization of organoclay ?
AC H50MH100M
H200MBD50M
BD100MBD200M
BT50MBT100M
BT200MNa-M
ZEOH-ZEO
BD-ZEOBT-ZEO
SERH-SER
BD-SERBT-SER
0.0
5.0
10.0
15.0
20.0
25.0
0.0
10.0
20.0
30.0
40.0
Amou
nt s
orbe
d (g
/ kg
)
0.0
10.0
20.0
30.0
40.0
Phenol
Benzene
Toluene
Hyamine- &
BDTDA-Mont.
Excellent
adsorbents of
Organic
pollutants
(BTEX)
This histogram shows sorption capacity of organic pollutants (phenol, benzene and toluene) by manufactured organo-modified minerals.
-
Less than 4~5% nanocomposite organoclayis mixed with major materials for the
light and strong parts of cars and cameras.
Ablation performance.
Environmental stability, etc.
Improvement of mechanical properties (strength and thermal stability).
Flammability resistance.
Recent New Utilization : Nanocomposite organoclayRecent New Utilization : Nanocomposite organoclay
-
Thank you for your attention !
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