new understanding of clay minerals - esdmpsdg.bgl.esdm.go.id/makalah/s.m.koh(presentation).pdf ·...

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


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


Tetrahedron structure



Three ways of tetrahedral sheet



Octahedron structure


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


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


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


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


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


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

New Field of Clay Minerals

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 ?


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 ?


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 !

new understanding of clay minerals - esdmpsdg.bgl.esdm.go.id/makalah/s.m.koh(presentation).pdf ·...

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