or heating

Themochimica Acra, 135 (1988) 319-334 Elsevier Science Publishers B.V., Amsterdam

319

POSSIBILITY OF FELDSPAR FORMATION IN BENTONITE SUSPENSIONS DURING STORAGE,DRYING AND/OR HEATING

E.T.

STcPKOWSKA,l 3.L.

P.J.

SANCHEZ SOTO,* S.A.

1 Institute

of

PEREZ-RODRIGUEZ,* A.

Hydroenginaerlng

2 Centro

de Recursos

3 King’s

College

JUSTO,’

3EFFERIS,3 PAS, Gdahek

Naturalsa

/Poland/

y Agroblologla,

Savllla

/Spain/

/U.K/

London

ABSTRACT Study

in

microstructure8

TG-analysis/

indlcataa

ferably

cluster

from

or due

to storage

of

that

bantonlta

feldspar

structure,

euapanalona

grain8

either

at

/XRD,

may be formed, elevated

SEM, pre-

temperature

and drying.

INTRODUCTION Study uaad

ne, sformation

in in

microstructure8 Civil

/XRD peaks

tonlta

suapanalons

phases

/parallel floe-aggregate

rious

new phases even

alllca bite

in

at

whereas 121, lactron shift

in

binding to

thoaa

which

favour

at

pH and

zones

montnorillonlta energy

electron

va-

a suitable

Authlganlc

by Hay [f].

No+ ion at

at

161.

taapa~atura

heated

and Auger

No-albite

with of

of

energetically

baa also

woo reported

environment

ban-

grains

[4],

lowest

that

formation

concentration

a high

tran-

atruc-

raollta-like

room tamparatura

in

of

found

cluster-aggregate

f aldapar-

deposits

phase

mlcroatructural

is

marina

detected

was

various

formation

saline-lake

auspanslo-

posaibla

evidence

Into

Feldspar

bantonita the

arrangement,

[14 /.

saturated was

Also

atructura/,

and eilica

feldspar

and SEM/.

/paragonits-,

raapac tivaly , see poaalbla

commarcial Indicated

may distribute particle

tura,

Na* ion

of

Engineering,

1100 kinatic

prevailing, 120

‘C,

In al-

- 125

‘C

Na-photodenergy

173.

Thermal Analysis Proc. 9th ICTA Congress, Jerusalem, Israel, 21-25 Aug. 1988 0040-6031/881$03.50 0 1988 Elsevier Science PublishersB.V.

both

320 THEORETICAL

In

the

be&en.

era,

CONSIDERATIONS

clay-water

colloidal

aggragetea/

and

at

repulsion,

external

In

which

case

is

dition tween

of

the

of

Decrease

in

change

attraction energy

forma.

This la,

It

is

VA4

of

is

E,

feldspar

was indeed

probability

of

thoas

stored

MATERIALS

and [lo],

v,_/

must

prefera-

in

water

I 0.

2,

This

distance

conbe-

content

at

redlatrlbution, into

/3/

various

al-

change

tn

site

of

with

alza

of

increases

for

new mineral

higher,

the

in-

that:

/I/

la

formed

in

phases

activation

or

change

thermal Its

of

Barkbsnt

final

energy

in

from zaollte

bantonite

tranaformatlon multiplfsd dried

oomaarcially /B/B/

and various

[ll):

ener-

other

the

on nlcroatructure

structure,

a prolonged

Into

more dense

preferably

observed

sir

In a po-

a negative

in

atruc-

lrmngement.

dependent

cluster

reaulta

drying

and

mey transform

la

phase

or

time

hsatsd air

the

parallal from

end

atruc[9),[11],

of

Indeed

suspensiona

sctlvatad

bentonitea stirring

wsre

action,

elmilar and

dried.

actions

to

Ns-form

prepared /energy

Brabent et

sy-

atruc-

floe

a function

by tI.ma and

phase

of

auapenslona

is

and

of

AND METHODS

concentrations [9]#

-VA,

of

energy

observed

Suapanaiona /B/R/

from

supplisd

ware

/i/

separation

equilibrium,

which

the

here

A

whish the

int

water

/2/

particle

paragonlta

forms

O/,

parallel

ture, i.e.

dVT/dg

change

/ r3r vR 70/

formation

ture, /2/

energy,

and

an extremum,

pT = -

conaolldatlon

repulsion

postulated

i.e.

of

at

Internal

local

L during of

transformation, stem,

forces

VT = VA + VR + VE vs.

/a/

attraction,

change

e.g.

intarnal

0, of

[B 1.

/a

gy or

/b/

of

elenentar bodies

to

vA<

of

by change

thlcknsaa,,

phases

ting

ture

swelling,

or

structural

due

attraction,

functions

curve.

system

/cluat-

definite

place

pressure:

the

particle

croatructural

altive

resultant elements

in

22:

as density

takes

interactions

elements

are

Balance

energy

in

structural

change

terac

total

fulfilled

consolidation

/c/

distance,

1/.

which

the

long-range

structure1

energies

pE /expressed

equlllbrium,

minimum

exist

other

eutual which

, Fig.

pressure, at

bly

13

there and

the

vR 7 0,

g /olvO-theory, exist

system

particles

various x time/,

In

321 I -pertide ~-cluster B-a99m9a2p

\ \vR

If %

interactions

_..16% consolidation

0.4 0.2 40° r*.

3

ntD:

20. 25’ 28 cu Kct F - foldmpmr, Cr e OrimtobBlit~, a

- qamrtr

m20.

sb

own

icr’

. fLkif”

322 Sample

number:

8/R-

1

2

3

B/8-

5

6

7

8

6%

5%

Concentratlonr Stirring

energy:

Stirring

time:

Serlea

time

Samples glass

re

were dried

studied

test,

co.

feldspar

ca.7% 6% oven 5000

a

b

d

e

f

2

4

4

5

8

RPM,

8/8-A

co.

6%,

5000

8/8-8

ca.

6%,

mixed

air

dried

either

h=(#m5em,

and

DTG and

at

will

formation

/series were

by XRD,

or

at

45’C,

rentloned

above.

prepered.

They

SEM, water

only

Here

O/

times

eaaplee

leboratories

months

15 aln

storing

some oriented

g 8

by hand.

18’C

after

TG analysis.

dry

RPM

15 min

0

various

In

DTA,

7000

10

0

containers,

Some oven

RPM

9 ca.6% 5% RPM

5 min

samples:

Unetored

In

2000

:

Storing

5%

4%

4

results

we-

8orption

pertaining

to

be presented.

RESULTS AND DISCUSSION Drying

pecking to

peaks

thick these

well

were

and 8OO’C for ht

losaee

nal ins. and

cluatar

for

the

crust

lh

of

es A 0.

rontrorlllenite

In

the

the

the

In of

the

tore,

by Seyama

5/.

extergrasurface Exeept

yellow

external

the

both the

4OO’C

and weig-

yellew sample

/Plg. in

[lo].

lndlcated

on the

brown

surfece

[9]

containing

content

aarple

heated

by

4 months

220°C,

see

tnterior

Identical

was observed

llO°C,

Si-

‘slide/.

eamples,

d /3-4g,

sample8

g

shown

on a glass

d/,

core

3.75

feldspar.

fl were

8/B

at

wee increased

was almost Na to

dried b end

aarple

to

dense

difficult

R or at

and 3.35

ltrueture

internal

3.3

powder

Heated

brown

which

in of

/air

parallel in

4.25

18h /series

or

and Internal

l truoture

at

in

grains

mey belong

statically

b/

resulted

some hard

series

stepwiee

ievealed

remaining elements Similar iigration ple

samples

/eeriea

decreased

et

detected

specimens

Na20-content,

and

either

II, which

peaka

recorded

crust

8EM study

of

heated

were

yellow

observed 3.2

not

and 8/e-8 of

oriented were

8/B-A

formation

bealdes

residuels

etorage/

were

around

peaks

Dried

samples and

reflections

these All

of

partfcles XRD peaks

grind.

or several ailar

llO°C

et

of

of

partakO]. sam-

powder

and Soma [7].

x3

. 28

Cu Koc

28 Cu KS

324 XRD was studied

of

some samples, -8b-

8/B-6b-,

terpreted

dehydrated

/2/

feldspar:

/Fig.

et

Fig. of

plea

lg,

2g,

dine

*in

etetu

sample

39,

8,

peek

samples,

small,

higher

/I=ll%/

2b/

heated end

in

et

/4/

/2/,

broad

peek it

ple [9].

The

ple

Fig.

/4/, Increase

It

found

intensity

8,

3.0-2.97 -

sample

to

weight

hfgh

B/8-9d-

chemical

end

unheated

morphology

eam-

of

In cluster

ran%-

structure

not

peeks

b, core

then

feldspar in:

/InlO%/

should

of this

sample

be noted

that

9.8

yellow

sample

first

of

w in

found 4e/. 3.06,

conpe-

surfece

ley-

the

sample the

peak was somewhat

ZIAC, /I=5%/,

cruet

B/8-9b-8OOeC/2/

the In

/8.7,

powder

eemple

heating

intensity

ones,

Fig.

% /G.Kranz,

/3/

the

hea-

3.

3.2

both

8,

were

yellow

Barkbent

of

and

were 2.7

peeks the

8/R

8/R-4b.

visible

Fig.

in

7.7

unheated

in

appeared

low

the

the

are

peak

end

after

a very

all

in

see /I/

/I=i6%/

peek

in

feldspar

grains,

com-

quartz

found.

3.19,

peeks

2.50

Also

/philfipsite/

3.27,

amphibole

beteen

were present

/4.98,

brown

/4.13-4.2,

and chemIoe1

samples.

sore

by SEM in

reolite

core

layers

and a weak order powder

/3/.

unground higher

moneamor.5 Sam-

%n barn-

25. in

8

In 8/R eem-

samples in

morphology

wee

disappeared

indicated

bend wee

surface

identified

8OO’C

/3/.

of

observed

8 was detected

of

brown

obaerved

and grains

compared

quartz

sample

tmorillonite

part

may be in-

2.

B/8

A grain

yellow

were

Appreciable

one

the

In

log.

samples,eeries

in

3.69-3.78

by 8EM in

layer

internal

3.2

morphology

by SEM in

peak

intexneities

Fig.

that

-ih.

ple

B/8

8,

of

in

x/

possibly

including

/2/

were

4.0

found

7.6-7.7

eurfece

2.69 s/. In all the

Relative

observed

were

crletobelite

poeeibly

8/8=2b,

Rerlln,

internal 8/R-2b-,-4b-,

7/.

3.35 at

which

some smell.

ratively

/Fig.

of

were

was

observed

Gypeum grelne

er,

4g end

et

elbite,

Some grains

nescendi”

were

/4.27

Also

the

i.e.

peaka

2.89,

low

especially

a gypsum

in

7.

Grains

positlon

/5/

the

peaks

grains

feldspar

8/R-2

R/.

ted

to

Feldspar-like

peaks

800°C,

All

3.49-3.5,

closer

composition

-2.6

and of

at

8 peak,

3.75,

were

ciretobalite,

/3/

heeled

4a/f

6.4

-800°C-18h,

of

/4/

3,

small

they

elbite.

part

surface

b,

montmorillonite

end others plea

the

and -9b-800°C-lh.

as

/l/

of

series

loss

D

G/llO°C-800%/

was observed

in

325 TABLE 1

Thermogravimetrlc atstic

heating

Sample

behsviour /series

Serlea

of

b/,

in

b

% 6.27

-2

6.12

-3

5.61

-4

6.28

g/

ruspensions and

in

in

DTG /series

surf int 120

11.7 13.7

65.3 71.6

567 564

658 656

surf int

9.4 10.1 9.7

44.0 56.3 56.1

559 569 569

645 645

111 113 112

* B/R-powder

bentonite

f/

DTA, series g, stored 8 months Dehydration : Dehydroxyla tion T DG Heat min Tdefl TmFn % mV.mln/G OC OC OC

stored 4 months G/110-800oC/

B/R-l

dried

DTA /series

4.65 DTG, series Oehydra tlon : T/completion/

f,

G,mg

OC

stored 8 months Dehydroxylatlon AG T/inflectfonAG % OC

: %

B/B-5

6.82

29

103

12.5

507

B/B&6

7.16

32

102

13.9

523

5.5

B/8-7

6.36

11

83

14.0

501

6.0

8/B-8

7.31

B/B-powder

4.58

-

surf

:

aurface

leyer,

int

-

internal

5.5

part.

go r-r -0 -J

-4 -5

momoDw4msww7woEo9w JEWERNURE

ru.

6

(DRR)

ItEAK!

OPR-1

wooo018w5ooEwmowwo TEWPERATURR

( OCR)

RIQAKU

OPSI

326 series

b in

crease

in

comparison

tFanaformstione cts

depend

of

the

A

samples

with

suspension

/Table

1/.

eerie8

f and

TG bahaviour

was detected.

structure/

and a

shorter

heating

/hare

~8, 30 mQ/ of

aempla

reported Also

pare

in

after

petterns, /emorphoua

matter/, the

4.48

8 etc./,

curve

about were

reolite

probably series

d,

suspensions

of

feldspar

stored

for

g stored

for

wee

estimated

in

structure of

thfa

of grain

/2f

its

DTA /g/

dlffe-

between

Series micro-

smaller

sample

Crumb%,

on water

The

sorption

dehydrated

Feldepar high

of

XRD

stirring /Fig.

of

high

In

are

8,

intensity on DTA

were

background.

4b

f9.7

a deflection

peaks

samples

bg-surface

drying

XRD peaks

feldspar

aamples

for

wesk,

unheated

present

heated

a short

also

greins size

cheFacteFistic

of

in

and

twinning separate

er

0 and a/. b and

80D°C./2/

In

b,

observed

series

chemical

feldspar. ca.

0,

not

fseries

/l/

at

the

were

D/B-9d-800°C-18h of

ware

time

found

atetically

here

series

grains

were

SEM, indicating

outline%

sample

peaks to

feldspar

stored

sample

of

similar

montmorillonite

quartz

/selected

that:

tha

com-

possible.

morphology

of

of

dUFinQ

by.the

quartz

cores

very

fnfluence

weak

aerles

internal

the

6.

samples

statically,

suspension

masked

and

In

DTA gave

corresponds

8 months;

end/or and

stirring with

b heated

background

g also

4 months

lee

phology

to

observed

In

present

is

Grains

grain

of

SEM results

of

by SEM in

A big

affe-

/different

8cFatChad

and

800°C

Fig.

f and Q/ indicates

atobalite

time or

series

indicates

This

,fphlLlipaite/

Analysis

or

microstructure ware

of

were

R/,

560-57O’C.

samples

in

differeneea

Of minute of

high

peaks

there

ft and 3.34

they

very which

the

/4.27

B/R

phcrae

Both

also

varied DTG /f/

time

layers

at

segregation

Besides

c/.

also

importance.

storing

Samples

Surface

the

energy and

in

heating

except and

and

XRD patterns

DTA than

4a end c.

4g

but

[9].

different

Fig,

2g and

in

in form

size

in

These

a longer

g heated

to in-

may be due

[121/.

increase

it

g heeted

to /I/

influence

the

and

either

was

It

/see

may be of

may be due SiZS

samples.

above

G increased

initial

concentration rent

powder

dehydF8tiOn

on microstructure.

of

In

of

mentioned

The value energy

to

tenp%rature

in

d,

eer-

COmpOSitiOn

both

cases

cri-

observed.

0.5

mm of

was

feldaper-like

found

/Fig. smectita

7/.

In

the

On the

particles

morcluster aurfaee are

vlsi-

327

TABLE 2

Feldspar

peaks /A/

in hsatsd

2b-yellow-4b

sarplss 4g %ntsrlour 8W°C looo”c

f300°c

6*37 4.03 3.83 3.75 3.69 3.49

4.004 3.86 3.49

3:06

:*:z .

J';gQ

4.036 3a88 3.53 3.344 3.229

3.69 3.49 3‘3544 3.206

2.998 2.508 2.455 Low elbite

2.526

/?/

6b-yellow-8b 8OO'C

bb-brown-8b 800°C

34:z 3.69 3.50 3.335Q 3.275

3.85 3.70

3%: 2:891 2.615 2.59 2.47 2.348

3.008 2.88

Zeolfts

2.519 2.459

4.004 3.87 3.74

3.8% 3.78

"3.EQ

3.24 3.33551

3:21 2.97

3.206 2.97

2.696 2.519 2.47

2.696 2.819 2.453

3.27

2.47 2.34

High alblte

/?/

pedkes

possik+Iy

JR/,

phillipsits

8/R-2b-800°C-lh yellow surfsce hyerr 4.983, 4.27. 4.17, 4.03* 3.75, 3-49, 3.27 3.39, 3.058, 2.876, 2.805# 2.690, 2.629

In

329

330 ble

and

seen,

arrangement

their

compare

Another

feldspar

re of

the

surface

hough

the

twinning

different compare

cluster

structure

may be

but

it

grain

part

of

Is

also

Is

was

found

within

the

sample

parallel

structu-

B/B-9d-BOO’C-18h.

visible,

the

characteristic

the

of

surface

Hare elt-

morphology

feldspar

as well

Is

/Fig.

8/,

[ 3 3.

A replica

of

twinning

was observad

in

sample

structure

the

double

In a.densa

[ 55.

of size

of

or a feldspar B/B-9b-8OO’C

“wavelength”

twinning

of

steps,

grain - lh,

ca.

“In atatu

Fig.

5,um as

Fig.

8,

as

nascendi” a “wavy”

compared

7 c and d,

to

equal

the

to ce.

5 - 6,um. In

examples 9, 10 and I.1 some other and their chemical compoe.ition is

figures are shown

ins

of

feldspar

gra-

indicated.

SUMMARY Study

presented

bentonite /l/

Indicates

that

feldspar

may form

in

suspensions:

during

drying

necessary of

above

the

at

Is

room temperature

supplied

final

dense

or at

by decrease packfng

of

in

llO°C,

if

the

internal

energy

and

structural

particles

energy /nV,/ ele-

ments, /2/

during

heating

at

elevated

transformation

depends

on sample

and

size

/3/

during

prolonged

/4/

cluster

structure

probability gement

Thus

of

of

both

clay

In this

time

prior

case

to

phase

drying

and

form,

storage

/8

gives

in

months/

of

by drying,

followed

Berkbent

development

bentonite

feldspar

due

the to

highest

suitable

arran-

particles.

postulates,

on microstructure

temperature:

on storing

i.e.

and

dependence

on action

of

/energy

phase

x time/

transformation found

some verl-

fication.

High stirring

energy

desintegration ted

to

crystal ples

of

sample

and quartz

ca created saturated

particles

surface

structure

of

of

a bentonite into

during silice

observed

the possibility solution.

suspension

amorphous

It

drying.

small of

observed

aaaples/.

formation

matter,

which

may transform

/cristobalite

in

resulted

of

in migra-

into in

some

big

sam-

This

aaorphous

aili-

faldapar

in

allica

331

Fitz.

9

332

Fig.

10

333

334 ACKNOWLEDGENENTS Research

was performed

Engineering

Dept.

due

Nash /euepenelone, /SEM/,

/2/

Berlin

/XRD,

P. gie,

TG, WS,

of

W. Eyeel/.

two papers

were

CPBR 6.4.

/5/

Civil

Prof.

J.K.T.

/XRD/,

Anatomy

Dept.

Chemle

DAW der

DDR,

University,

Geology

Natureles

Heldelberg

prepared

London,

late

Dept.

de Recurs08

SEM/,

Prof.

the

Anorganieche

Warsaw

Centro

DTA,

College

of

DTf,Geology

/3/

/4/

/XRD,

King’s

fiir

G. Kranr/,

Sevilla These

/I/

inepiration

Zentralinetitute

Driertanowski/,

courtesy

at

to

Dept.

y Agrobiolo-

University

partially

/SEM,

within

/DTG,

the

projects

end RPBR 28.lA.

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