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CHEM . RES . CHIN ESE U .

2004, 20( 2) , 200204

A Study of Ca-Mg Silicate Crystalline Glazes


An Analysis on Forms of Crystal s*
* *

LIU Pei-de , YU Ping-li and WU Ji-huai


I nstitute of M aterial P hy sical Chemistry , H uaqiao Univ ersity , Quanz hou 362011, P . R . China
Receiv ed D ec. 5, 2003
In the study on Ca -M g silicate cry stalline glazes , we found some disequilibra ted cry st allization phenomena,
such as no n-cry st allog r aphic small a ng le for king and spher oidal g r ow th, pa rasitism and w edg ing -for m of cr ystals, dendr itic gr ow th, seco ndar y nucleat ion, etc. T hose phenomena possibly r esulted fr om two facto rs:
( 1) par tial t emper ature gr adient , w hich is caused by heat asy mmetr y in t he electr ical resistance furnace,
w hen cry stals cr ystalize fr om silicate melt; ( 2) co nstitutio nal super coo ling near the sur face of cr ystals. T he
disparity o f disequilibrat ed cr ystallizat ion pheno mena in different main cr ystalline phases ca uses var io us mo rpholog ical featur es o f the cry st al ag gr egat es. A t the same time, disequilibrated cr ysta llizatio n causes g reat
str ess ret ained in the cr ysta ls , which result s in cr acks in g lazes w hen the tem per ature dr ops . A cco rding to
t he r esults, the aut ho r s analyzed those pheno mena a nd displayed cor relative fig ures and data .
Keywords Cry st alline g laze, Co stitutional super co oling , Heat dynamical condition , Disequilibr ated cry st allizatio n, M o rpholog ical feature o f cry stal ag g reg ates
Articl e ID1005-9040( 2004) -02-200-05

Introduction
T r aditio nal ceramic glaze is basicall y is silicat e
glass. T he crystall izat ion st at e of cry st alline in
glass direct ly af fect s t he appearance and t he perf ormance o f t he glaze. Cryst al lization has a bad impact o n t ransparent glazes, and abundant microcry st als f aciliat es opaque glazes. W hen a few cry stals becom e phaner ocry st alline, t hey are probabl y
hav e values for appreciat ion . Cry st alline glazes are
glazes of o rnam ent al por celain decorat ed by cry stals. Based on go od glaze f it , t he morpholog ical
feat ur es o f single cryst al s or cry st al ag gregat es determ ine t he values o f cry st alline glazes .
T he t hickness of cr yst alline g lazes ranges fro m
1. 5 t o 2 m m, w hich is t hicker than that of com mon
glazes. T he cryst alline grow t h is r estr ict ed by
space. U sual ly, cryst al s gr ow in t hree dimensions
at t he init ial stag e, and the gr ow th quickly chang es
int o one dimensional or t w o dimensional gro wt h
along t he cry st alline direct ions, and finally t he
cr yst als becom e f ibro us aggr eg ates o r t abular aggregat es.
Whil e t he t emper at ure of t he silicat e melt
dr ops about 100 fr om t he f iring region to t he
gr ow th region , it is in t he condit ions of heat disequilibrium and const itut ional super coo ling . Ev en if

it last s fo r a cert ain per io d at t he t emperat ure of


gr ow th region , t he t emper at ure field is not complet ely sy mmet rical in the electr ical resist ance furnace. T he undulat ion of co mposit ion and heat dynam ic condit ion af f ect s t he gr ow ing cryst al s, and
leads t o disequilibrated cry st allizat ion f orms.
M oreover , g row ing under disequilibr at ed condit io ns , the cryst als retain m uch st ress, w hich damages t he glaze fit and porcelain
s value. T he f orm s
of cr yst als and aggr eg ates direct ly infl uence t he
value f or appreciat ion. T heref ore, studying silicate
melt cryst allizatio n is im po rtant f or obt aining goo d
cr yst alline g lazes . According ly , t he aut ho rs w ill
gener all y analy ze some f orms of silicat e cryst al s
and t he possible inducements o f t hem.

Mineral Combination in Glazes


T he com ponent s of silicat e melt s are com plex .
T he aut ho rs onl y sem iquant it at ively st udied t he relat io nship bet w een t he m elt composit ions and t he
miner al combinat ions. T he result s are display ed in
T able 1. When t he rat io of m ( CaO ) / m ( Mg O) is
higher than 1. 5, t he m ain cr yst alline phases are
made up of w ol last onit e and cyclow ollasto nit e; and
w hen t he rat io is clo se t o 1, t he m ain cry st alline
phases are clinopy rox ene and m elilit e . In the same
sam ple, t her e are several mineral co mbinat io ns:

* Suppor ted by the N atura l Science Fo undatio n of F ujian Pr o vince( N o . D0210012) .


* * T o w ho m cor respondence can been addr essed.

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L IU Pei -De et al .

w ollasto nit e + cy clow o llast onite , w ollast onit e +


clinopyrox ene , clinopyr oxene + melilite , w o llasto nit e + clinopy rox ene + melilit e, cy clow ol last onit e
+ clino py rox ene .

vious in cryst all ine glazes and t he cr yst als ag gregat es are radiat ing ( Fig . 2) .

Table 1 The relationship between the ratio of m( CaO) /


m( MgO) and mineral combinations in crystalline glazes system*
m ( C aO ) / m( M gO )

m( SiO 2 ) / m( A l 2O 3 )
13

15

17

19

20

2. 467

A/ B

A/ B

A/ B

1. 836

B/ C

1. 229
0. 733

D
C/ D

C/ B
C

B
C

* A . Cyclow ollast onit e; B. w ollast onit e; C. cli nopyroxene;


D . melilit e .

Analysis on Forms of Crystals and Aggregates


1Basic Growing Forms of Crystal s
In cryst alline g lazes, basic f orms of crystals
are determ ined by crystal st ruct ures and glazes
space. In t he cyclo w ollast onit e cryst al st ruct ure,
4t he arrang ement of [ SiO 4 ]
t et rahadra is an
[ Si3O 9 ] ring . T he cry st al shape of cy clow o llasto nit e is usually equig ranular. Because of the disequilibrat ed cr yst allizat ion caused by melt co mpositio ns and heat dynamic conditions in superco oling
glaze melt , cyclow ollasto nit e gr ow s in 2-dimension
and becom es flaky cry st als. Hex agons are t he centers o f cry st als of cyclo w ollast onit e, w hich become
hex agonal skeleto n cryst als. As t he skelet on cry stals devel op, t he hex agonal o r irregular flaky cry stals superpo se and become ret iculat ed agg regat es
( F ig . 1) .

Fig. 2Wollastonite [ crystal aggregate of


several rounds , d = 5. 4 mm( - ) ] .
( - ) : Polarizing microscope wit h s ingle pol ar.

T he crystal st ruct ure of diopside makes it s


cr yst al co lum nar and the columnar-gr anular ag gre[ 1]
gat es are co mmo n in nature . T he diopside cry st al s appear in a col umnar f orm in cry st alline glazes;
t he ag gregat es o f diopside are radiat ing w it h various appearances( F ig. 3 and Fig . 4) .

Fig. 3Pyroxene [ radial crystal aggregate,


d= 5. 4 mm( + ) ] .
( + ) : Pol ariz ing m icros cope w it h cross pol ars .

Fig. 4Pyroxene [ radial crystal aggregate,


d= 5. 4 mm( + ) ] .
Fig. 1 Six-sided crystal center and net-shaped crystal
aggregate of cyclowollastonite ( d = 1. 5 mm
RLM) .
R LM : R ef rect ed ligh t m icros cope. d : long axis of visu al area.

T he crystal st ruct ure of w ollast o nit e is a chain


st ruct ure fo rmed by bi-t et rahedra [ Si2O 7 ] and tetr ahadra [ SiO 4 ] , w hich ar e par al lel t o b-ax is and
appear al ternatively . And t his st ruct ure is f av orable t o t he for ming of t abular or fibrous w o llasto nit e par allel t o b -axis . T he cry st al behavior is ob-

M elilit e belongs t o a t et rag onal syst em and t he


t abular cr yst als have square tr ansects . Small -sized
melilit e in t he crystall ine glazes is g ranular w hich is
cl ose t o a square or polyg on wit h salient angles of
90
. Under a micr oscope, t he cryst al s of melilite
are act ually sing ular or penet rat ing dimorphous
( Fig . 5) . Big ones are limit ed by t he space . T he
t ransect s of t he singular cry st als are square , and
t he edges of t he crystals of penet rat ing tw ins ex po se on the surf ace of glazes which m akes t he cry st al s r adiating.


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CHEM . R ES . CHIN ESE U .

Fig. 5Melilite[ insert twin, square section of


crystal , d = 5. 4 mm( - ) ]

2Unequi librated Crystall ization Phenomena


2. 1 N oncry st all ograp hic Smal l A ngle Forking
and Sp heroid al Grow ths
In t he init ial gr ow ing stag e , bot h w ol last onit e
and clino py rox ene sho w obvious sphero idal
gr ow th . A low rat e of molecule mov em ent is f av or[ 2, 3]
.
able t o t he spheroidal g row t h of cry st als
T herefo re , silicat e m elt
s high viscosit y and a large
amount of impurities are t he import ant out er causes
t o t he spher oidal grow t h .
T he spherical cryst als are for med w hen t he
so lid-liquid int erf ace is dist urbed and t he cry st alline
ang le deviat es slight ly . Because of small angle
fo rking , tw o ends o f t he crystals cont inually g row
in mult iple direct ions , first t hey become dendrit ic
or radiat ing cryst al s, t hen spherical cr yst als . In
cr yst alline g lazes , spher ical cry st als are limit ed by
t hin melt , and f inally they f orm radiat ing planar
agg reg at es.
T he ang les of small angle f orking ar e indefinit e
and have no co nnect ion wit h cr yst al lat t ice. All t he
spherical crystals, w hich ar e fo rmed by t he small
ang le f orking o f the sing ul ar crystals, ar e made up
of fibrous cryst al s radiat ed f rom t he same center [ 4] .
In cryst all ine glazes, when t w o or m ore cry st al
centers ar e nex t to each ot her, t he gro wt h of fibr ous cry st als of the spherical crystals of w o llasto nit e m ay be limit ed by t he space; and the unlimited part co nt inuousl y gr ow s int o a part of t he
sphere ( Fig . 2) . T he indefinit eness o f t he branches
of sm all ang le fo rking makes t he f ibr ous radiat ing
cr yst als of w o llast onite bend w ith v arious radiat ing
fo rms. Non-cry st allog raphic small ang le for king also appears in clinopyrox ene aggr eg ates w it h various
radiat ing and dendritic cr yst als. Com pared w it h
t hat of w ollast onit e, t he ability of non-cryst allographic small angle for king of clinopy rox ene is
much w eaker, w hich makes t he clino pyr ox ene aggregat es and w o llast onit e agg regat es dif f er fro m
each ot her .

V ol . 20

2. 2Outl ine of Dend ritic Grow th


In cryst all ine glazes , the cry st allizat ion o f cyclo wo llast onite most ly begins w ith dendrit ic
gr ow th and wit h hex agonal skelet on cry st als as
centers ( F ig . 1) .
Dendrit ic g row t h o f clino pyr oxene is obvious
and occurs in every st age of cryst allizat io n. In t he
beg inning of the gr ow th , the branches are for med
w ith the radiat ing crystals of spherical cry st als as
t runks ( Fig . 6) .

Fig . 6 Dendrite of pyroxene[ d = 2. 16 mm( + ) ] .

During t he gro w th, because t he dissipat io n of


t he lat ent heat at t he tips of the cry st als is f ast er,
and t he deg ree o f superco oling is hig h, w hich is
beneficial for t he g row t h of the f lang es and t he f ormat ion of slender tr unks of t he branches. T he inst abilit y of the int erf ace of t he supercoo ling liquid
around t he t runks causes t he fo rmat ion of branch
cr yst als. Because of t he cont inuous cryst allizat ion,
t he int er-spaces o f branches ar e f illed w it h or cover ed w it h newl y-fo rmed cr yst als, which makes t he
f ormed br anch cry st als unobservable . A sudden
dr op in t em perat ure breaks the cryst all ization
rapidly , and t he g row ing f orm of t he branch cry st al s r em ains ( Fig . 7) .

Fig. 7Pyroxene( dendritic growth at the edge of


crystal aggregate, SEM ) .

In t he same radiat ing aggr eg at e o f py rox ene ,


t he slender t runks of t he branch crystals can be
st raight o r cur ved( F ig . 8) , which means t hat t here
is dif ference in dynamic conditio ns and co mposit io ns among diff erent regions in t he melt . When
cr yst als are g row ing , eit her t he com positional difference in the melt beside t he t runks or dist urbance

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L IU Pei -De et al .

t o the st abil it y of sol id -liquid w ill cause t he gro wt h


of the cry st al t o deviat e slight ly and t he t runks t o
bend. T he occurrence of t he py rox ene br anch cry stals and t he bend o f t he t runk show t he inst abilit y
of the solid -liquid int erface. A ll the pheno mena of
dendrit ic gr ow th show t hat during t he process of
dendrit ic grow t h at a const ant t em perat ur e, t here
are some inst able facto rs in t he melt such as t he
co mpo sit ion of t he m el t and heat -dynam ic conditio ns .

t he sides of the m ot her -crystals ar e clo se t o a


square .
Parasit ical cr yst als and wedg ing -fo rm ar e likely t o occur in regions w it h higher st ress and defect s , w hich indicates t he ex ist ance of st ress in t he
pr ocess of cry st allizat io n, and st ress is a v it al f act or causing cracks in glazes .
2. 4S econdary N ucleation
T he nucleat ion ov er ex ist ing cr yst als is called
[ 5]
secondary nucl eat ion . Secondary nucleat ion o ccurs around existing ag greg at es , and enriches cry st al pat t er ns of cryst all ine gl azes . P yro xene ag gregat es have v arious secondary nucleat ion f orm s.
Secondary nucleat ion o f pyro xene in cry st alline
gl azes f orm s branches ( F ig . 10) and various f labellat e aggr eg at es( Fig . 11) . T he shapes of ag gregat es
bring t he magnificent f ringes of cr yst alline glazes.

Fig . 8 Pyroxene [ radial crystal aggregate and curved


radiated tuf ts, d= 1. 5 mm( RLM) ] .

2. 3P arasit ism and W edgi ng -f orm of Cry stal s


T he occurr ence of parasit ism and w edging fo rm of cry st als is obv ious in m elilit e . T he singular
melilit e has a square crystallized cent er , it s out line
is similar t o cryst al agg regat es ( F ig . 9) . T he f our
ang les of the sing ul ar melil it e are w edg ed . T he
w edging -f orm of cry st als is t he result of t he f ast er

Fig . 9 Melilite ( square center of crystal ,


wedge-shaped crystal at corner, SEM) .

gr ow th at t he t ips of t he cryst al s. T he fast dissipatio n on t he t ips of t he cryst als and a hig h degree of
surper cool ing around t he cr yst als l ead t o t he f ast
gr ow th. T he depo sit ion o f t he so lut e in t he melt
cr eat es a large amount of parasit ical cryst als in t he
mot her-cry st als. T he direct ion of parasit ical cry stals is parall el to t he mot her -cryst als and t he t ips
are higher t han t he ot her part . T he parasit ical
cr yst als and mo ther-cry st als sho w ex tinct ion pro per ty under a cro ssing -polarizing microscope, w hich
belo ng t o a parallel or ient at ion . P arasit ical crystals
hav e t he same gr ow ing st ate as t he mot her -cry stals. T he parasit ical cryst als in diago nal direct ion
are w edged w hile t he par asitical crystals par allel t o

Fig. 10 Pyroxene crystal aggregate [ dendrite caused by


secondary nucleation, d= 2. 16 mm( + ) ] .

Fig . 11 Pyroxene crystal aggregate [ f an-shaped


edge caused by secondary nucleation,
d = 2. 16 mm( + ) ] .

Secondary nucl eat ion usually occurs w hen t he


[ 5]
t em perat ur e of cr yst al grow t h f al ls . F or t he purpo se of chang ing t he f orm s of crystal agg regat es ,
w hich makes crystalline glazes mor e valuable f or
appreciat io n, w e can change the const ant t emperat ure of cry st al grow t h .

Discussion
Fr om t he analyses above, t he aut ho rs f ound
t hat cr yst alline phases w ith dif f erent m ineral combinatio ns have various cry st alline phenom ena
caused by t he disequilibrat ed condit ion. Small angle f orking and spheroidal grow t h pheno mena occur
mo st o bvio usly in w ollast onit e, secondly o bviously


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CHEM . R ES . CHIN ESE U .

in pyr oxene . Dendrit ic g row t h mainly occurs in


so me minerals , such as py rox ene and cy clow o llasto nit e . M elilite is charact erized by parasit ism and
w edge f ormat ion of cryst als. Seco ndary nucleat ion
is obvious in pyro xene aggr eg ates .
T he inducements of t hose disequilibrat ed cry stall ized f orm s abov e are heat dy nam ic condit ions
and the het ero geneit y of t he melt com po nent s ,
such as local t em perat ur e gradient and co mponents
fl uctuat ion .
Crystallizat ion chang es the melt composit ion
near t he so lid-liquid int erface , w hich leads t o melt
co mpo sit ion changing w it h dist ance aw ay f rom t he
int erf ace , and even causes the composit ional dif ference bet w een the t w o sides of t he interf ace. T he
co mpo sit ional diff erence of melt po ssibly results
fr om heat dynam ic f act or s, such as: ( 1) melt
mov em ent caused by slig ht temperature f luct uat ion
in the isot hermal process; ( 2) com positional f luctuat ion of t he m elt surf ace caused by t he heat convect ion in elect rical resist ance f urnace. Heat dynam ic unst able f act ors possibl y result f rom :
( 1) t he t em perat ur e asymm et ry in the elect rical resist ance f urnace; ( 2 ) t he diff erent temperature
fields in t he dif ferent r eg io ns of solid-l iquid int erface, w hich is caused by t he latent heat produced
by cry st allizat io n. T he br anches and sphero idal
cr yst als caused by sm all ang le for king are produced
w hen t he st abilit y of t he so lid-liquid int erf ace is dest roy ed.
In additio n, t he patt erns of gro wing crystals
are lim ited by space in glazes. In cryst al gro wt h
pr ocess, cer am ic g laze is a shallow lay er of a silicat e m elt . T herefo re, t hree-dimensio nal g row t h of
t he cry st als is lim it ed. One dim ensio nal or t w o dimensional cr yst al g row t h com monly occur s, and fibr ous or t abular-co lum ner cryst als com e out frequent ly . Cry st al agg regat es and int erface int er sect
t o fo rm or nam ent al
cryst al flo w ers . T ake w ollast onite f or inst ance, t he surface o f g lazes and
but t -glaze int er face limit t he spheroidal cry st al f ormat ion , and cryst al agg regat es appear as ro und radiat ing cr yst als made up of fibrous cr yst als on t he

V ol . 20

surf ace o f t he glazes . W hile m el il it e cryst als present int erpenet rat ed sect ions of sing ul ar or m ult icr yst als . P yro xene can f orm branch cryst al s or
dendrit ic cryst al s at any t ime . T he dendr it ic cry st al s or br anches f ormed lat er fill t he int erspaces of
f ormer cryst als and can no t gro w up f or the limit ed
spaces ( F ig . 12) . T he existence of radiating cryst al s
and small dendritic cr yst als , as w el l as the sect or
edge for med in the secondary nucleat ion , make t he
macro -f eat ures o f t he radiat ing pyrox ene aggr eg ate
change and t heref ore , reinfo rce the out er value f or
appreciat io n.

Fig . 12 Pyroxene [ small radiated tufts in


aperture between large-sized
radiated tufts , d = 5. 4 mm( - ) ] .

Disequilibr at ed crystallizat ion keeps a high


st ress in glazes. T he st ress does harm t o porcelain
because t he st ress can l ow er capabilit y of combinat io n fo r porcelain, w hich m akes the crystals crack,
t he glazes cr ack or f lake, and so on.
Disequilibr at ed cryst allizatio n is unavoidable in
cr yst alline glazes. Ho w t o cont rol it pro perly and
t o m ake f ull use of cr yst al ag gregat esappearance
f ormed by unst able fact or s, and t o low er t he harmful inf luence on t he g laze qualit y are quest ions t o be
st udied.
References
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[ 2 ] M cm illen P. W. ; Transl at ed by Wang R. Q . , G lasses Ceramic, China A rchi tect ure Press , Beijing, 1988, 60
[ 3 ] U lm an D . R . . A d v ances i n N ucl eati on and Cryst all iz ation in
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[ 4 ] M in N . B. . P hysic al and Chemical Foundat ion of Crystal
Grow th, Sh angh ai Scient if ic and T ech nological Pres s, S hanghai , 1982, 227
[ 5 ] Zh ao X . Z. , Zhang G . Y . , Y ao S. Q . e t al . , S il icat e Report , 1984, 3( 5) , 1217