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Characteristics of Quartz Fiberss
Characteristics of Quartz Fiberss
of quartzfibers'
Characters
CLrprono FnoNorI-
Department of GeologicalSciences,Haruard Uniuersity
Cambridge,Massachusetts02 138
Abstract
trapezohedrons,such as x {516-l} or the trigonal pyra- tion. The general effect presumably results from di-
m i d s { l 1 2 1 } ,a n d a c o r r e s p o n d i n gp o s i t i v ec h a r g ea t rected strain associatedwith the initial dislocation
the opposite pole. This descriptionis independentof ( E s h e l b y ,1 9 5 3 ;G o m e r , 1 9 5 8 )i n t h e n u c l e a rc r y s t a l
the chirality. Tension reversesthe effect.Temperature that destroys the formal crystallographic equiva-
gradientsproduce internal stressesand thus also pro- lences.
duce charges (pyroelectricity); on cooling, the
charges correspond to those of compression. The Polar orientation
rates of solution and growth as measuredon spheres Since the [ 120] direction is polar, the question
or on platescut perpendicularto [ 120]are greaterin ariseswhether there is a preferredpole of attachment
the axial direction away from the pole which becomes of the fibers to the site at which crystallizationiniti-
n e g a t i v eo n c o m p r e s s i o n . ated. In the technique used here, thin plates were
Structurally, the Si and O ions are arranged in sawn at right anglesto the fiber elongation,electrodes
special positions in the enantiomorphous space were plated on, and the piezoelectriccharges pro-
groups C3r2 and C3r2. The enantiomorphism arises duced by axial compressionwere identified. Exami-
in helical arrangementsof the Si and O ions along the nation of several hundred parallel-fibrousand radi-
[0001]direction.This arrangementand the associated ally-fibrous crusts, geodes,and agates from world-
optical activity are lost when the structure is dis- wide localitiesestablishedthat a preferredorientation
solvedor melted. The chirality of quartz as described is commonly present.The attached pole is that one
by conventional morphological and optical rotatory becoming negatively charged on compression.This
criteria is opposite to that of the crystal structure. description is independent of the quartz enan-
tiomorph involved. The same polar orientation is
Fiber elongation shown by large quartz single crystals, describedbe-
The common direction of fiber elongationas deter- y o n d , t h a t a r e e l o n g a t e da l o n g [ 1 1 2 0 ] .A n o r i e n t e d
mined by X-ray diffraction and piezoelectrictech- piezoelectricresponsewas weak or absentin many of
niquesis along one of the polar (l 120)directions.The the fibrous specimens examined, notably in cha[-
earlier X-ray work and the general literature on fi- cedony crusts from hydrothermal veins, closely
b r o u s q u a r t z a r e s u m m a r i z e d b y B r a i t s c h ( 1 9 5 7 ) . banded or deeply pigmented agates,and material in
Quartz fibers also occur elongated along the non- which the fibers have a feathery character or are in
polar [0001] direction but are rare and appear to be the submicron range of size.The angular divergence
typical of particular geochemicalenvironments(Folk of the fibers is also a factor. More or less equal
and Pittman,l97l). mixtures of fibers of opposite polarity also would be
In the formation of fibrous quartz, the direction of representedhere.
elongation as predicted by periodic bond-chain the- The microscopic fibers that constitute chert and
o r y ( H a r t m a n a n d P e r d o k , 1 9 5 5 ;H a r t m a n , 1 9 7 3 )i s flint are randomly arranged as seen in thin section.
related to chains of strong Si-O-Si bonds running Platescut from such aggregatesdid not give a piezoe-
through the crystal structure.The strongestof these lectric response. Optically the flbers generally are
chains are in the ( I 120)and [0001]directions.A prob- length-fast; they hence are elongated in the (0001)
l e m a r i s e sh e r e i n t h a t t h e ( l 1 2 0 ) d i r e c t i o n sc o m p r i s e plane, but the identity of the specificdirection therein
a three-fold symmetry-equivalentset. The growth is not known.
rates henceshould be equal in each of the equivalent The polar orientation is viewed as a rate-of-growth
directions,as shown by the equant cross-sectionnor- effect connected with the dislocations to which the
mally seen across (0001) in single crystals.The ob- fiber elongation itself is ascribed. It is believed to
serveddimensional elongation of quartz fibers along derive from the different core structure of screw dis-
one of the three equivalentdirections(hereafterdes- locations propagated in opposite sensesalong [ 120]
i g n a t e d t 1 1 2 0 1 )i s b e l i e v e dt o b e c o n t r o l l e d b y d i s - (Ashbee, 1973),resulting in different growth rates as
locations implanted during nucleation and growth. the dislocationsare emergentat oppositefiber poles.
The same feature of dimensional elongation along When the faces terminating the fibers can be dis-
one direction of a symmetry-equivalentset is shown cernedthey are found to belong to either {1010}or to
by whisker crystals (Doremus et al., 1958 Webb e/ a { 1 0 1 1 }o r { 0 l l l } r h o m b o h e d r o n I. t m a y b e n o t e d
a l . , 1 9 5 7 R i e b l i n g a n d W e b b , 1 9 5 7 )o f v a r i o u s s u b - that fibers terminated by these or other non-polar
stances, and derives from screw-dislocationswith forms, if free from dislocations,would have identical
their Burgers vector along the direction of elonga- growth ratesregardlessofthe polar senseofthe axis.
FRONDEL,QUARTZFIBERS
;\,
The surfaces of some are smooth and continuous
z
(Tschermak's closed type); other crystals are com-
posite, and composed of partly merged individuals
(open type). In thin section the most perfect crystals
r),ro.. I
show undulose extinction, and afford X-ray single F i g 4 S c h e m a t i cd r a w i n g s h o w i n g t h e r e l a t i o n b e t w e e nt w i s t
crystal photographs with uniformly stretched-outre- s e n s e ,h a n d a n d p o l a r a t t a c h m e n t i n q u a r t z s i n g l e c r y s t a l s a n d
fibers elongatedalong [120] The free end is that acquiring a
flections.As with the fibers,there is a rough tendency
positive piezoelectric charge on axial compression.
for the twist period to increasewith increasingcrystal M o r p h o l o g i c a l l y r i g h t - h a n d e dc r y s t a l .T h e t w i s t s e n s ei s r e v e r s e d
size. Most of the known occurrencesare in hydro- i n a l e f t - h a n d e dc r y s t a l .
thermal quartz veins, cavity deposits of the Alpine
type, and pegmatites. cavity fillings formed in rhyolitic flows and welded
tuffs and in basaltic flows, gash veins in sandstone
Twisting around [0001] and quartzites,cavity and vein fillings ofthe so-called
Quartz fibers elongatedalong [0001]are rare. They Alpine type, quartz veinscontaining silicatesand sul-
can be identifiedoptically (length-slow),but the pres- fidic minerals of moderate to high temperatureaffili-
ence of twisting around [0001] cannot be recognized ations, pegmatites,and miarolitic cavitiesin granitic
optically in the uniaxial case. A few instances of rocks. In a general way, the twist period and the
twisting around [0001] in large single crystals have crystal size increase and the incidence of twisting
b e e n n o t e d b y T s c h e r m a k( 1 8 9 4 ) , L e m m l e i n ( 1 9 3 6 , decreasesin the order given. The range of temper-
1937), Frondel (1936, 1962), and Sadanaga and ature representedfor the crystallizationof the quartz
Bunno (1974\.Ten additional instanceswere found in in these occurrencesis conjectural. Study of liquid
the course of the present study. The twist sensehas inclusions in the twisted crystalswould be informa-
been reported as in the same senseor the opposite tive of the actual temperatureof crystallization.
senseas the morphological hand. Nearly all instances It is not known if the twist period is a linear or
are of the latter type. Identification of the twist sense more complex function of temperature,or if the rela-
sometimesis ambiguous becauseof the presenceof tion is directly with the temperature or with some
twinning. The twist period, in terms of a 120' turn, is characterof the crystallizingsolution that is temper-
variable. In the specimensexamined here it ranged ature dependent.
from about 54 to 800 cm. The maximum turn ob- There is also a marked variation in the incidenceof
served was about 45o over a length of 2l cm. The twisting around [1 120] over the observed range of
occurrencesare all from high temperature environ- temperature. Twisting is quite general in fibrous
ments. The crystals usually are relatively elongate quartz formed at low temperaturesand is quite un-
along [0001]. common in crystals formed at higher temperatures.
Probably less than 1500 examples of twisted single
Origin crystals are preserved in Museum collections. The
The [1120] twist period in fibers and singlecrystals twisted single crystals occur as isolated individuals
varies continuously from about 20 microns to over associatedwith quartz crystalsof normal habit elon-
300 cm. There is a small gap in this range,from a few gated along [0001] and of contemporaneousforma-
cm up to about 20 cm, in which only a few doubtful tion. Single crystals twisted around [0001] are ex-
measurementsare available.On either side there are tremely rare-probably less than 50 examples are
several hundred measurementsthat are rather uni- known-and seem to be typical of crystallizationat
formly distributed. high temperatures.
The types of occurrenceinclude geodalconcretions The twisting of quartz is believed to derive from
and crusts produced in the meteoric circulation and screwdislocationswith their Burgersvector along the
by weatheringprocesses, cavity fillings formed during direction of elongation and twisting. The primary slip
the chloritic and zeolitic stagesof post-magmatichy- systemsin quartz have Burgers vectors along (1120),
drothermal action in basic igneous flow rocks, gas [ 0 0 0 1 ] ,a n d ( l 1 2 0 ) + [ 0 0 0 1 ] .T h e y h a v e b e e ni n v e s t i -
22 FRONDEL QUARTZ FIBERS
, n d L e m m l e i n( 1 9 3 6 ,
B i l l o w s ( 1 9 0 9 ) ,R o s i c k j ' ( 1 9 3 3 ) a
1937), but the observed relation is very crude. It is
often found, for example,that separatecrystalsof the
same thickness or overall dimensions will vary in
twist period by a factor of 2 or more. The degreeof
supersaturationseemsa more likely control for both
the crystal size and the twist period. It influencesthe
rate of nucleation, or ultimate averagecrystal size,
and as found by Kozlovskii (1962) the step height of
screw dislocations increaseswith decreasingsuper-
saturatlon.
Fiber enantiomorphism
F i g . 5 P e r i o d i c s t r i a t i o n s i n a p a r a l l e l a g g r e g a t eo f t w i s t e d
quartz fibers. Striation spacing approximately 2.4 mrcrons.
If the nucleation of quartz as right or left enan-
C r o s s e dn i c o l s , s h o w i n g o p t i c a l e x t i n c t i o n b a n d i n g .tiomorphs is a matter of chance,the two enantiom-
rophs should be equally frequent.This appearsto be
gated especiallyin connection with the plastic defor- the case.The chirality of 27,043large quartz crystals
mation of quartz at elevatedtemperaturesand pres- has been determined by morphological, optical ro-
s u r e s( C h r i s t i ee t q \ . , 1 9 6 4 ;C h r i s t i ea n d G r e e n , 1 9 6 4 : tatory, or etching techniques:13,481are left-handed
B a E t aa n d A s h b e e ,1 9 6 9 ;M c l a r e n e t a I . , 1 9 6 7 :M i u s - and 13,5'72are right-handed. The data have been
k o v e t a | . , 1 9 1 1 ) . T h e s l i p v e c t o r sa r e i n f l u e n c e db y drawn from studies by Gross (1972), Lemmlein
temperatureand the presenceof water in the quartz (1944), Heritsch (1952), Bussiereand Maisonneuve
s t r u c t u r e( B l a c i c , 1 9 7 4 ) . ( 1 9 7 1 ) ,C . S . H u r l b u t ( p r i v a t ec o m m u n i c a t i o n ,1 5 4 9
A structural model for the propagation of screw left- and 1551right-handed),and other sourcescited
d i s l o c a t i o n sa l o n g [ 1 1 2 0 ]h a s b e e nd e s c r i b e db y A s h - by Frondel (1962). Becauseof presumedseedingef-
b e e ( 1 9 7 3 ) . T h e p a r t i c u l a r o r i e n t a t i o n a n d s t e r e o - fects some local quartz populations in igneousrocks
specificrelation taken by the screw dislocations in- are predominantly right or left (Heritsch, 1952;Bus-
volves choices (as described for morphologically s i e r ea n d M a i s o n n e u v e ,l 9 7 l ) . O f 3 0 1 s i n g l ec r y s t a l s
right-handed quartz) between the rectangular and t w i s t e d a r o u n d [ 1 1 2 0 ] f o r w h i c h d a t a a r e a v a i l a b l e ,
h e x a g o n a lc h a n n e l sa l o n g [ 1 2 0 ] , d e f i n e d b y r i g h t - 1 4 9w e r e l e f t - a n d 1 5 2r i g h t - h a n d e d .
handed and left-handed helicesof (SiO,) tetrahedra It is found that most aggregatesof twisted fibers
respectively,and the triangular and hexagonalchan- are more or less equal mixtures of the two enan-
nels along [0001], defined by left-handed and right- tiomorphs. In some instances, however, sizeable
handed helicesrespectively.The energeticsinvolved areasof fibrous geodesand agates,as seenin section,
include the sign of the Burgers vector along [ 120]. are all of the same hand, right or left. Occasionally
Whisker crystals of centrosymmetric substances theseobjectsapparentlyare wholly of the samehand.
show twisting to the right or the left dependingon the
c h a n c es e n s eo f t h e i n i t i a l d i s l o c a t i o n .T h e s e n s eo f
the twist or stressfield produced is opposite to the
screw senseof the controlling dislocation.In twisted
whisker crystalsthe twist period has beenobservedto
vary from small to immeasureablylarge valuesin the
same substance.Featuressuch as the temporary ces-
sation of twisting along the whisker axis, such as seen
in quartz fibers, also have been observed.
The twisting of whisker crystals and of planar or-
ganic spherulitefibers apparentlyis primarily a func-
t i o n o f t e m p e r a t u i e( G e i l , 1 9 6 3 ;K e l l e r , 1 9 5 9 ) , a l -
though fiber or crystal thickness and the degree of
supersaturation have been discussed in this con-
nection. A relation between crystal size and twist
period in quartz single crystals has been sought by Fig 6 Samefield as Fig. 5, in ordinary light.
FRONDEL: OUART-Z FIBERS z-)
Fiber aggregates
In the manifold varietiesof fibrous quartz the two
main modes of aggregation are either random or
spherulitic. Random orientation of essentiallyiso-
lated fibers is characteristic of chert and flint, al-
though some degree of organiza'i.ionaround the site
of nucleation is shown by the occurrenceof sheaf-
l i k e , f a n - l i k e ,s u b - r a d i a l a
, n d o c c a s i o n a l l ys p h e r u l i t i c
forms. In fibrous quaftz aggregatesthat have formed
by crystallization from solution at an interface, the
fiber organizationgenerallyis not random. The three
casescommonly observedare, in idealizedform: nu-
cleation at a single point on the interface, usually
giving rise to a hemispherical, divergently-fibrous
spherulite; nucleation at many points on a planar
interface, usually affording a parallel-fibrouscrust;
and nucleation at many points on the walls of a F i g 9 D i a g r a m s i l l u s t r a t i n gt h e f o r m a t i o n o f a p a r a l l e l - f i b r o u s
spheroidal cavity, usually forming an inwardly con- crust at a planar surface (A, B) and of an inwardly-convergent
vergent radial aggregate. f i b r o u s a r r a y i n a s p h e r o i d a lc a v i t y ( C ) .
FRONDEL'QUARTZ FIBERS 25
F i g . l 0 I n t e r s e c t i o no f t h r e e s p h e r u l i t i cs e c t o r si n a n a g a t e T h e
t w i s t e d I i b e r si n t h e t h r e e s e c t o r sa r e a t d i f f e r e n ta n g l e st o t h e p l a n e Fig l2 Periodic striations crossing a spherulite sector
o f t h e s e c t i o n .c r o s s e dn i c o l s . F i e l d w i d t h 7 0 0 m i c r o n s b o u n d a r y . S t r i a t i o n s p a c i n g3 m i c r o n s . O r d i n a r y l i g h t .
zo FRONDEL QUARTZ FIBERS