GEOPHYSICAL RESEARCH LETTERS, VOL. 28, NO.

13, PAGES 2517-2520, JULY 1, 2001

Vitreous forsterite (MgzSiO4):Synthesis,structure, and

thermochemistry
JeanA. Tangeman
l, BrianL. Phillips,andAlexandra
Navrotsky
Department
of Chemical
Engineering
andMaterialsScience,
University
of California
at Davis

J. K. RichardWeber,April D. Hixson,andThomasS. Key

Containerless
Research,Inc., Evanston,Illinois

Abstract. Here we reportthe first synthesis

of a forsterite
(Mg2SiO4)
composition
glassasanessentially
phase-pure
bulk
material. Under containerless
conditions,with heterogeneous
nucleationsitesminimized,glassformsby coolingca. 1 mm

coolingratesof 10L108K/sec)but the resultingmaterial

consisted
of onlyapproximately
10%glassamongthequench
crystals.In the presentstudy,containerless
techniques
were
usedto synthesizeseveralgramsof Mg2SiO4 glasswith a
liquidMg2SiO
4 droplets
in oxygen
at 700K/s. 29SiNMR negligible proportionof crystals (-1%). Elimination of
spectroscopic
dataindicatethattheSiOntetrahedra
andMgO6 containersurfacesallowed pure bulk glass formation at
octahedra
existin a comersharingarrangement
in the glass, relativelymoderatecoolingratesof---700K/sec.
but uponcrystallization
the polyhedralunitsreorganizeto
form edge-sharing
linkages. Transposed
temperature
drop Synthesismethod and glasscomposition
calorimetry
showsthattheglassis 61.4+ 1.3kJ/molhigherin
Vitrification of forsterite was achieved in an aero-acoustic
enthalpythanthecrystal.
[Weber et al., 1994] or aerodynamiclevitator [Weber and
Nordine, 1995]. Sampleswere levitatedin a streamof pure
oxygen, melted using a continuous-waveCO laser, and
Introduction
cooled by blocking the laser beam. In this manner,both
Forsterite
(Mg2SiO4)is an orthosilicate
andend-member
of contaminationand heterogeneousnucleation by crucible
the ubiquitous(Mg, Fe)2SiO
4 (olivine) solid solution. surfacesare avoided. The coolingrate was controlledvia the
Forsteriticolivine is the primarymineralconstituent
in the samplediameter- smallerspheroids
cooledfasterdueto their
Earth'supper mantle [Ringwood,1975] and in meteorites larger specificsurfacearea. Productionof glassyforsterite
[Hashimoto,1990] and Mg-rich olivine also appearsin requiredcoolingrates of---700 K/s or greater(Fig. 1), and
variousglassyandcrystalline
formsin interplanetary
[Bradley
et al., 1999] and interstellardust[Nuthand $tencel,1986;
Dorschnerand Henning,1995;Molsteret al., 1999], comets
[Crovisieret al., 1997],andthe dustdisksthatencirclestars
[Molsteret al., 1999]. Despiteits importancein natural

systems,
studyof the non-equilibrium
behaviorandrelative
stabilityof phaseswhichcanformfromtheMg-orthosilicate
1800
liquidremaindifficultbecause
of the inabilityto synthesize
bulk olivine-composition
glasses. Synthesisof magnesium
silicateglassesby standardmelt-and-quench
methodsis
1600
............................
typicallylimited to molar SiO2concentrations
of 50% or
greater[Cooneyand $harrna,1990]. Usingrf-sputtering,
amorphous
magnesium
silicatefilmswith SiO:concentrations , 1400
aslow as40 tool% canbe synthesized
[Hanadaet al., 1988].
To producea pure forsteritecomposition
(Mg2SiO4)glass
1200
............
(33.33 tool % SiO:), however,alternativetechniquesare
1100
required.
Jeanlozet al. [ 1977]reported
thefirstobservation
of
I
1.5
2
2.5
3
3.5
4
4.5
5
Mg-richolivine(Mgo.88Feo.02SiO4
glass,whichcomprised
a
Time (sec)
small fraction (1-2%) of a sample producedby shock
pressures
of about56 GPa. Williamset al. [ 1989]synthesized Figure 1. Coolingcurvesfor 3.5 and40 mg liquidMg2SiO4
Mg:SiO4glassby ultra-rapidchilling(splat-quenching
with samples under containerlessconditions. The apparent
Now at Containerless
Research,Inc., 906 UniversityPlace,
Evanston,IL 60201.

Copyright
2001by theAmerican
Geophysical
Union.
Papernumber2000GL012222.
0094-8276/01/2000GL012222505.00

2517

temperaturewas measured with an optical pyrometer.

Levitatedspecimenswere heatedto 2270 q- 20 K (---100K
abovethe meltingpointof Mg2SiO4)andheldfor---5seconds
prior to cooling the liquid to ensure completemelting.
Coolingrates determinedat the 1350 K crystalnucleation
temperaturewere 250-750 K/sec; smaller samplescooled
faster. Crystalsnucleatedin largersamplesat a temperature
of 1350 K. Smaller samplesformed glass. Inset showsa
photograph
of glassspheroids.

2518

TANGEMAN ET AL.' VITREOUS FORSTERITE

Table 1. Composition
andThermochemistry
of ForsteriteGlass
MeasuredComposition
of Glass:ElectronMicroprobe
Analyses
Sample MgO (wt%)
SiO2(wt%)
Total
MgO (mol%)
SiO2(mol%)
Fooglass 56.74
44.33
101.07
65.61
34.39
(0.99)
(0.61)
(0.50)
(1.44)
(0.47)
*Averageof 35 analyses;
7 spheroids
analyzed,5 spotanalyses
on each;Coveredtherangeiri
sizeandbubblecontent;Errorsin ( ) are2 standarddeviationsof themean.
Transposed
Temperature
Drop Calorimetry
Thermochemical
cycle:
(1) Mg2SiO4(glass,298 K) = Mg2SiO4(xl, 1075K)
(2) Mg2SiO4(xl, 298 K) = Mg2SiO4(xl, 1075K)
(3) Mg2SiO4(glass,298 K) = Mg2SiO4(xl, 298 K)
Avg.
Avg. ofi Std.Dev. Err.
AH(1) kJ/mol =
59.84
20
1.20
0.99
AH(2) kJ/mol 121.28 14
0.34
0.57
AH(3) = AH(1) - AH(2) = Enthalpyof Vitrificationof Mg2SiO4Glassat 298 K
= 61.44 + 1.25 kJ/mol

Calculated
Valuesfor theAverageHeatCapacityof theSupercooled
LiquidandtheEnthalpy
andEntropyof Fusionof Forsteriteat 2163 K

Avg.Cp,liq(1040-1773
K) = 225.0J/mol'K
AHfusion(2163
K) = 102.8kJ/mol
ASfusion(2163
K) - 47.5 J/mol.K
The C,of the crystalis fromRobieandHemingway[ 1995]. The AHfu.ion
usedto calculatethe
averageC,of the supercooled
liquidis fromNavrotskyet al. [ 1989],andwasobtainedfrom
solutioncalorimetryin the Mg2SiO4-CaMgSi206-CaA12Si208
systemat 1773K.

hence a samplediameterof 0.1 cm (Fig. 1, inset). The

resultingsmooth,transparent,colorlessglassspheroidseach
weigh 2-4 mg and containone or more small (ca. 5% total
volume) internal shrinkagevoids. At coolingrates slower
than 700 K/sec, crystalsnucleatedat about 1350 K (-800 K
below the meltingpoint of Mg2SiO4 crystal). Crystallization
occurredrapidly and was accompanied
by a "thermalevent"
duringwhich the sampletemperatureincreasedby about300
K (Fig. 1).
The glasswas synthesized
from high purityMgO and SiO2
powders,mixedandfusedinto-0.5 gramboulesof crystalline
Mg2SiO4 which were crushedto make samplesfor levitation.
Electronmicroprobeanalysesof initial batchesof the meltprocessedMg2SiO4 showedslight preferentialloss of MgO.
Forsterite-composition
glass(Table 1) wasmadefromstarting
materialcontaining1.25 molar % excessMgO.

scanningcalorimetric(DSC) scanshowedthat only forsterite

waspresent;no otherphaseswere detected.

29SiNMR results' Glass structure

Comparison
of 298iNMR spectra
of glassyandcrystalline
forsterite (Fig. 2) indicated significant structural
dissimilarities.The narrowpeak at -61.8 ppm was due to a
small amount of crystallineforsterite[Magi et al., 1984],
whereas most of the intensity, correspondingto the
amorphous
phase,occurredin a broad,slightlyasymmetrical
peak (7.5 ppm full-width-at-half maximum) having an

average
chemical
shiftof-70.4+ 0.2ppm.Thefull298iNMR
peakwidth for the glassincludesthe chemicalshiftrangefor

dimericgroups([8i207]
6', Q species)
in crystalline
Mg-

silicates(-72 ppm for akermanite[Merwin et al., 1989];-79.0

Most of the glassspheroids
showedno cracksor surface ppm for wadsleyite[Phillips et al., 1997]) and is consistent
crystalsat up to 60X magnification.X-ray diffraction(XRD)
with the presenceof a smallconcentration
of this species,as
patternsfrom a few milligramsof the crushedspheroids
were inferredfrom IR and Raman spectrafor Mg-silicateglasses
characteristicof amorphousmaterial and crystalswere not [McMillan, 1984; Williamset al., 1989].
observedin samplesimagedusing back-scattered
electrons.
The chemical shift differencebetween crystallineand
NMR measurements
confirmedthat the sampleswere -99%
amorphousforsteritecan be relatedto a changein the spatial
amorphous(Fig. 2). The -1% crystallineforsteritedetected relationship
betweenthe Si and Mg bondingpolyhedra. For

by 298iNMR is mostlikely dueto boththe presence

of

Mg-orthosilicates,
the298ichemical
shiftfallsin two distinct

crystals disseminatedthroughoutthe spheroidsand small

crystallizedportionson the surfacesof a few spheroids.The
NMR analysiswas performedon a sampleof-200 glass
spheroids,
a few of whichwere later foundto havetiny areas
of surfacecrystals,but this small volume fraction cannot
accountfor the entire 1% crystallinity. The surfacecrystals
probablyformedin atypicaleventswherethe levitatingbead
cameinto contactwith the sidesof the aerodynamic
levitator.

rangescorrespondingstructurallyto forsterite-likesites in

A, B, and superhydrousB) [Phillips et al., 1997]. The

averagechemicalshift for the forsteriteglassis nearestto that
of the Si-sitein phaseA (MgsSiO4(OH)6)
that sharesonly
comerswith nineMg-octahedra,
soassuming
thatmostof the

XRD and298iNMR analyses

(Fig.2, inset)of a portion
of the

Si-sites
areQ0,thenthoseQ0sitesareprimarilycomer-linked

whichthe [SiO4]
4' tetrahedra
shareedgesandcomerswith
[MgO6]
m'octahedra
(-61.8to -64 ppm)andsitesthatshare
onlycomers
with[MgO6]
'units(-70.6to -75.8ppm;phases

glass sample crystallizedfrom a preliminary differential to Mg-octahedra,rather than both comer- and edge-linked.

Si MAS-NMRSpectrum

of Mg2SiO
4 Glass

.............

.............
Forsterite
=-61.8
ppm
I............................

(,,o)
=-70.4
ppm1
I......
'
........
Amorphous
phase:

-30

-40

-50

-60

and Johari, 1990] despite the absenceof any crystalline

phasesin the glass. Suchliquidsare poorglass-formers
and
considered
extremely'fragile' [Angell, 1995;Ito et al., 1999].
Annealingof thesetruly amorphous
materialsat temperatures

justbelowT canremove
theexothermic
effect,whichis due
-10

-80

-30

-50

-90

-70

-90

-100

-110

-130

-110

ChemicalShift(ppm)

Figure2. 29SiMAS-NMRspectrum
of forsterite
glass.The
smallpeak arisesfrom a small amount(-*1%) of crystalline
forsterite(15= -61.8 ppm) present in the sample. The
amorphous
phaseexhibitsan averagechemicalshift of-70.4
ppm andpeakwidth 7.5 ppm (full-widthat half-maximum).
Inset showsthe spectrumof a portionof the sampletaken
after crystallization. Spectrawere obtainedat 79.5 MHz
using standarddirect-polarization
techniqueswith 3-4 gs
pulses(g/4 tip angle) and 200 s relaxationdelays. Glass:
spinningrate 4.5 kHz, for 1720 acquisitions;
no changewas
observedupon increasingrelaxationdelay to 1000s. Inset:
spinningrate 7.0 kHz, 1164 acquisitions.Frequencies
are
referencedexternallyto tetramethylsilane.

to enthalpy or structural relaxation, and reveal a glass

transitionendothermupon reheating. Preliminaryannealing
experimentscoupledwith DSC scanson Mg2SiOn did not
reveal such an endotherm,suggestingthat nanocrystalline
phasesareindeedpresent.
The fragility of Mg2SiOnliquid cannot be determined
quantitativelyfrom the DSC trace, but qualitativeviscosity
measurements
provide evidenceof the 'extremely fragile'
natureof Mg2SiOn liquid. Great difficulty was encountered
when attemptingto pull fibers from the levitatingmolten
dropletusinga tungstenstinger[Weberet al., 1998]. Such
difficulty suggeststhat the temperaturewindow for fiber
pullingis very narrowandthatthe risein log viscosityvs. 1/T
is steep,a feature characteristicof fragile liquids [Angell,
1995].
Although the absenceof a glass transition precluded

determination
of theconfigurational
heatcapacity
at T and

the heat capacityof the supercooled

liquid, the enthalpyof
vitrification at 298 K, was measured (Table 1). The
transposed
temperaturedrop calorimetricmeasurements
were
performedin a twin Tian-Calvetmicrocalorimeter
at 1075 K
[Navrotsky,1997]. Powderedglasssamples(5 mg pellets)
were droppedinto emptyPt crucibleswithin the calorimeter
andthe heateffectsresultingfrom crystallization
of the glass
The breadth of the peak for forsteriteglass suggestsa weremeasured.Usingthe appropriatethermodynamic
cycle,a
continuous distribution of local structural environments that
valueof 61.4 + 1.3 kJ/molfor the enthalpyof vitrificationwas
spans
forsterite-like
sitesto Q-typespecies
butis dominatedobtained. An independentvalue of 60.1 + 2.0 kJ/molfor the
by Si-sites in a comer-sharingarrangementwith Mg- enthalpyof vitrificationwas determinedfrom integrationof
octahedra.
Thus, nucleation of forsterite requires the crystallization
exothermon the Cptrace. The two values
reorganization,
or a simplerotationof thepolyhedral
units,to agree. Moreover, a value of 61.1 + 4.0 kJ/mol for the
form edge-sharing
linkagesbetweenthe SiO4tetrahedra
and enthalpyof vitrificationof forsteriteglasswas estimatedby
MgO6octahedra.
Navrotskyet al. [1990] andis in excellentagreement
with the
For crystallinephases,the changefrom forsterite-likeSi results of this study. For comparison,the enthalpy of
sitesto comer-shared
sitesis accompanied
by a smallincrease

in theaverage
Si-Obonddistance
of about
0.02A.Molecular

200

dynamicscalculations[Tosselland Lazzeretti,1986] and

experimental
datafor Ca-orthosilicates
[Skibsted
et al., 1990]

suggest
a decrease
in 298ichemical
shiftwith increasing
averageSi-O bonddistance,
thelatterstudygivinga slopeof

about-350ppm/A. Thesetrendsare consistent

with the
presentdataandstructural
interpretations.

100........................ Onset
=1040
K
ofcrystallization

" -100

.........................

Calorimetric results:Relative stability of phases

In additionto the structural
analyses,
successful
production
-300
of essentiallysingle-phaseforsterite compositionglass
enableda complementary
thermochemical
study. The heat
,-400
capacityof the samplefrom400-1450K wasmeasured
using
a Netzschdifferentialscanningcalorimeter(DSC-404). No
-500
glasstransition
wasdiscernible
in thecalorimetric
trace(Fig.
Temperature(K)
3) priorto theonsetof thecrystallization
exotherm
at 1040K.
The absence
of a glasstransition
is attributed
to nucleation
of Figure 3. Heat capacitytraceshowingcrystallizationof a 12
on a
crystals
immediately
uponenteringthe.glass
transition
region. mg sampleof powderedMg2SiOnglass. Measurements
Netzsch DSC-404 were performedunder flowing Ar (60
Thusweestimate
T - 1040K.
If crystalsare dispersedthroughoutthe as-synthesized ml/min), using a scan rate of 10 K/min. The onset of
glass,nucleationsitesare alreadypresentand virtuallyno crystallizationoccurred at 1040 K. Integration of the
crystallization
exothermresultedin a valuefor theenthalpyof

barrierto crystallization
existsonceT is reached.On the

vitrification

at 1040 K of 60.1

+ 2.0 kJ/mol.

The heat

other hand, Mg2SiO

4 liquid may exhibit glasstransition capacityresultsfor the glass and crystal are only semiphenomenologysimilar to that observed in some quantitativebecauseof the small sample mass. X-ray
of thecrystallized
productshowed
thatthematerial
hyperquenched
melts,e.g.glassy
metalalloys,whichshownc diffraction

glass-liquid
transition
endotherm
priorto crystallization
[Ram wasphasepurecrystallineforsterite.

2520

TANGEMAN

ET AL.: VITREOUS

FORSTERITE

vitrificationof an enstatite(MgSiO3) compositionglassis Jeanloz,R., T. J. Ahrens,J. S. Lally, G. L. Nord Jr., J. M. Christie,

andA. H. Heuer,Shock-produced
olivineglass:first observation,
42.2 kJ/mol [Herrig et al., 1985]. The enthalpy of
Science197, 457, 1977.
vitrificationof Mg2SiO4 on a kJ/molbasisis thussignificantly
Magi, M., E. Lippmaa, A. Samoson,G. Engelhardt,and A. -R.
more endothermic
thanthat of MgSiO3 andprovidesthe first
Grimmer,Solid-statehigh-resolution
silicon-29chemicalshiftsin
directquantitativemeasureof the relativestabilityof the end
silicates,
J. Phys.Chem.88, 1518, 1984.
McMillan, P. F., A Raman spectroscopic
studyof glassesin the
memberorthosilicate
glass.
systemCaO-MgO-SiO2,Am. Min. 69, 645-659, 1984.
Merwin, L. H., A. Sebald, and F. Seifert, The incommensurate-

Conclusionsand applications
The measuredenthalpyof vitrification can be used to
constrainthe averageheat capacityof the supercooled
liquid
(between 1040 and 1773 K) as well as the enthalpyand
entropyof fusionof forsteriteat 2163 K, its normalmelting
point. Thesenew estimates(Table 1) can in tum be usedto
constrainmelting and crystallizationprocesses
occurringin
magmaticsystemswithin the Earth and the energeticsof
chondruleformationin the earlysolarsystem[Wasson,1996].

Moreover,
theglassstructure,
asdeduced
fromthe29SiNMR
spectra,and the measuredenthalpy of vitrification, when

commensuratephase transition in akermanite,CaMgSi207,

observed
by in-situ29SiMAS NMR Spectroscopy,
Phys.Chem.
Mineral. 16, 752, 1989.
Molster, F. J., I. Yamamura, L. B. F. M. Waters, A. G. G. M.

Tielens,Th. de Graauw,T. de Jong,A. de Koter,K. Malfait, M.

E. van den Ancker,H. van Winckel, R. H. M. Voors, and C.
Waelkens, Low-temperaturecrystallizationof silicate dust in
circumstellardisks,Nature 401,563, 1999.

Navrotsky,A., ProgreSS
and new directions
in high temperature
calorimetryrevisited,Phys.Chem.Minerals24, 222, 1997.

Navrotsky,
A., P. Maniar,andR. Oestrike,Energetics
of glasses
in
the systemdiopside-anorthite-forsterite,
Contrib.Mineral. Petrol.
105, 81, 1990.

Navrotsky,
A., D. Ziegler,R. Oestrike,
andP. Maniar,Calorimetry
of
combined with additional studies on the kinetics of
silicatemeltsat 1773K: measurement
of enthalpies
of fusionand
crystallizationof forsterite glass under containerless of mixingin the systemsdiopside-anorthite-albite
andanorthite-

conditions may help to elucidate the crystallization forsterite,Contrib.Mineral. Petrol. 101, 122, 1989.
Among
mechanisms
whichoperateas amorphous
magnesium
silicate Nuth, J. A. and R. E. Stencel,Eds., Interrelationships
Circumstellar,Interstellar,and InterplanetaryDust, NASA
dustevolvesfrom precursor
interstellar
cloudsto planetary
ConferencePublication2403, 1986.
systems[Molster et al., 1999]. Finally, the viscosity- Phillips,B. L., P. C. Burnley,K. Worminghaus,
andA. Navrotsky,
29Siand H NMR spectroscopy
of high-pressure
hydrous
temperature
profile(albeitqualitative)
andthereluctant
glassmagnesium
silicates,
Phys.ChemMinerals24 179, 1997.
formingnatureof Mg2SiO
4 suggestthat vitreousforsterite
S. andG. P. Johari,Glass-liquid
transition
in hyperquenched
couldbe themostfragileglass-forming
silicateliquidstudied Ram,
metalalloys,Phil. Mag. 61,299, 1990.
to date. Clearly,containerless
technologywill facilitatethe Ringwood,
A. E. Composition
andPetrology
of theEarth'sMantle,
McGraw-Hill, New York, 1975.
studyof glasses
andsupercooled
liquidsin otherwisedifficult
properties
of
to vitrify systems
andwill providean environment,
parallelto Robie,R. A. andB. S. Hemingway,Thermodynamic
at 298.15 K and 1 bar (105
that in outerspace,which is appropriate
for investigating mineralsand relatedsubstances
Pascals)pressureand at higher temperatures,
US Geololgical
materialsprocessing
in ourgalaxy.
SurveyBulletin2131, 1995.
Skibsted,J., J. Hjorth,andH. J. Jakobsen,
Correlationbetween9Si
Acknowledgments.Experiments
at UC Daviswere supported
by
NMR chemicalshiftsand meanSi-O bondlengthsfor calcium
the Center for High PressureResearch,an NSF Science and
silicates,Chem.Phys.Lett., 172, 279 1990.
TechnologyCenter. Materialssynthesisat Containerless
Research, Stebbins,J. F. and M. Kanzaki, Local structureand chemicalshifts
Inc. wassupported
by NASA.
for six-coordinated
silicon in high-pressure
mantle phases,
Science251,294, 1991.

Tossell,J. A. and P. Lazzeretti,Ab initio calculations

of 9SiNMR
References
chemicalshifts for some gas phase and solid-statesilicon
fluoridesandoxides,J. Chem.Phys.84, 369, 1986.
Angell, C. A. Formationof glassesfrom liquidsand bipolymers,
Wasson,J. T., Chondrule
formation:energetics
andlengthscales,in
Science267, 1924, 1995.
Chondrulesand the Protoplanetary
Disk, R. H. Hewins, Ed.,
Bradley,J.P., T. P. Snow, D. E. Brownlee,and M. S. Hanner,in
CambridgeUniversityPress,45, 1996.
Solid InterstellarMatter: The ISO Revolution,L. d'Hendecourt,
Weber,J. K. R., J. J. Felten,B. Cho, andP. C. Nordine,Glassfibres
C. Joblin,A. Jones,Eds.,Springer,Berlin,297-315,1999.
of pure and erbium- or neodymium-doped
yttria-alumina
Cooney,T. F. andS. K. Sharma,Structureof glasses
in the systems
compositions,
Nature 393, 769, 1998.
Mg2SiOn-Fe2SiO4,
Mn2SiOn-Fe2SiO4,
Mg2SiOn-CaMgSiO4,
and Weber,J. K. R., D. S. Hampton,D. R. Merkley,C. A. Rey, M. M.
Mn2SiOn-CaMnSiO4,
J. Non-Cryst.Sol. 122, 10, 1990.
Zatarski, and P. C. Nordine, Aero-acousticlevitation: a method
Crovisier,J., K. Leech,D. Bocke16e-Morvan,
T. Y. Brooke,M. S.
for containerless
liquid-phase
processing
at high temperatures,
Rev. Sci.Instrum. 65(2), 456, 1994.
Hanner,B. Altieri,H. U. Keller,andE. Lellouch,Thespectrum
of

liquid-phase
cometHale-Bopp
(C/199501) observed
withtheInfraredSpace Weber,J. K. R. and P. C. Nordine,Containerless
Observatoryat 2.9 astronomical
unitsfrom the Sun,Science275,
1904, 1997.

Dorschner,
J. and T. Henning,Dust metamorphosis
in the galaxy,
Astron.Astrophys.
Rev. 6, 271, 1995.
Hanada,T., N. Soga, and T. Tachibana,Coordinationstate of
magnesium
ions in rf-sputtered
amorphous
films in the system
MgO-SiO2,J. Non-Cryst.Sol. 105, 39, 1988.

processingat high temperatures,Microgravity Sci. and

Technology,VII, 279, 1995.

Williams,Q., P. McMillan,andT. F. Cooney,Vibrationalspectraof

olivine compositionglasses:the Mg-Mn join, Phys. Chem.
Minerals 16, 352, 1989.

B. Phillips,A. Navrotsky,and J. Tangeman,Departmentof

Hashimoto,
A.,Evaporation
kinetics
offorsterite
andimplications
for Chemical Engineeringand Materials Science, University of
the earlysolarnebula,Nature 347, 53, 1990.
Californiaat Davis,DavisCA 95616,USA. (email:blphillipsand
Hervig, R. L., D. Scott,and A. Navrotsky,Thermochemistry
of
anavrotsky@ucdavis.
edu,tangeman@containerless.com)
A. Hixson,T. Key, and R. Weber, Containerless
Research,Inc.,
glassesalongjoins of pyroxenestoichiometry
in the system
CaSiO6-Mg:Si:O6-A1406,
Geochim.Cosmochim.
Acta 49, 1497,
906 University Place, Evanston, IL 60201, USA. (email:
1985.
weber@containerless.com)
Ito, K., C. T. Moynihan, and C. A. Angell, Thermodynamic
determination
of fragilityin liquidsanda fragile-to-strong
liquid (ReceivedAugust17,2000;revisedJanuary12,2001;
transitionin water, Nature 398, 492, 1999.
accepted
January18, 2001.)