ARD-AI?i 916 EXPANSION COEFFICIENT ON OXIDES AND OXIDE CERANICS(U) /NAVAL WEAPONS CENTER CHINA LAKE CA J COVING NAY 86

IFE NUC-TP-6663 SBI-AD-E9SS 596

UNCLASSIFIED F/G U12

ia

4 2.

11

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MICROCOPY RESOLUTION TEST CHARTNATIONAt BURELAU OF STANDARD4, 19hi A

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NWC TP 6663 7

Expansion Coefficient on Oxidesand Oxide Ceramics

0D

byJosephine Covino

Research Department

* I MAY 1986

DTICEL ECTE

NAVAL WEAPONS CENTER AG1 51986CHINA LAKE, CA 935556001 Uj

I B

Approved f or public release; distribution is unlimited.

C-2

NN..

* Naval Weapons Center

FOREWORD

Since the production of Cer-vit ceased, we have become increasinglydependent on Schott's Zerodur and Corning's ULE (type 7971) for use inapplications requiring ultra-low thermal expansivity. There are timeswhen neither ULE nor Zerodur are acceptable, particularly for lasergyros. In our search for a replacement for Cer-vit, we have begun bycompiling the data found in the open literature through June 1985 onexpansion coefficients of oxides and oxide ceramics. This report is theresult of our gathering of this data.

This compilation was performed for Andrew Glista under NAVAIRProgram Element 637-28-N, Project Number 137-831, Task Number W-1050,and Work Unit Number 137-831.

The report was reviewed for technical accuracy by Charlotte K.Lowe-Ma.

Approved by Under authority ofR. L. DERR, Head K. A. DICKERSONResearch Department Capt., USN15 May 1986 Commander

Released for publication byG. R. SCHIEFERTechnical Director

NWC Technical Publication 6663

Published by .... ............. .. Technical Information DepartmentCollation ......... ...................... .Cover, 22 leavesFirst printing ......... ....................... ... 85 copies

-*1

UNCLASSIFIEDSECURITY CLASSIFICATION OF THIS PAG E"o. A17/ ri

REPORT DOCUMENTATION PAGEla REPORT SECURITY CLASSIFICATION lb RESTRICTIVE MARKINGS

UNCLASSIFIED2a SECURITY CLASSIFICATION AUTHORITY 3 DISTRIBUTION /AVAILABILITY OF REPORT

Approved for public release; distribution2b DECLASSIFICATION DOWNGRADING SCHEDULEisulmtdis unlimited.

4 PERFORMING ORGANIZATION REPORT NUMBER(S) 5 MONITORING ORGANIZATION REPORT NUMBER(S)

NWC TP 6663

6a NAME OF PERFORMING ORGANIZATION 6b OFFICE SYMBOL 7a NAME OF MONITORING ORGANIZATION(If applicable)

Naval Weapons Center I

6c ADDRESS (City, State, and ZIP Code) 7b ADDRESS (C;ty, State, and ZIP Code)

China Lake, CA 93555-6001

8a. NAME OF FUNDING /SPONSORING 8b OFFICE SYMBOL 9 PROCUREMENT INSTRUMENT IDENTIFICATION NUMBERORGANIZATION (if applicable)

Naval Weapons Center I

8c ADDRESS (City, State, and ZIPCode) 10 SOURCE OF FUNDING NUMBERS

PROGRAM PROJECT TASK iVORK N T

ELEMENT NO NO NO NO

China Lake, CA 93555-6001 637-28-N 137-831 W-1050 137-831

11 TITLE (Include Security Classification)

EXPANSION COEFFICIENTS ON OXIDES AND OXIDE CERAMICS

12 PFRSONAL AUTHOR(S)

Josephine Covino

13a TYPE OF REPORT 13b TIME COVERED 114 DATE OF REPORT (Year, Month. Day) 15 PAGE COUNT

Final I FROM 84 Dec TO 85 Jun 1986, May 4216 SUPPLEMENTARY NOTATION

17 COSATI CODES 18 SUBJECT TERMS (Continue on reverse if necessary and identify by block number)

FIELD GROUP SUB-GROUP Expansion Coefficients, Oxides, Structure Type,

11 02 Unit Cell Parameters

19 ABSTRACT (Continue on reverse if necessary and identify by block number)

(U) Expansion coefficients for existing oxides and oxide ceramics have been compiled.

In some cases, where data is available, a description of how the thermal expansion

coefficient was measured will be noted.

20 DISTRIBUTION /AVAILABILITY OF ABSTRACT 21 ABSTRACT SECURITY CLASSIFICATION

[UNCLASSIFIED/UNLIMITED 0 SAME AS RPT 0 DTIC USERS UNCLASSIFIED22a NAME OF RESPONSIBLE INDIVIDUAL 22b TELEPHONE (Include Area Code) 22c OFFICE SYMBOL

Jse2hne Covino 619-939-1608 3854

DD FORM 1473, 84 MAR 83 APR edition may be used untI exhausted SECURITY CLASSIFICATIONOF THIS PAGEAll other editions are obsolete C S-E

aUNCIASSIFIED

NWC TP 6663

CONTENTS

Introduction ............. ........................... 3

Discussion ... .......... ....... ................ 3

Conclusions .......... ........................... . 28

References .......... ............................ . 29

Figure:1. Expansion of Coefficients Versus Temperature Plots

for Some Commonly Used Laser Gyro Materials ........ ... 26

Tables:1. Thermal Expansion of Crystals Data ..... ........... 52, Coefficients of Thermal Expansion at Very

Low Temperatures of Solids ... ............... .. 153. Thermal Expansion of Fixed-Structure and Simple-

Structure Compounds for Which Bond ThermalExpansion is Equal to Bulk Linear Expansion ........ ... 17

4. Polyhedral Thermal Expansion, Variation of IsotropicTemperature Parameters and Bonding Parameters FromComplete Three-Dimensional, High-Temperature (>400*C)Crystal Structure Refinements .. .............. 20

5. Oxides With Very Low to Intermediate ThermalExpansion ......... ........................ .. 27

SAce':= on Par

NTI ,

DTICS ELECTEAUG 15 198 6 jJ

c '! t "

NWC TP 6663

INTRODUCTION

Since the production of the glass ceramic Cer-vit ceased, we havebecome increasingly dependent on Schott's Zerodur and Corning's ULE(type 7971) for applications requiring ultra-low thermal expansivity;however, there are applications where neither ULE nor Zerodur areacceptable. For example, ULE has a high helium permeability and cannotbe used for laser gyros. Zerodur cannot be used for all laser gyroapplications because it is unstable on thermal cycling between -23 and177*C (-9 and 3500 F), which is the operational range of laser gyros.Furthermore, Zerodur is not of a reproducibly acceptable quality nor isit readily available. Because of these problems, the Navy needs newoxide glass ceramics with ultra-low expansion coefficients and lowhelium permeability.

This report is a compilation of data on expansion coefficients forexisting oxides and oxide ceramics. Some of these materials may besuitable for laser gyro applications.

DISCUSSION

In the past 20 years, there has been an enormous growth ofresearch effort in the measurement of thermal expansion coefficients ofmaterials. These methods can be classified under the two generalheadings of microscopic (lattice) expansion measurements and macro-scopic methods. The observations on thermal expension can be madeusing either a static or a dynamic procedure. In the static procedure,the temperature of the material under investigation is maintained con-stant for a certain interval of time, and the variation of the lengththat takes place from one temperature to the other is measured.

The linear thermal expansion coefficient, a, at temperature T inkelvin units, can be calculated from the following empirical equation

Cv (1)XT V

3

NWC TP 6663

whereXT = the isothermal compressibility of the solidy = the dimensionless quantity referred to has the GrUneisen

constant (y is about 2 and is temperature independent)Cv = molar specific heatV - volume of the solid, cm

At high temperatures, the empirical equation for a range oftemperatures is given by

aT = A + B (T-T0 ) + C (T-T0 )2 (2)

while at very low temperatures

aT = Bt + DI? + ET5 + • (3)

whereA = the linear thermal expansion coefficient at temperature To

(K) and it is a facyrfxpression in 10 -6/K,B - factor expressed 10 fK-C = factor expressed l0I ,

Dfactor expressed 10 1KE = factor expressed i1 ,i andT - temperature in K

Equations 2 and 3 are purely empirical tn that they have beenderived from experimental results and observations. The numericalvalues of the quantities, A, B, C, etc., are given to two or threesignificant figures after the decimal point. The number of figuresafter the decimal point varies in Tables 1 and 2 because some materialshave been studied more precisely than others. The columns entitledMethod and Remarks give some indication of how a was measured. Thedetails of the methods applied for measuring coefficients of thermalexpansion reported in Tables 1 and 2 can be found in chapter 2 ofR. S. Krishnan's book, Thermal Expansion of Crystals (Reference I).

Table I presents a compilation of aT for oxides at high tempera-tures and Table 2 presents some low-temperature data. Much of thedescription of structural variation with temperature depends on the useof thermal expansion coefficients of volume and linear structuralunits. Thus, it is important to recognize the limits in the accuracyof reported coefficients. Unit-cell expansion coefficients may bedetermined on single crystals or powders using either X-ray diffractionor dilatometry. Although the reported precision for many of thoseexperiments is about 1% of the expansion coefficient, several studieson the same material commonly differ by ±10%.

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NWC TP 6663

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NWC TP 6663

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NWC TP 6663

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NWC TP 6663

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NWC TP 6663

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10

NWC TP 6663

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NWC TP 6663

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NWC TP 6663

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NWC TP 6663

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NWC TP 6663

TABLE 2. Coefficients of Thermal Expansion atVery Low Temperatures of Solids.

Lattice, TemperatureCompound, silica D(10-'/K) range, K Method Reference

Spectrosil 1000 -41 ±1 1.5-10 3T-C 90

Spectrosil 1400 -35 ±2 1.5-10 3T-C 90

Vitreosil 1000 -40 ± 1 1.5-10 3T-C 90

Vitreosil 1400 -35 ti 1.5-10 3T-C 90

A variety of factors including material impurities, crystallinedefects, or sample preparation may lead to the disagreement betweenthermal expansion studies. However, even in well-crystallized purecompounds, such as MgO or A1203 , a considerable range of publishedexpansion coefficients exist. It appears that systematic experimentalerrors are very common in thermal expansion measurements, therefore,

*standardized procedures are needed to increase the accuracy of thesestudies. Until standardized procedures are developed, the accuracy ofany given study must be conservatively accepted as no better than ±5%.

In Tables 1 and 2, the column labeled Compound lists the formulaname and composition of both naturally occurring minerals and syntheticoxides. The second column in Table 1, labeled Crystal systems, liststhe structure type. The temperature at which the measurement was made(TO) is in kelvin units. The columns labeled A, B, and C are thevalues that are needed to solve equations 2 or 3 for the linear thermal

expansion coefficient. The eighth column, Range of temp, K, indicatesthe temperature range for which the given data is applicable.

The compounds reported in Tables 1 and 2 have not been classifiedin any way. However, most of the compounds are arranged according tothe crystal systems to which they belong. In the case of anisotropiccrystals, the direction of measurement in the crystal is indicated inthe column labeled Axis. Some solids listed have only a at a particu-lar temperature; this is a reflection of what appears in theliterature.

In Table 2, coefficients of thermal expansion at very low tempera-tures are listed for some commonly used silica glasses. A capacitancetechnique was used to make these measurements. In the capacitance

15

5,€~

NWC TP 6663

dilatometer, the specimen dilates, thus altering the distance betweenthe plates of the condenser producing variations in capacity. Athree-terminal capaci ance method is used to measure detection of move-ments as small as 10- cm and 10- 10 cm; this allows measurements of ato be within an error of -10- 10 /K. A detailed description of thismethod is reported by White (Reference 91).

Table 3 lists thermal expansion of fixed-structure and simplestructure compounds for which bond thermal expansion is equal to bulklinear expansion.

In a fixed-structure compound, the specific cations and anions fixthe structure, while a simple structure compound (e.g.,Mg0 .33 Fe0 .670) is one in which there is only one cation and oneanion (e.g., NiO). The first column lists the compound type, followedby the bond and structure type. Zc is the cation valence, Za is

the anion valence, and n is the coordination number. The expansioncoefficient a*100 0 can be calculated by the following equation.

- 2 d1 00 0 - do

1000 M do + dlo00 980 m510 (4)

where

d= mean cation-anion bond distance at 200CdO = mean cation-anion bond distance at 1000C

Table 4 lists polyhedral thermal expansion coefficients, takinginto consideration the variation of isotropic temperature parametersand bonding parameters from complete three-dimensional, high-temperature (>400C) crystal structure refinements.

Attempts have been made to relate thermal expansion to bondingparameters or other physical properties. Cameron and others relatedexpansion coefficients of metal-oxygen bonds to. bond strengths (Refer-ence 132) where the expansion coefficient

a = 4v1 2 C2 (5)

wherea =expansion coefficientv = M-0 stretching frequency

= reduced massC = speed of light

Although their relationship successfully modeled the bond expansion oftheir study, the Cameron equation does not nredict many of the featuresof Tables 3 and 4. Cameron's equation does not predict that compoundshaving the rock salt-type structure such as Ni-O, Mg-(), Fe-, and Ba-O

16

NWC TP 6663

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*z ~ z z zz z zz z z z z z z z zzz z

0 00 000 C- 00 0~0 0L L L L

0000 00000000- 74L. ) U,

17

NWC TP 6663

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NWC TP 6663

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NWC TP 6663

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20

NWC TP 6663

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21

NWC TP 6663

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NWC TP 6663

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NWC TP 6663

have similar expansion coefficients. The data in Tables I and 2 aremeasured values, while the data in Tables 3 and 4 are calculatedvalues.

Some authors have attempted to relate thermal expansivity to otherphysical variables as was demonstrated by Hanneman and Gatos (Refer-ence 159). The relation between compressibility and thermal expansioncoefficients in cubic metals and alloys is that thermal expansion andcompressibility are proportional for cubic metals and alloys. VanUitert and others found a simple inverse relation between the coeffi-cient of thermal expansion and the melting temperature for a largenumber of close-packed structures (References 160 and 161).

Many investigators have examined the relationships between thermalexpansion, thermal vibration amplitudes, and specific heat. The numberof attempts to predict thermal expansion and relate expansion to otherphysical variables attest to the usefulness that such relationshipswould be for modeling the high-temperature behavior of solid-state

materials.

A few simple empirical relationships, which allow the predictionof bond distance changes with temperature, can be deduced from Tables 3and 4. The first important observation is that all cation coordinationpolyhedra of a given type (i.e., silicon-oxygen tetrahedra, magnesium-oxygen octahedra) show similar expansion coefficients. For example,Tables 3 and 4 contain 48 compounds containing silicon tetrahedra thathave coefficients near or equal to zero within two standard errors. Ofthe remaining five compounds, two tetrahedra have positive expansioncoefficients. In the case of anorthite, the positive expansion of Si-Ois accompanied by a large contraction of adjacent AI-O bonds. It seemsthat these anomalies are caused by disordering of Si and Al rather thanchanges in bonds of a fixed composition. The other three nonzero Si-Oexpansivities occur in the tetrahedral chains. In each of these tetra-hedral sites, the bridging oxygen to silicon distance shows significantshortening with increasing temperature. Therefore, this anomalousbehavior can be due to the changing topology of the material withtemperature. The positive expansion in grossular garnet, is still asmall, and possibly insignificant, expansion. All of the Mg-O thermalexpansion coefficients are consistent with a value of 14 x 10-GC - 1

(±10).

An important conclusion that can be made from these observationsis that the thermal expansion coefficient for each type of polyhedronis independent of structural linkages of the polyhedron, as long as thesite chemistry and the nearest neighbor configuration of the structuredo not change with temperature. Therefore, for each type of cation-oxygen polyhedron, a value for an expansion coefficient exists that maybe used to predict behavior at high temperature. A second generaliza-

tion evident from Table 4 is that all oxygen-based polyhedra with the

25

NWC TP 6663

same Pauling bond strength (cation valence, Zc, divided by coordina-

tion number, n) have the same Y1000.

Bulk thermal expansion coefficients are not only a function of

bond distance and bond strength, but also how these polyhedra are

linked together. Two polyhedra may be linked by a shared face, a

shared edge, a shared corner or merely by Van der Waal's forces. The

type and distribution of these polyhedra linkages are the most impor-

tant "actors in determining the bulk thermal expansion of a compound.

The most rigid polyhedral linkage is one in which polyhedra share faces

or edges in three dimensions. For example, in the rock salt-,

corundum-, spinel-, and garnet-type compounds in which a fully edge-

linked structure exists, the bulk thermal expansion is small. The bulk

thermal expansion is similar in magnitude to the thermal expansion of

metal-oxygen polyhedra.

Table 5 lists a variety of nominally single phase oxides with very

low ((M x 10-6/K'), low (1-4 x 10-6/K), and intermediate (4-9 x 10- 6 /K)

thermal expansion coefficients (References 162 through 164).

Three expansion coefficients versus temperature plots are illus-

trated in Figure 1. These are materials that are commonly used as

low-expansion materials in the temperature region of 0 to 600 K. As

can be seen in this figure, the expansion coefficient is not constant

as a function of temperature.

100

I'\S\CER-VIT

" I I(Cl0l)

I'

0

- 0 -

X I/ ZERODUR

"" COR NING (ULE)

7971

-100

0 100 200 300 400 500 600

TEMPERATURE, K

FIGURE 1. Expansion Coefficients Versus Temperature Plots for Some

Commonly Used Laser Gyro Materials.

26

NWC TP 6663

TABLE 5. Oxides With Very Low to Intermediate Thermal Expansion.

a a 106 Porosity, Refer-

Material (K ) mp (K) Crystal systemc ence

Very low

Ta1 6 W18 094 -5.1 >2050 31 Tetragonal 162Ta2 WOB -2 to 2125 1-36 Orthorhombtc 162

3.2Nb2 Hf6 017 (Solid 'olutton)

-0.7 1700 38 --- 163

Nb20( (Solid solution)

(Hf 0 -8 W0 -STal -6 )08 0.0 1690 41 Orthorhombic 163Ta2 W08 type

Hf1 "26 ri '71) 0.0 >2475 16 Orthorhombic 163HfTiO4 type

Ta22 W4 0$7 0.6 2150 40 Orthorhombic 162A12 Ti(s 0.8 2060 12 Orthorhombic 163

Low

(Hf0 -9 4 5 H0 -3 15 Ti0 " 74 )04 2.2 2135 12 Orthorhombic 163HfTiO4 type

Zrl .7 1 Nb1 0 -2' 4029 2.5 1680 32 Orthorhombic 163Ti2N4bl 0 0 2 9 type

Hfl "71 Nbl0 2 4029 3.2 1700 35 Orthorhombic 163Ti2 kNBI 0 02 9 type

Ta2 Ti 7 3.4 1920 36 Monoclinic 163HfTiO4 3.6 2455 29 Orthorhombic 163Nb, Ti 7 3.6 2155 2 Monoclinic 163

Intermediate

NiT,2 06 e 4.1 1965 18 Tetragonal 163Zr4 "29 4Tal -76505 4.2 2000 36 Hexagonal 163

6-Ta2 05 typeAlHfTaO 4.4 2435 30 Orthorhombic 163AlTa04 e 5.0 1935 21 Hexagonal 163(Hf 0 "315 H0 "315 Ti 0 "37 )02 5.9 >2625 5 Monoclinic 163

HfO 2 type(A[0 -76 H. 0 *38 '00 -38 Ti 0 "67 )04 6.4 1925 36 Orthorhombic 163

I HfTi04 typeYHfTaO6 6.6 21S5 13 Orthorhombic 164MgTa2 06 6.8 2000 38 Tetragonal 163AlTiTaO6 7.1 1970 28 Tetragonal 164

YTiTaO6 7.5 2025 28 Orthorhombic 163Y2 Ti( 8.8 2115 22 Orthorhombic 164

a Coefficient of thermal expansion assuming linear thermal expansion from295-1275 K.

b Melting point values measured by differential thermal analysis.C Single phase by X-ray diffraction.

j d Sample contained some Ti 2 as a second phase as determined by X-ray diffraction.e Sample contained some 6-Ta2 05 determined by X-ray diffraction.

27

.......................................................|

,c t . . ..

NWC TP 6663

CONCLUSIONS

This paper reports expansion coefficients for a variety of oxides

and oxide ceramics and discusses some rules for predicting low expan-

sion oxides. Some of the structure types in which low thermal expan-

sion should be expected are rock salt, corundum, spinel, and garnet.

This information can make it possible to synthesize new materials with

somewhat predictable expansion coefficients. It is possible that a

multiphase material can be engineered to have a net zero expansion at a

given temperature by forming a ceramic composite with components that

have both negative and positive expansion coefficients. This is the

approach taken in Zerodur and in ULE, but clearly, some improvements

need to be made. However, just having a powder that has the right

composition to Rive a low expansion ceramic is only part of the prob-

lem. Studies have indicated that processing can drastically alter

expansion properties of oxides. It has been found that fine-grained

(<10 tm) anisotropic ceramic materials, such as hafnium oxide, hafnium

titanate, and tantalum tungstate may exhibit thermal expansion hystere-

sis effects with minimal observable microcracking or grain boundary

separations (References 165 through 167). In ceramic materials, ther-

mal expansion hysteresis can be accounted for by reversible phasetransitions or by microcracking.

For large-grained bodies of materials, microcracking is the common

cause of thermal expansion hysteresis. Considering fine-grained mate-

rials data shows that all materials will have a critical grain sizebelow which no observable microcracking can occur (Reference 168).

However, fine-grained ceramic materials have a greater tendency to

deform without cracking since mechanical strength is greater, and there

is decreased localized grain-boundarv stress resulting from thermal

expansion anisotropy (Reference 16Q). Therefore, for ceramic mate-

rials, any effect of cyclic plastic deformation (strain induced fromthermal cycling) should increase :is the grain-size decreases.

Whenever thermal expansion hysteresis is apparent and phase trans-

formations or microcracking are not apparent, hysteresis in the thermal

expansion courses of ceramics could be accounted for by a plasticdeformation component (caused by thermal stresses at polycrystalline %grain boundary) added to the elastic strain (thermal expansion or con-traction). Because of the factors that can affect the expansion coef-ficient of a material, synthesis of "low expansion" (<10 /K) materials

for laser gyro, structural ceramic applications are an area of continu-

ous research.

28

I,

NWC TP 6663

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.... .. -.

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127. E. P. Meagher and G. A. Lager. "Polyhedral Thermal Expansion in

the Ti0 2 Polymorphs: Refinement of the Crystal Structures ofRutile and Brookite at High Temperature," Caznadian kineraZ., 17(1979), pp. 77-85.

128. M. Horn, C. F. Schwerdtfeger, and E. P. Meagher. "Refinement ofthe Structure of Anatase at Several Temperatures," Z. Krista7-Zogr., 136 (1972), pp. 3913-16.

129. E. P. Meagher. "The Crystal Structures of Pvrope and Grossulariteat Elevated Temperatures," Am. Mineral., 60 (1975), pp. 218-28.

130. R. M. Hazen. "Effects of Temperature and Pressure on the CrystalStructure of Forsterite," 4lm. Mineral., 61 (1976b), pp. 1280-93.

131. G. E. Brown and C. T. Prewitt. "High-Temperture Crystal Chemistry

of Hortonolite," Am. Mineral., 58 (1973), pp. 577-87.

132. J. R. Smyth and R. M. Hazen. "The Crystal Structures of Forster-ite and Hortonolite at Several Temperatures up to 900°C," Am.Mineral., 58 (1973), pp. 588-593.

133. J. R. Smyth. "High Temperature Crystal Chemistry of Payalite,"Am. Mineral., 60 (1975), pp. 1092-97.

134. L. W. Finger, R. M. Hazen, Y. Yagi. "Crystal Structures and Elec-tron Densities of Nickel and Iron Silicate Spinels at ElevatedTemperature or Pressure," 4m. Mineral., 64 (1979), pp. 1002-9.

135. M. Taylor and G. E. Brown. "High-Temperature Structural Study ofthe P21 /a-A2/a Phase Transition in Synthetic Titanite, CaTiSiO5 ,"Am. Mi.neraZl., 61 (1976) pp. 435-47.

136. B. A. Wechsler. "Cation Distribution and High-Temperature CrystalChemistry of Armalcolite," Am. Mineral., 62 (1977), pp. Q13-20.

137. A. M. Glazer and S. A. Mabud. "Powder Profile Refinement of Lend

Zirconate Titanate at Several Temperaturesq. 11. Pure PbTiO 3 ,"Acta CrystalZogr., B34 (1978), pp. 1065-70.

38

NWC TP 6663

138. S. Sueno, M. Cameron, and C. T. Prewitt. "Orthoferrosilite: HighTemperature Crystal Chemistry," Am. M"neraZ., 61 (1976),pp. 38-53.

139. J. R. Smyth. "An Orthopyroxene Structure up to 850°C," Am.Mineral., 58 (1973), pp. 636-848.

140. J. R. Smyth. "The High-Temperature Crystal Chemistry of Clino-hypersthene," Am. Mineral., 59 (1974), pp. 1069-82.

141. M. Cameron, S. Sueno, C. T. Prewitt, and J. J. Papike. "High-Temperature Crystal Chemistry of Acmite, Diopside, Hedenbergite,Jadeite, Spodumene, and Ureyite," Am. Mineral., 58 (1973),pp. 594-618.

142. C. T. Prewitt, S. Sueno, and J. J. Papike. "The Crystal Struc-tures of High Albite and Monalbite at High Temperatures," Am.Miner Z., 61 (1976), pp. 1213-25.

143. J. K. Winter, F. P. Okamura, and S. Chose. "A High-Temperature

Structural Study of High Albite, Monalbite, and the Analbite-Monalbite Phase Transition," Am. MineraZ., 64 (1979),pp. 409-23.

144. J. K. Winter, S. Chose, and F. P. Okamura. "A High-TemperatureStudy of the Thermal Expansion and the Anisotropy of the Sodium

Atom in Low Albite," Am. Mineral., 62 (1977), pp. 921-31.

145. F. F. Foit and D. R. Peacor. "The Anorthite Crystal Structure at410 and 830*C," Am. Mineral., 58 (1973), pp. 665-75.

146. N. Foreman and D. R. Peacor. "Refinement of the Nepheline Struc-ture at Several Temperatures," Z. Kristallogr., 132 (1970),pp. 45-70.

147. M. F. Hochella, G. E. Brown, F. K. Ross, and G. V. Giggs. "High-

Temperature Crystal Chemistry of Hydrous Mg- and Fe-Cordierites,"Am. Mineral., 64 (1979), pp. 337-51.

148. H. Takeda and B. Morosin. "Comparison of Observed and Predicted

Structural Parameters of Mica at High Temperature," Acta Cnystat-Zogr., B31 (1975), pp. 2444-52.

149. J. K. Winter and S. Chose. "Thermal Expansion and High-

Temperature Crystal Chemistry of the AI2SiO 5 Polymorphs," Am.Mineral., 64 (1979), pp. 573-86.

150. W. W. Pillars and D. R. Peacor. "The Crystal Structure of

b-Eucryptite as a Function of Temperature," Am. MineraZ., 58(1973), pp. 681-90.

39

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NWC TP 6663

151. S. Sueno, M. Cameron, J. J. Papike, and C. T. Prewitt. "The HighTemperature Crystal Chemistry of Tremolite," 4m. Mineral., 58(1973), pp. 649-64.

152. D. E. Cox and A. W. Sleight. "Mixed-Valent Ba2 Bi3+Bi5 +06 : Struc-

ture and Properties Versus Temperature," Acta CrystaZlogr., B35(1979), pp. 1-10.

153. G. E. Brown, C. T. Prewitt, J. J. Papike, and S. Sueno. "AComparison of the Structures of Low and High Pigeonite," 7.Geophys. Res., 77 (1972), pp. 5778-89.

154. A. S. Koster, J. P. P. Renaud, and G. D. Rieck. "The CrystalStructures at 20 and 1000C of Bismuth Uranate, Bi2 UO6 ," ActaCrystaIZogr., B31 (1975), pp. 127-31.

155. J. R. Smyth. "Orthopyroxene-High-Low Clinopyroxene Inversions,"

Earth Planet. 5ci. Lett., 6 (1969), pp. 406-7.

156. J. R. Smyth. "Protoenstatite: A Crystal-Structure Refinement atlO0°C," Z. Kristallogr., 134 (1971), pp. 262-74.

157. J. R. Smyth and C. W. Burnham. "The Crystal Structures of Highand Low Clinohypersthene," Earth Planet. Sci. Lett., 14 (1972),

pp. 183-89.

158. S. Sueno, J. J. Papike, C. T. Prewitt, and G. E. Brown. "CrystalStructure of Cummingtonite," 47. Geophys. Res., 77 (1972)pp. 5767-77.

159. R. E. Hanneman, H. C. Gatos. "The Relation Between Compres-sibility and Thermal Expansion Coefficients in Cubic Metals and

Alloys," 7. Appt. Phys., 36 (1965), np. 1794-96.

160. L. G. Van Uitert, H. M. O'Brvan, H. J. Guggenheim, R. L. Barns,

and G. 0. Zydzik. "Correlation of the Thermal Expansion Coeffi-cients of Rare Earth and Transition Metal Oxides and Fluorides,"Mater. Res. Rull., 12 (1977), pp. 307-314.

161. L. G. Van Vitert, H. M. O'Brvan, H. .J. Guggenheim, R. L. Barns,and G. 0. Zydzik. "Thermal Expansion--An Empirical Correlation,"Mater. Res. RuZZ., 12 (1977), pp. 261-268.

162. C. E. Holcombe, Jr. "Thermal Expansion Coefficients for LowExpansion Oxices," q9igTh Temp. qci., 12 (1980), pp. 63-66.

163. C. E. Holcombe, Jr. "Thermal Expansion Coefficients for LowExpansion Oxides," (eramic M411., 59(12) (1980), pp. 1219-20.

40

d' *" , "2"% ' "" "" "" . . :" " ' ' "" "' " "" ' ".' . W '''V .. ." ' '' '

NWC TP 6663

164. C. E. Holcombe, Jr. "Ternary Tantalate Compositions," J. Akter.Sci., 14(9) (1979), pp. 2255-60.

165. C. E. Holcombe and D. D. Smith. "Characterization of theThermally Contracting Tungstates, Ta2 2W4 06 7 , Ta2WO8 , andTal6 W1 8 094 ," J. Am. Ceram. Soc., 61 (1978), pp. 163-69.

166. R. Ruh, G. W. Hollenberg, S. R. Skaggs, S. D. Stoddard, and F. D.Gac. "Axial and Linear Thermal Expansion of ZrO 2 and HfO2 ," Am.Ceram. Soc. RuZl. 60(4) (1981), pp. 504-506.

167. R. Ruh, G. W. Hollenberg, E. G. Charles, and V. A. Patel. "PhaseRelations and Thermal Expansion in the System HfO2 -TiO 2 ," J. Am.Ceram. Soc., 59 (1976), pp. 495-99.

168. J. J. Cleveland and R. C. Bradt. "Grain Size-Thermal ExpansionAnisotropy Effects on Strength and Fracture of Pseudobrookites,"Cer'am. Soc. Bul., 55 (1976), p. 396.

169. J. E. Blendell, R. L. Cable, and R. J. Charles. in CeramicMicrostructures: Proceedings of 6th (1976) InternationalMaterials Symposium, Westview Press, Boulder, Colo., 1977 (R. W.Fulrath and J. A. Pask, eds.). Pp. 721-730.

41

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NWC TP 6663

INITIAL DISTRIBUTION

7 Naval Air Systems CommandAIR-33E. Andrew Glista (5)AIR-723 (2)

2 Naval Sea Systems Command (SEA-09B312)I Commander in Chief, U. S. Pacific Fleet (Code 325)1 Commander, Third Fleet, Pearl Harbor2 Naval Academy, Annapolis (Director of Research)3 Naval Ship Weapon Systems Engineering Station, Port Hueneme

Code 5711, Repository (2)Code 5712 (1)

1 Naval War College, Newport1 Air Force Intelligence Service, Boiling Air Force Base (AFIS/INTAW, Maj. R. Lecklider)

12 Defense Technical Information Center3 Kimble Applied Research & Development, Toledo, Off (T. W. Brock)5 Litton Systems Inc., Woodland Hills. CA (Frans G. A. DeLaat)4 Singer Company, Little Falls, NJ (Michael Tarasivich)

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