NSWC TR 86-242

OhCFILE coJP Y

CALCULATION OF MULTICOMPONENT REFRACTORYQ)COMPOSITE PHASE DIAGRAMS

0)

,%N

iN

BY 1. KAUFMAN (MAN LABS, INC.)

* ~ FOR NAVAL SURFACE WZAPONS CENTERSTRATEGIC SYSTEMS DEPARTMENT

~h~ 1 JUNE 1986

Approved for public release; distribution is unlimited.

I

-•,

~~~~ S• ELECTEEHAEDIGRM

._• ~~~~ ~ ~ A 1• 71988UMA MNLB, N.

"NAVAL SURFACE WEAPONS CENTERSDahigren, Virginia 22448-5000 0 Silver Spring, Maryland 20903-5000

18 3 10 009

--- ------ --.... ..... .... . . .... ... ....

UNCLASSIFIEDSECURITY CLASSIFICATION OF THIS PAGE

REPORT DOCUMENTATION PAGE............Ia. REPORT SECURITY CLASSIFICATION lb. RESTRICTIVE MARKINGS

UNCLASSIFIED ............2a.. SECURITY CLASSIFICATION AUTHORITY 3 -DISTRIBUTION/ AVAILABILITV OF REPORT

Approved for public release, distribution2b. DECLASS!FICATION/ DOWNGRADING SCHEDULE .is unlimited.

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

NSWC TR 86-242

6a. NAME OF PERFr'tMING ORGANIZATION' 6b OFFICE SYMBOL 7a. NAME OF MONITORING ORGANIZATION

ManLabs, Inc. (If applicable) Naval Surface Weapons Center

6C. ADDRESS (City, State, and ZIP Code) 7b. ADDRESS (City, State, and ZIP Code)

21 Erie Street 10901 New Hampshire Avenue ,..Cambridge, MA 02139 Silver Spring, MD 20903-5000

Ba. NAME OF FUNDING/SPONSORING 8b. OFFICE SYMBOL 9. PROCUREMENT INSTRUMENT IDENTIFNCATION NUMBERORGANIZATION (If applicable) N60921-86-M- 1034

8c. ADDRESS (City, State, arc" ZIP Code) 10 SOURCE OF FUNDING NUMBERSPROGRAM PROJECT TASK IWORK UNITELEtVENT NO. NO. NO. RS61- IACCESSION NO.

62761N RS61-543 543-42C8 6K14KS

11 TITLE (Include Security Classification)

Calculation of Multicomponent Refractory Composite Phase Diagrams

12. PERSONAL AUTHOR(S)Kaufman, L.

13a. TYPE CF REPORT 113b TIME COVERED 114. DATE OF REPORT (Year, Month, Oay) IS. PAGE COUNTFinal . FROM _.1L1/86L TO6,"/ 1986, June 1 54

16. SUPPLEMENTARY NOTATION

This technical effort is part of the Surface Launched Weaponry Materials Technoloav Proaram17. COSATI CODES 18. SUBJECT TERMS (Continue on reverse if necessary and identify by block number)

FIELD GROUP SUB-GROUP High-temperature materials Phase stability11 06 Refractory materials Intermetallic compounds07 , 04 Phase dianrams

19. ABSTRACT (Continue on reverse if nece.uary and identify by block number)

Coupled phase diagram/thermochemical description of the Hf-B, Hf-C, Zr-B, and Zr-C

binary systems have been developed and combined with previously derived descriptions of

the B-C, Zr-Si, Hf-Si, Si-B, and Si-C binary systems in order to calculate the temperatures

at which melting First occurs in the composition ranges betweei- C-ZrC-ZrB2-B4C,

C-HfC-HfB2 -B4 C, HfC-SiC, ZrB2 -SiC, and HfB2 -SiC. These systems are being investigated for

advanced applications for use at temperatures as high as 50000 F.

20. DISTRIBUTION/AVAILABILITY OF ABSTRACT 21. ABSTRACT SECURITY CLASSIFICATION

U UNCLASSIFIED/UNLIMITED C0 SAME AS RPT. ODTIC USERS UN!CLASSIFIED?22a. NAME OF RESPONSIBLE INDIV/IDUAL 22b. TELEPHONE (include Area Code) 22c, OFFICE SYMBOL

Mark M. 0peka (202) 394-4019 K22---

DO FORM 1473,84 MAR 83 APR edition may be used until exhausted. SECURITY CLASSIFICATION OF THIS PAGEAll other editions are obsolete. UNCLASS IF I ED

NSWC TR.86-.242

F FOREWORD

.This work was performed -for and funded-by the Surface Launc-hed:WeaponryMaterials Technology (SURFMAT) rogram which has fo'cused on the devel1opmentof materials for use at temperatures as high as 5000 0 F. The calculation of.temperatures at which melting first occurs provides a guide to thelimitation of such matcrials. The current work shows that HfB2-fcomposites begin melting above 3413K (5683F), ZrB2-ZrC above 3090K (5102F),HfC-SiC above 2910K (4778F), ZrC-SiC above 2685K (4.373F), HfB2-SiC above2620K (4256F), and ZrB 2-SiC above 2408K (4004F). These results provide aguide for the development of materials which might be used in advancedhigh-temperature systems.

_________________Approved'by:

Access~ion For

NTIS GR8k&T

JDTIC TA3Utiannounced 0 D. B. COLBY, HeadIjustification Strateqic Systems Department

ByDistribution/Availability CodeS

Dist Special

AII

NSWC TR86-242

PREFACE

~-'Candidate materials are being studied w ich a be sed aýý temperaturesas high as 50000~F. In order to attain this goal a ser .ies ofI refractorycompounds are being co'nsidered which~ can -bi -used as compo ites. These

composites are based on combinations betweent(Cl(1r), e') and(S'i) or C Band Si. In order to investigate where melting can be expected in thecandidate compos ite systems,* coupled phase di agram/thermochemi caldescriptions of the Hf-B, Hf-C, Zr-B and Zr-C binary systems have beendeveloped and combined with previously derived description of the B-C,Zr-Si, Hf-SI, SI-B and. Si-C binary systems in order to calculate thetemperatures at which melting occurs in the composition ranges between.

C- ZrC-.7.rB 2-B4c., C-HfC-HfB 2-B C, HfC-SiC, Zr3 '-SiC a nd HfB2-Sic. <I

I 2

NSWC TR 86-242

CONTENTS

Chapter Page

1IBACKRODUC IND . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 TECHNICALLDES SCRTIOT.I.N.... .... .. .. .. . ... .. .. . I.

PURE COMPONENTS AND BINARY SYSTEMS .. . . .. .. . .. . . . . 2

TIERNARY SYSTEMS. . .. .. . . . . . . . . . .. .. .. .. .. 2

QUATERNARY SYSTEMS .. .. ..... . ............... .. .. .. .. 4

REFERENCES . . . . . .. . . . . . . . . ..... .. .. ... . . . 40

NSWC TR 86-242

ILLUSTRATIONS

Figure Page

1 CALCULATED QUASI-BINARY JOIN BETWEEN Mo. 33 3Si.667 AND

Si0 ,5 C0 . 5 WITH THE ADDITION OF O.O4Zr and 0.048. . . . . . . . . 5

2 CALCULATED B-C PHASE DIAGRAM.................. 6

3 CALCULATED C-Zr PHASE DIAGRAM .............. . . . . . . . 7

4 CALCULATED C-Hf PHASE DIAGRAM................... 8

5. CALCULATED Zr- PHASE DIA . .....................

6 CALCULATED Hf-B PHASE DIAGRAM ........ ................... 10

7 CALCULATED ISOTHERMAL SECTIONS IN THE B-C-Zr SYSTEM ............ 11

8 CALCULATED QUASI-BINARY JOIN BETWEEN Zr82 ,AND ZrC WITH TWO

DIFFERENT TERNARY LIQUID INTERACTION PARAMETERS COMPARED

WITH EXPERIMENTAL RESULTS ....... .................... .. 12

9 CALCULATED AND OBSERVED QUASI-BINARY JOIN BETWEEN ZrB2 AND C , . 13

10 CALCULATED AND OBSERVED QUASI-BINARY JOIN BETWEEN ZrB2 AND B4C , 14

11 CALCULATED ISOTHERMAL B-C-Zr SECTION AT 3273K .......... 15

12 CALCULATED ISOTHERMAL B-C-Zr SECTION AT 3073K ..... ........... 16

iv

NSWC TR 86-242

ILLUSTRATIONS (Cont.)

Fioure page

13 CALCULATED ISOTHERMAL B-C-Zr SECTION AT 2873K. . . . . . . . . . . 17

14 CALCULATED ISOTHERMAL B-C-Zr SECTION AT 2673K. . . . . . . . . . . 18

15 CALCULATED ISOTHERMAL B-C-Zr SECTION AT 2573K. . . . . . . . . . . 19

16 CALCULATED ISOTHERMAL SECTIONS IN THE B-C-Hf SYSTEM. . . . . . . . 20

17 COMPARISON OF EXPERIMENTAL HfB2 -HfC QUASI-BINARY JOIN WITH

CALCULATED RESULTS (DASHED CURVE) BASED ON

TRNL a -12552 JOULES/G.AT. . . . . . . . . . . . . . . .. 21

18 COMPARISON OF EXPERIMIENTAL HfB2-C QUASI-BINARY JOIN WITH

CALCULATED RESULTS (DASHED CURVES) BASED ONTRNL -12552 JOULES/G.AT. ... ......... . . . . 22

19 COMPARISOV OF EXPERIMENTAL HfB2 -B4 C QUASI-BINARY JOIN WITH

CALCULATED RESULTS (DASHED CURVES) BASED ON

TRNL a -12552 JOULES/G.AT. . . . . . . . . . . . . . . . . . . . 23

20 CALCULATED B-C-Hf SECTION AT 3473K ....... ............... 24

21 CALCULATED B-C-Hf SECTION AT 3373K ...... ................ .. 25

22 CALCULATED B-C-Hf SECTION AT 3073K ...... .................. . 26

23 CALCULATED B-C-Hf SECTION AT 2673K ..... .................. 27

24 CALCULATED B-C-Hf SECTION AT 2573K . . ......... .......... .. 28

25 CALCULATED QUASI-BINARY JOIN Si. 5 C. 5 - Zr. 55 C.45 . . . . . . . . . 29

V

NSWC TR 86-242

ILLUSTRATIONS (Cont.)

Figure pages

26 CALCULATED QUASI-BINARY JOIN Si 5C 5 - Hf. 5 3 C4 7 ... ..... 30

27 CALCULATED QUASI-BINARY JOIN Si.sC.s - Zr, 3 3 3 B.6 6 7 . . . . 31

28 CALCULATED QUASI-BINARY JOIN Si 5Cs - Hf, 3 3 3 B 6 6 7 . . . . . . . . 32

NSWC TR 86-242

TABLES

Table

1 LATTICE STABILITY VALUES FOR THE ELEMENTS. . . . . . . ...... 33

2 ANALYTICAL DESCRIPTION OF THE CARBON-BOiuN SYSTEM. . . . . 34

3 ANALYTICAL DESCRIPTION OF THE ZIRCONIUM-CARBON SYSTEM . ...... 35

4 ANALYTICAL DESCRIPTION OF ThE HAFNIUM-CARBON SYSTEM ........... 36

6 ANALYTICAL DESCRIPTION OF THE ZIRCONIUM-BORON SYSTEM.........• 37

6 ANALYTICAL DESCRIPTION OF THE HAFNIUM-BORON SYSTEM ............. 38

7 DESCRIPTION OF rHE PARTIAL GIBBS ENERGY OF EACH COMPONENT IN A

FIVE COMPONENT SOLUTION ON THE BASIS OF BINARY (i.e., FIIJJ)

AND TERNARY (i.e., FIIJJLL) TEMPERATURE AND COMPOSITION

DEPENDENT INTERACTION PARAMETERS ACCORDING TO THE KOHLER"MODEL......... ..... ..... ..... ..... ............... . .39

=?• vii

NSWC TR 86-242

CHAPTER 1

INTRODUCTION

Candidate materials for advanced, high-temperature applications are

being studied that are based on combinations of C, B and Si with Zr or Hf

for use at temperatures as aigh as 5000OF. In order to further these

studies coupled themochemical calculations of phase diagrams1-5 have been

applied to calculate the temperature at which melting first occurs in such

Sys- "is.

BACKGROUND

In order to determine the conditions where melting can occur in a

multicomponent system such as the five compoent Zr-Mo-Si-8-C example shown

in Figure 1, coupled phase diagrams/thermochemical descriptions of the

Hf-B, Hf-C, Zr-B, and Zr-C binary systems have been developed and combined

with previously derived description of the B-C, Zr-Si, Hf-Si, Si-B, and Si-Cbinary systems. These descriptions were applied to calculate the

temperatures at which melting occurs in the composition ranges betweenC-Z.-C-ZrB2-84 C, C-HfC-HfB -B4 C, HfC-SiC, ZrB2-SiC, and HfB2-SiC.

Identification of tdese melting temperatures detine the highest

temperatures at which such compositions would be effective.

SUMMARY

The current work shows the ZrB2 -ZrC composites begin melting above

3090K (5102F), HfB2-HfC above 3413K (5683F), ZrC-SiC above 2685K (4373F),

HfC-SiC above 2910K (4778F), ZrB2-SiC above 2480K (4004F), and HfB2-SiC

above 2620K (4256F). These results provide a guide for the development of

advanced high-temperature materials.

NSWC TR 86-242

CHAPTER 2

TECPNICAL DESCRIPTION

PURE COMPONENTS AND BINARY SYSTEMS

Table 1 shows the current values of the lattice stability of B, C, Zrand Hf. 1 "5 These values were used to define the Gibbs energies of thesolution and compound phases of interest. Table 2 and Figure 2 show the

description of the B-C system3 while Tables 3 through 6 and Figures 3through 6 show the thenmochemical description and phase dicgrams calc~latedfor the Zr-C, Hf-C, Zr-B, and Htf-B derived here. Relevant data on Zr-Si,

Hf-Si, $t-3, and Si-C were taken from earlier studies. 3" 5

It would be noted that the thermochemical description of che liquid andsolid phases contained in Tables 1 through 6 can be employed to'compute thebinary and ternary phase diagravis as well as the various thermochemical

properties of all components in these systems. The thermochemicalproper'*ies include: activity and activity coefficients, heats of fusion

and mixing, etc.

TERNARY SYSTEMS

The Gibbs energy of ternary liquid was modeled by employing Kohler'sequation shown at the bottom of Tible 4 for the B-C-Hf system. All of the

binary parameters, i.e., LBBCC, LCCBB, LBBHF, LHFBB, LCCHF. and LHFCC aredefined form Tables 2 to 6 and the previous work. As a first approximationthe ternary interaction parameter TRNL can be set equal to zero. In the

B-C-Zr case illustrated by Figures 7 to 10, this procedure was followed asa first approximation. Figure 8 shows the result obtained in the

calculation of the ZrB2-ZrC eutectic temperature which was calculated at

3250K (5408 0 F) as compared wi'th the experime .tal value of 3090K (51020F)

2

L--__

MSWC TR 86-242

reported by Rudy. 6 By means of iterative adjustm'.its it was fc',nd a value ofTRNL a -225520 Joules/g.at. was necessary to reduce the eutectic temperatureto 3090K (51024F) in agreement with the experimental results. Figures 8 through

15 show the prtsent B-C-Zr calculation while Figures 16 through 24 show the

B-C-Hf calculations.

In the latter case a much smaller ternary liquid interaction parametcr,

TRNL a -12552, was found to provide an accurate reproduction of theHfB2 -HfC eutectic at 3413K (5683*F) as shown in Figure 17. Figure 8 shows

the Zr82 -C join where the calculated eutectic is 2700K (4400OF) and the

result proposed by Rudy 6 is 2663K (43334F). In Figure 10 the calculatedeutectic on the ZrB2-B 4 C Join is 2493K (40270F). Figures 11 through 15 show

the isothermal sections computed at 3273K (54310F), 3073K (50716F),

2873K (47110F), 2673K (43514F), and 2573K (41710F) with TRNL a -125520 and those

proposed by Rudy. 6 The general level of agreement is seen to be quite good.

Figure 16 presents the isothermal calculations to be performed in the

B-C-Hf system with reference to the component binary systems. As indicated

above, a value of TRNL much nearer to zero, i.e., -12520 J/g.at. is required

(to provide agreement with Rudy's proposal 6 ) than in the B-C-Zr case. Thisis illustrated in Figures 17 through 19 where the calculated and observed

HfB2 -HFC, HfB2-C, and HfB2 -B4C are displayed at 3413K (5683*F), 2823K (4621*F)calculated and 2788K k45580F) experimental and 2603K (4225 0 F), respectively.

Thus with TRNL = -12552 for B-C-Hf good agreement is attained between

experimental and calculated eutectic temperatures. Similarly, good agreementis displayed in Figures 20 through 24 at 3473K (5791°F), 3373K (5611*F),

3073K (5071 0 F), 2673K (43510F), and 2573K (41710F).

Consequently, the forgoing tests of the model parameters in the calculations

of the B-C-Zr and B-C-Hf ternary systems in the range of temperature and

compositions of interest provide, a good measure of confidence in thepredictive capability of the computational system and permit consideration

of higher order systems.

3

NSWC TR 86-242

QUATERNARY SYSTEMS

The extension to higher order systems was performed by expanding theKohler Model (Table 4) to multicomponent eystems. Table 7 shows thedescription of the partial Gibbs energies for a five component system.Calculation of the SiC-:rC, SiC-HfC, SiC-ZrB2 , and SiC-HfB2 joins displayedin Figures 25 through 28 was performed by equilibrating the partial Gibbsenergies of the individual components in the liquid and solid phases. Theresults show a eutectic in SiC-ZrC at 2685K (4373 0 F), in SiC-HfC at 2910K (4778 0 F),in SiC-ZrB2 at 2480K (4004 0 F), and in SiC-HfB2 at 2E20K (4256 0 F). Theseresults suggest that the SiC-HfC composi';e could provide the highesttemperature capability before encountering degradation due to melting at2910K (4778 0 F).

4

NsWC TR 86-242

H, Mo.333S' 667 (Dashed Curves when no Zr or B Is present) SI .C . H.

I A -1 10..5.

T (K)3130300 ,, "30673000 • , ....... .

L (Liquid)

28C0 -

2600

2400 -2336 , 0K TE . - -

- ----- a J- 320K E--

227912200 2270K -

2000M + H

1800

A I I I

M, o.3 0 6 . 6 14 .. 4 6 C. 4 6 '

FIGURE 1. CALCULATED QUASI-BINARY JOIN BETWEEN Mo.3 3 3 Si.66 7 AND Sio.5Co.g WITH THEADDITION OF .04Zr AND .04B (FULL CURVES) (DASHED CURVES REPRESENT NO Zr OR 81

NSWC TN 86-242

37S0

25000

2SS

FIGURE 2. CALCULATED B-C PHASE DIAGRAM

6

NSWC TR 86-242

ToK

L (Liquid)

3750 3718

3190

s ,* 2500

G +S 1960SS5+3

•- 1 2 S 0

1140

S+-E

C Zr

FIGURE 3. CALCULATED C-Zr PHASE DIAGRAM

7

NSWC TO 86-242

L '4200

3750

3460 S+L

2500 2690

G+SS+E

I ,!_ _ __,,_ _ __,_ _ _ _ _ _ _ _ _

C Hfl

FIGURE 4. CALCULATED C-Hf PHASE DIAGRAM

I

NSWC TR 86-242

L (lZquid)

3730

"2500 "

S1950 2025

1250

1140R-- +D D,+ R

Zz N

FIGURE 5. CALCULATED Zr-S PHASE DIAGRAM

i _ _ _.9

NSWC TR 36242

3000

2000 2080

10

NSWC TH W6242

14L

(Glen 1t

+11+

fmft 1• 0-24a ,

al to")n most W04! q specimePI etp•ll J

3 a Itaftma l m ,ef ,(?jag 3Tests) 3720

TRNL*O

3 .30 0

LqO 06 TRNL*12SS20 J/g.at.'

3300

3200 3260(.28)

A A

" I, 3090(.33)

DBaZr 3386 S=Zr

FIGURE 8. CALCULATED QUASI-BINARY JOIN BETWEEN ZB 2 AND ZrC WITHTWO DIFFERENT TERNARY UQUID INTERACTION PARAMETERSCOMPARED WITH EXPERIMENTAL RESULTS

12 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

NSWC :R 86-442

i Incipient amellign noted •530K 0 Specimen Isflepled

3473 * Isothermol melting (Tin:.ýTs.).M bl SDTA% .0

\ /3273 0 \/ L-C

0 L*/

3073 \ /4L-ZrB2

2873 0\ /O • I

4 in 0A 2700K'2673

2663KP.% 2%

2473 ZrB;-C

3, 20 40 60 so bOcZrBl MOOLE % CARBON -- & C

FIGURE 9. CALCULATED AND OCSEPVED QUASI-BINARY JOIN BETWEEN ZrB2 AND C (THECALCULATED BOUNDARIES ArE SHOWN BY THE DASH-DOTTED CURVES AND LINESWITH TRNL - -125,520 JOULES/g.at)

13

MWC mR U-242

T0K

3473 3S29A bepf mentani

0 Specimen collapsedm By DTA

3273

3073 L

28730 2730

2673 L. ZrB -

I• ... /. 42473 249 * S4

ZrBt*S14C 2443.0

0 20 40 60 o0 IOOZers -MOLE % 94 C -. 4c

FIGURE 10. CALCULATED AND OBSERVED QUASI-BINARY JOIN BETWEEN ZrBi AND 4C (THECALCULATED BOUNDARIES ARE SHOWN BY DASH-DOTTED CURVES AND LINES WITHTRNL - -125.&20 JOULES/g.at)

__ 14

me=C Th U-24a

'0.0

'7I

isi

... ~W ...... .4

+

16__ _ _ _ _ _ _ _ _ _

?amw TN Wa"4

17

NSWC TR 80-242

+ +)

us

fnL

U.

.4 13

NSWC TR 86-242

NN

.... ... ... .... --

ca% +c

cl mvi tI,+

I:z1

NSWC TR 86-242

40+064 os

40oo

FIGR E 6oACLTDIOhRA E~OSI H -- fSSE

j ____ 0 __44

NSWC TR 86-242

A. £ incipient Melting

o Specimen Collapsed 4200* Isothermal Melting (Tinca TcoIL)4Single. Phase X-ray* Metallography . .....

40"73 1 Two Phase

3873calculated

L L + HfC3675

0

3473 0 %"

27.4

HfB 2 + HfC3073 m -

0 20 40 60 80 100HfB - Male Percent HfC -- HfCo 9

FIGURE 17. COMPARISON OF EXPERIMENTAL6 HfB2-HfC QUASI-BINARY JOIN WITH CALCULATEDRESULTS (DASHED CURVE) BASED ON TRNL , -12.552 JOULES/g.at

21

NSWC TR 88-242

T(K) '3675 A Inolplent melting observed

0 Specimen collapsedS3473 •0 Isothermoa melting.(TeT,.)

" calculated SulatA

L ",>.. alculated3273 L"

•%/ 0.

3073 LH°

0 / L'C calculated

2873 A 0 1 p 2823\ _.ý - . . ...A

2673. - B 382 27883%

Hf 82eC

0 20 40 60 so 100Hf B2 - MOLE % CARBON C

FIGURE 18. COMPARISON OF EXPERIMENTAL 6 HfB2-C QUASI-BINARY JOIN WITH CALCULATEDRESULTS (DASHED CURVES) BASED ON TRNL " -12,552 JOULES/g.at

22

NSWC TR 86-242

T(K)

367 A Incipient melting observed3673 3675 0 Specimen collapsed

NSBy OTA

34/3Calculated

3273

L3073 L.HfBa

02873

2673 23A

2473 <2% 2603 <I%78-4%

Hef2B+4 C

.0. 20 40 60 80 100HfS- MOLE % 84 C 84C

FIGURE 19. COMPARISON OF EXPERIMENTAL HfB 2 -8C QUASI-BINARY JOIN WITH CALCULiTEDRESULTS (DASHED CURVES) BASED ON TRNL - -12,552 JOULESIg.at

II 23

NOWC TN 86242

44

L __ ~24_ _ _

NSWC TR 86242

U IA4c I

oom A, Ig tj

~ __ ___ __ 5 __ ___ ___ ___ ____ ___ _ _ ____ ___ ___ ___

NWC TR W6242

0+

in

L + +

26 ____ _ _

NSWC iR W6242.

+U

d'e-.

IuIx

I. __ ____27 _

NM TR W342

viIAda+

+ +tj soqr ca

am CL N+

"i

+ CL

ccgm

CIQ

+

++ x

LP

L +

28

NOV TR -242

iiii I I - lll I I I

37W0 37Z0

35W0 L

3300

31303100 ""

2900

L+H L+S

2700 ,.85

144S

H+S

I I I I a _ _I

Si5 C . H S Zr C• 5 .5 S.S .4s

FIGURE 25. CALCULATED QUASI-BINARY JOIN SI.sC 5-Zr~* 6C.4s

29

NSWC 1th e-24,1

ll(K) i

4200

4000.L

3800

3600-

3400-

L4 S

3200-

3130

3000 -L +H

2910

2800-H ,s

3 C5 H S3 .f3 4 7

IGROM 26. CALCULATED GUAM&INR JOIN 81.5G s-.Hf3CA7

- --- -30

1(K) ..

3600

3530..

3400

- ~L =

3200 "

3130

3000 INI

2800

2600 1K10

42480

H +DOB

StSC5 D8 .Zr 33 38. 667

FIGURE 27. CALCULATED QUA&SI-NARY JOIN 81.CsC-Zr.aB.g7

31

-NWC Th 86-242

T(K)[ I

3e00

3600

3400

3200

3000

2800 - L +H L +0D8

2600 2620

H + 08

2400

S 1 . 5 c H 08 Hf f 333 B.667

FIGURE 28. CALCULATED QUASI-BINARY JOIN Sl 5 ,5 Hf 6 7

32

NSWC TR 86-242

TABLE 1. LATTICE STABILITY VALUES FOR THE ELEMENTS(Units of J/mol and J/m3 l K)

(L-1 Liquid# R a Rhombohedral, foe - tace centered cubicbec v body centered cubic, hcp a hexagonal alone packed,D - Diamond cubic, 0 - Graphite, Y a "B4C" Structure)

Element,

B °OL - *OR - 50208 - 21.84T

S- °*fc - 6694 - 9.623TOL- *Gbc - 8.368T

DOL " °0hop * - 12.134T

OL OD 30.OOT

OGL _ 0 - 27.20T

OGL - oaY 44560 - 20.836T

C *GL "GY - 61923 - 53.974T

L - OGG -114223 - 27.196T

L " 0bco *" 32635 - 12-552T

00bo. I OGhcp 32635

O0 hcp " *Gfec * - 24267

°oL " °GR - 21.84T

Zr °oL OG - 27.20T

L- °Gbcc - 17782 - 8.368TOGL - °Ohcp - 22092 - 12.134T

oG C - 18744 - 12.134T

-GL 0 *OG - 25.10T

-OL _ OGR - 21.84T

Hf *QGL - O * - 27.20T

•°GL _°obcc , 20878 - 8.368T

GL _- °GhcP - 28535 - 12.134T

°GL _-°Gf0 c * 25188 - 12.134T

O -L _ OGY a - 25.10T°OL _ *OR a - 21.84T

33

_ __ _ _

NSWC TR 86-242

Jr0 m

"L64 Q a"

F-

E- to 3 go

'44 x0 10 14

caaa 0

-I

40 41 ' 4 4'

00L

ogccC

10 17* b. W4

* 34

NSWC. TR 86-242]

*~ 01 0 01

t 40. V S ' 0 h

OL O~ e~cc

10

544v I .

o- ... N

04 a% 0% a%m 0 - C C;'4'

M Q3 Q 0 0 L

N V

t. N ,%m ONU*A 61%3 4 @mo 1. .

~ *.N N@ 2 N N N N

N 0% % 04~ S. w4* N 00 0 1#3 ~ ~ w tj.NN US

@2 N 3 #3 35 0

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

NSWC TR 86-242

0 L

A' 16a Ca b0 ac clo 1O6!~

10o* 4) 14 0O

caaF" 03

Z L

~.. bitto 0P0

X=0

+4 *-A

aa

CD

+ be

421 C;

Z Sfa

36 ,K

NSWC TR 86-242

, a 0

A "a M

@6 106 ow 106

0 'a a a '

a*a 0 a.ao

IAS

S 99

020N a

Em is

- - -

0 37

NSWC TR 86-242

* .1141 . ~ ~ - 0.3 *3t 0~ (cm'

V al dS ~t: CD.3.a~Q VS N SAs" ooa

0

S1 M

= 0

41P'

a m

arWI 0 N4

=4 +4 +44004

9 J= 16a~- %-AN 4CIDg ' incoi

'4 N0

CL IN ~ 6I.A _ _Ua6 A

N3

NSWC TR 86-242

TABLE 7. DESCRIPTION OF THE PARTIAL GIBBS ENERGY OF EACHCOMPONENT IN A FIVE COMPONENT SOLUTION ON THE BASISOF BINARY (i.e., FIIJJ) AND TERNARY (i.e., FIIJJLL)TEMPERATURE AND COMPOSITION DEPENDENT INTERACTIONPARAMETERS ACCORDING TO THE KOHLER MODEL(SEE TABLE 4).

0 + RTtnXi

1 •+ _xi xj x i~ + 1-xi F~i

j=l,5

+ x+x xJJI

- j--1,5j,'i X.7 F% F Ix2

. =,FJJLL L)]i + FLLJJL +X 3

j ,Z=1 i

-sj'&Z

S+ y (1 -l 2Xi) FIIJJLL

j 0

39

NSWC TR 86-242

REFERENCES

1. Kaufman, L. and Bernstein, H., Computer Calculation of Phase Diagrams, IAcademic Press, New York, NY, 1970.

2. Kaufman, L., Hayes, F., and Birnie, D., "Calculation of Quasibinary and

Quasiternary Oxynitride Systems - IV," CALPHAD, Vol. 5, 1981, 163.

3. Kaufman, L., Uhrenium, B., Birnie, D., and Taylor, K., "Coupled Pair

Potential, Thermochemical and Phase Diagram Data for Transition MetalBinary Systems - VII," CALPHAD, Vol. 8, 1984, 25.

4. Kaufman, L. ahd Nesor, H.; "Phase Stability and Equilibria as A-'fected bythe Physical Properties and Electronic Structure of Titanium Alloys,"

Titanium Science and Technoloay_, Jaffie, R. I. and Burte, H., Eds., Vol. 2,

1973, 773.

S. Kaufman, L. and Nesor H., "Coupled Phase Diagrams and Thermochemical Data

for Transition Metal Binary Systems - IV," CALPHAD, Vol. 2, 1978, 295.

6. Rudy, E., Compendium of Phase Diagram Data, AFML-TR-65-2, Part V, AFML,

Metals and Ceramics Division, Wright-Patterson AFB, OH, 1969.

40

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