NSWC TR 86-242 OhCFILE coJP Y CALCULATION OF MULTICOMPONENT REFRACTORY Q)COMPOSITE PHASE DIAGRAMS 0) ,%N iN BY 1. KAUFMAN (MAN LABS, INC.) * ~ FOR NAVAL SURFACE WZAPONS CENTER STRATEGIC SYSTEMS DEPARTMENT ~h~ 1 JUNE 1986 Approved for public release; distribution is unlimited. I -•, ~~~~ S• ELECTEEHAEDIGR ._• ~~~~ ~ ~ A 1• 71988UMA MNLB, N. "NAVAL SURFACE WEAPONS CENTER SDahigren, Virginia 22448-5000 0 Silver Spring, Maryland 20903-5000 18 3 10 009
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CALCULATION OF MULTICOMPONENT REFRACTORY Q ...HfB2-HfC eutectic at 3413K (5683*F) as shown in Figure 17. Figure 8 shows Figure 8 shows the Zr8 2 -C join where the calculated eutectic
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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.
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.
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
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)
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)
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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