MARTIN W4RlEITAENCR(iY S Y S T f M S 1IbPAPlES

3 4 4 5 b 0351333 9

Metals and C~ramics Division

P. F. Tortorelli and P, S . Bishop

Date Piiblished - January 1991

NOTICE: This document contains inforimation of a preliminary nature. It is subject to revision or correction and therefore does not represent a final report.

Prepared for the Deputy Assistant Secretary for Conservation and Renewable Energy ED 02 13 (x, 0

Prepared by the OAK R I M E NKI'IONAI, I .ABOKATBRY Oak Ridge, Tennessee 37831-6285 managed by MARI'IN E/IARW,:S"X'AENERGY SYSTEMS, INC. for the E W OF ENERGY under contract DE-ACOS-84OR21400

3 4456 0 3 5 3 3 3 3 9

LIST OF TABLES .................................................................................. LIST OF 'I;XCJURES.................................................................................

vii 1

ARSTMACX ..........................................................................................
1 -

INTRODUCTTION ................................................................................... EXPEKIMENIAL PROCEDUR-ES .............................................................. RESULTS ............................................................................................ WEIGHT CHANGES ....................................................................... MICROSIFRUCI'UlZAI. ANALYSES ..................................................... SALT ANALYSES ........................................................................... DISCUSSION ....................................................................................... SUMMARY .......................................................................................... REFERENCES ......................................................................................

4 4 10 13
13 23 24

1 2

1I1

...

LIST OF FIGURES
Fig. 1
Fig" 2
~~~~~a~~ drawing of spxge nmlaltcn nitriare salt cn1cihlc

s ..............................~..........~....................l. .........~........ ~ ~ . . ~ .
"

Ave~igbs: weight change Cr different C O I I I ~ ~ S ~ ~ ~ofIFeo O IS 35.8 at. % AI exposed to ~ a ~ ( A t IB)~ ~ ~ roximately 24 h ................................. ............... ....... Average weight loss as a function or alumninunn c ~ ~ or i o n aluminides exylosed at 650C fer 20-30 h: (a>NaN03MN03-Na202 (salt 1B) and (h)WaNO3-Na2 2 (salt zn) .. c e ~

~ 5 ~ 8

~ ~

Fig. 3
Fig. 4

. . . . . . . . I . . . .

...... .....

Average 24-h weight loss for iron aluminides exposed to N,?N03-K.NO3-Na2* at 65 "@ as a fiinction of chromium and aluminum concentrations (in at. 5%) " . I . . ................... ..................... . Weight loss versus exposure time for Fe-35 at. % A1 exposed t~ NaNO3-KN03-Na2@ at 650C ............... .....................................

Fig. 5

Fig. 6

Cumulative weight loss versiis time for Fe-35 at. % A1 exposed to N ~ N ~ ~ 661 and 684C. Peroxide at ~ ~ ~ ~ ~ a ~ ~ was refreshed during each exposure segment. ....................................... 11 Polished cross sections of iron aluminides exposed a t 650C: (a) FA-325, NaNO3-NqO2 (salt lB), weight loss of 4 4 g/rn2; . (b)F,4-328, ~ a ~ ~ ~ (salt - W), weight loss ~ 1 ~ ~ of ~ ~ 5.9 8/n12; (c) FA-325, ~ ~ ~ ~ (salt 2B), weight N o ~ ~ ~ ~ 3 loss ~ f 5.1 g/rm2; and ( )FA-328, NaNOyNa~02 2 8 ) , weight d (salt loss of0.7 " ........................................................................ Polished cross section of Fe-35 at. CTn AI exposed to NaN03-KN03Na2@ (salt 13) for 24 11 at 650C. Energy dispersive X-ray analysis indicated presence of a sodium-contiaining product at A ..............................................................................

Fig. 7

~
2

~
12

ig. 8

14
15

Fig. 9

Polished cross sections of unexposed iron aluminides (starting sunface roughness): (a)FA-325 and (h)FA-328 *,. ..................... ............

Fig. 10 Polished cross sections of FA-325 exposed at 650C to NaN03K N O ~ - N (salt O ~ (a>weight loss of 40.0s/m2 and ~ ~ IB): ( h ) weight loss of 4.4 s/m2 .......................................................... Fig. 11

_ " . 16

Polished cross sections of FA-326 exposed at 650C to NaN03N a 2 e (salt 2B): (a> weight loss of 118.7 g/m2 and (h)weight loss of 5.2 g/m2 .........................................................................

17

vii

Some of the uses of molten nitrate salts include removing or providing heat for chemical reactions,] heat treatment bahhs,l and coolant and thcrmd energy storage materials for solar power tower^.^ In addition, the chcmkaf properties of nitrate salt can tW exploited
"Research sponsored by the U.S. Department of Energy Assistant SecreFary for Coaiservation and Renewable Energy, Office of Imdushial Technologies, A~~~~~~~~~ ~~~~~s~~~~~ Concepts Division and tbe Imnproved Energy ~ ~ ~ Division ~ ~ co~it~act v i t ~ ~ ~ under ~ t ~ DE-AC0.5-840112 1400 with Martin a-ictta Energy Systems, he.

2 to produce high-purity oxygen and nitrogen gases at a substantial energy savings compared
to cryogenic production of oxygen.3 Because s f these types of applications mci the

scientific interest in these melts, a number of investigators have conducted electrochenical and corrosion studies with molten sodium and sodium-potassium nitrate salts (see, for example, refs. 4-15). Recently, a study of the corrosiori of a variety of matcrials by a highly oxidi.rjng molten nitrate salt showed that iron alurninidcs had relatively grmd resistance when cornpared to standard nickel- and iron-based alloys. l5 Therefore, as part of an effort to develop Fe-A1 alloys with greater than 30 at. 95 AI, the corrosion behavior of such materials in nilrate salt was investigated. The resulting corrosion data for &-AI alloys as a function of aluminum, chrorniuin, and other minor elements are presented and discussed below. EXPERIMENTAL PROCEDURES A cross-sectional view of the crucible assembly used for the exposures of the specimens to the molten nitrate salt is shown in Fig. 1. Continuous sparging of the melt with dry air was maintained during specimen exposures using gas bubbler tubes. The crucibles and tubes were alumina and were replaced after each melt cycle. A specimen was suspended on the end of a wire (usually 0.5-mm-diam zirconium) in the salt. Above the salt-gas interface, the other end of the wire was attached to a 6.4-mm-diam nickel rod, which was supported by the comp~essiom an O-ring in one of tkc end flange fittings. Specimens were of normally positioned approxiimaacly halfway down into the salt. Details of the experimcntal equipment and procedures are given elsewhere. l5 Two different nitraic salt base compositions were used in the prcsent study. Salt cornposition 1A consisted of 49 mol % NaN03 (44.7% by weight) and 5 1 mol % K N 0 3

(55.3%). Additions of 1 mol % Na202 (0.85%) were made to obtain the IS composition. Salt 2A was 100% NaNO3; 0.4 mol % Naz02 (0.4%) was added to 2 8 to yield 2B. All of
the salt components were reagent grade. They were weighed on a 0-0-to 3 1 1.O-g mechanical balance. 'Lo facilitate additions to the molten salt during operation, NaZ03 was measured into individual containers in an inert atmosphere (to reduce moisture absorption). Single portions were then added to the melt through the crucible vent. 'l'he salt charge in an individual crucible was kept molten between specimen exposures and was only periodically replaced. With one exception (described below), all the iron aluminides used in this study wcre prepared from arcmelted 500-g hcats. Table 1 shows the compositions of the iron aluminides examined in this study. To prepare specimens, material was sheared or cut as

4
close to the nominal diInensions, 5.1 x 2.5 x 19 inm, as possible, In some cases, a 1.hnm-diain hole was drilled at one end of the specimen, Rough edges were removed by gritiding and sandirsg. Selected specimens were lightly etched to remove surface films and then annealed at 850C in air for 1 h. Final preparation involved surfice cleaning using conipahble solvents. All dimensional measurements were made with a dial caliper and all weights were K ~ G - ~ S U E ~ an electronic balance. with Upoil removal from the salt, specimens were visually inspected, and my miusual
obsewations were noted. Specimens were allowed to cod in air and rinsed in hot water. The wire was removed and die spccimen was again rinsed After air drying, the specimen weights and dimensions were recorded. The corroded surfacer, and polished cross sections

of selectcd specimens were analyzed by optical arid scanning electron micrmcopy and energy dispersive X-ray (EDX) analysis. A few corroded and rinscd surfaces were exilrllirjed by X-ray diffraction. Salt extracted from cnacible melts was analyzed for selected elcments by atomic absolption.

RESULTS
WEIGHT CHANGES

Table 2 shows weight change averages aftter 2441exposures for ovcr 20 hears of various iron aluminides used in crucibie experiments wt nitrate salts at 650C:. Yhc nurnkr ih of duplicatc experiments with a particular alloy ranged from 0 to 20, Data from a series of exposares conductexl in one particular salt charge (norminally 1l3) were not included in these averages because weight changes from experiments with this salt mixture were consistently higher than the average of weight losses from all the other batches of salt in the 1B condition. ' h i s is clearly illustrated In Fig. 2, which compares the aveiage weight losses of different iron aluminides exposed to the atypical salt with those from exposures to all other 1B salt charges (denoted 1B). The former salt was significantly more corrosive toward all four iron-aluminide compositions exposed in this environment. Table 3 , a subset of the resirlts shown in Table 2, is a comparison of the average weight chariges of similar compositions (in tcrms of aluminum and chromium) that differed only in the amount of minor alloying elements. Although there are differences in average weight losses, the effects of small amounts of B, Zr, Nb, and C axe indeterminate when standard deviations are considered. Any influencz of these elements on weight change was not sufficiently significant to causc any averages to fall outside the uncertainty limits. Likewise, as shown in Table 4,there was essentially no or little effect of pretreatment

Table 2. Average weight losses for iron aluminides exposed to nitrate salts at 650C for approximately23 h Weight change (g/m2) 1B -85.1 k 97.9 -18.3 k 19.5 -17.3 F 19.7 -31.3 2 19.8 -10.8 F 2.7 -9.8 k 5.5 -29.6 2 41.7

Hear No. (FA-)

104 118 119 300 301 303 307 308 3 10 311 3 12 324 325 326 328

2B

ORNL-DWG 90-11761

350

76B 6040"

353 38 39 61

6060Nb*

-4.3 -t 1.5 -9.0 k 13.6 -2.6 F 0.3 -196 -23,8 2 30.6 -87.4 F 45.9 -19.4f 10.8 -13.3 I 8 , 2 -19.9 F 17.5

-5.6 & 5.6 -3.4 k 0.9 -1.2

-77.3 k 80.2 -24.4 -70.8 F 67.6 -26.6 i 4.3 -45.2 k 59.3 -6.0 k 9.7 -5.3 k 4.3 -2.4 k 2.3 -21.6 F 18.1 -6.3 -t 7.7 -240.1 -33.1 k 22.4
-70.9 k 28.3
FA-324

Lo

F A-325

FA-328

FA-350

*NO; of FA series. part

Fig. 2. Average weight change for different compositions of Fe-35.8 at. 5 AI. exposed to NaN036 K.VOj-Na202 (salt lBa>at 650C for approximately 24 h.

6
Table 3. Comparison of zffects of minor alloying elements on 24-h corl-osion :asses of iron aluminides in NaN6)3-KP\JO3-Na2O2 (salt 1R)
AI concentration (at. %)

Minor alloying element (at. 5%)

Weight change

Wm29

35.8 35.8 35.8 35.8

0 0.06B
0.123 0.035, 0.05Zr

-5.6 -t 5.6 -3.4 -t- 0*9 -0.8 k 0.5 -9.0 k 13.6

-4.4

35.8 + 5Cr 35.8 3 5Cr

40 40

0.03t3, 0.05Zr O.O6B, O.1Zr 0 0.2NbC

+- 4.2

-4.3 -t 1.5 -13.3 31 8.2 -19.9 f 17.6

Table 4. Effects of pseoxidiation in air (I h at 8SO0C> 24-h weight loss on (g~rn2) molten nirrate salt in (salt 1B)

A1 concentraticn
(at. %)

Reoxidized

All conditions
-18.3 rl: 19.5

30A1-20
40A1

40-40 40-8Cr 35.8A1 35A1 4OAl

-27.1 k 28.6 -34.5 i 13.9 -1 1.6 3- 3.5 -11.8 -1 1.4 I 16.4 -22.0 I- 113.2 -12.5 i 8.5

-31.3 k 19.8 -10.8 f 2.7 -7.8 k 5.5 -9.81- 13.6 -19.6 10.8 -13.3 -t- 8.2

7
(oxidation from the 850C annealing treatment in air) on the weight change results. Selccted specimens of Fe-35.8R1 were mechanically polished to a metallographic su5ace finish to check for effects of swface roughtiess or preparation on the weight change measurcme~~ts and none were found. Based on these results, effects of variations in the concentrations of aluminum and chromium on short-term weight change results can be compared without rcgard to the exact specimen preparation or concentration of tninor alloying additions. A series of Fe-AI binary alloys (with only very small, if any, concentrations of minor

alloying elements) were used to examine the effect of alurnilnum concentration on corrosion by the nitrate salts over a range of 26 to 40 at. % Al. The weight losses of the iron aluminides decreased with increasing aluminum concentratiori up to 30 at. 5% A!, but were not sensitive to aluminuin content at higher concentrations. This trend was observed at 650C for both the NaN03-KNOyNa202 [salt 113, Fig 3(a)] and the NaNO3-Na202 [salt 2B, Fig. 3(h)] environments, A binary Fe-35.84 alloy composition (FA-350) was used to determine possible effects on corrosion resistance resirlting from scaling up ironaluminide heats from 500 g to 10 kg. The average 2 4 4 weight loss for material from the 10 kg FA-350 (4.4 rt: 4.2 gIni2) was less than for the 500-g heat (1 1.4 k 16.4 gJni2), but the standard deviations overlap. Thus, no significant effect of scale-up on corrosion in the nitrate salt can be established from the present data, Specific experiments to investigate the influence of chromium on corrosion by the molten salt were also conducted. The results for salt condition In are shown in Fig. 4, which indicates no discernible influence of chromium on 24-h weight changes for exposures to NaNO3-KNO3-Na2@, outside the limits set by the scatter in the measurements (see 'Table 2). A similar conclusion was obtained from consideration of data from experiments in Salt 2 (Table 5); no major trend was apparent and any possible small effect was masked by the relatively large standard deviations in certain cases. The presence of chronGum in the iron aluminides did not seem to affect the dependence of the weight loss on aluminum concentration (see above): the average weight loss for Fe-Al-4Cr was significantly higher for a 28 at- % AI coniposition (FA-1 18, 85.1 @m2) than for one with 40 at. 96 A1 (FA-301, 10.1 g/m2>. A lirnitcd number of experirnents were conducted at longer exposure times and at different temperatures using the Fe-3541 heat (FA-76B). As reported previously,l5 the influence of the peroxide addition on corrosion is relatively short-lived; most of the weight change occiirs within the first 24 h unless the NaNO2 i s periodically refreshed (see Fig. 5). This type of behavior was also observed in more recent experiments, which are descrikd by the results shown in Table 6. For a giver1 composition and salt condition, 48-h weight

I
1

I -

9
Table 5. Irilluence of chromium concentration on 24-h weight loss in nitrate salts
Al concentration (at.%)

Cr concentration Heat No. (at.%) (FA-)

0 0 5 0 2
4 6

Weight change (s/nn2) for 2

35.8 35.8

35.8
36.5 36.5 36.5 36.5

325 326 328

* -2.4 * 2.3

-6.0 9.7 -5.3 4 4.3

-77.3 -t 80.2 -24.4 -70.8 -t- 67.6 -26.6 -t- 4.3

308 3 10
311 3 12

150

100

50

Peroxide Only Added At Start Of Initial Exposure.Period

10 Table 6. Effect of peroxide additions as a function of exposure time for iron aluminides in nitrate salts Heat No. A I concentration Cr concentration Exposure time (at, 9%) (FA-) (at.%) (h) 350 350 350 324 353 353 353 353 104 184 326 326 35.8 35.8 35.8 35.8 35.8 35.8 35.8 35.8 28 28 35.8 35.8 0 0 0 0 0 0 0 0
24 48

Salt Weight change condition (g/m2) 1B 1B 2B 2B

1B 1B 2B 2B 1B 1R

48 24 24 48 24 48
24

-9.0-t 13.6 -3.3 -40.4 -45.2 k 59.3

-2.6 f 0.3 -6.7 -6.3 Tb_ 7.7

-3.8

72

-85.1 1 9 7 . 9 -68.5

24 70

2B 2B

-5.3 -t 4.3 -9.0

changes were thc same as those measured after 24 h. When peroxide is added evcry 24 h, thc increase in weight loss with time is approximately linear. Ihis type of behavior, described originally in a prior report,l5 is shown in Fig. 6, which plots cumulative weight loss (obtained from succcssive exposure of the same specimen) versus exposure time under

salt cordition l B where 1 mol % Na202 was added e the melt at the beginning of each o exposure segment. Note the sensitive dependence of the weight losses and corrosion rates (obtained from slopes of the fitted lines in Fig. 6) on temperature.

MICROSTRUCTURAL ANALYSES
Polished cross sections of selected specimens from alloys 1;A-324, -325, -326, and -328 were examined by optical metallography. Microstructural observations for other FA-76B specimens are described elsewhere.15 Representative microgmphs we shown in Fig. 7, which also includes the weight changes measured for the respective specimens. As can be seen from the figure, no evidence of a conusion product layer was found. I,i kewise, X-ray diffractisn of several specimen surfaces after exposure and cleaning did not dctect anything but the base material. Only isolated areas of a possible sodium-containing product

ORNL-DWG 89-11749R

500

e w

400

s
p

300

200

20

40

60

ao

Cumulative Exposure Time (h)

Fig. 6. Cumulative weight loss versus time for Fe-35 at. % A1 exposed to Na.N03-KN03-Na2@ at 661 and 684C. Peroxide was refreshed during each exposure segment.

12

Y -215487

Y215405

Fig. 7. Polished cross sections of iron aluminides exposed at 650C: (a)FA-325, NaNO3-PPJqO2 (salt 1W>, weight loss of 4.4 g/m2; (b)FA-328, NaN03-KN03-Na202 (salt lB), weight loss of 5.9 d m 2 ; (c) FA-325, NaN03-Na202 (salt 2B>,weight loss of 5.1 g/m3.;and (6) FA-328, NaN03-Na2 2 (salt 2B)7weight loss of 0.7 g / d .

13 layer (area marked A in Fig. 8) were detected by scanning electron microscopy and EDX spectroscopy even when the salt was not removed from the surface (see Fig. 81.15 The surface roughness evident in the micrographs comprising Fig. 7 was not necessarily a result of the corrosion process. Specimens that were not mechanically polished prior to exposure to the salt (most were not) had varying degrees of surface roughness depending on the particular heat of material. Examples of cross sections of starting surfaces of specimens that were lightly etched and annealed are shown in Fig. 9. (Examination of the surfaces of as-received material revealed that such roughness was not due to the surface preparation treatments.) Furthermore, there was no correlation between the measured weight losses and the surface roughness of the specimens exposed to the salt. h fact, comparison of two FA-325 specimens that suffered weight losses of 40.0 and 4.4 g/m2, respectively, show just the opposite trend (Fig. 101, as did FA-326 (Fig. 11). In these instances, the corrosion process seemed to result in smoother surfaces. In both Figs. 10 and 11, the specimen shown in (a) was exposed to the atypical salt described above. SALT ANALYSES Results of salt analyses as obtained by use of atomic absorption spectroscopy are shown in Table 7, which includes data for salts that contained only iron-aluminide specimens. Random samples of salt were taken after exposures of multiple specimens. Salt 3-2 was the one in which the trend of significantly higher weight losses was discovered

l (see above). Note that, for this salt, the concentrations of Fe, Al, and Cr were al higher compared to the other salt samples and that it contained a relatively high amount of silicon.
DISCUSSION
It has already been sh0wnl~9~5 weight change can differentiate the relative that corrosion resistance of materials exposed to this aggressive nitrate salt where significant variances in susceptibilities exist and that the superior behavior of FeAl in this environment can be demonstrated with the use of such measurements. However, the relatively large uncertainty limits typically associated with weight change measurements of specimens exposed to this type of salt (see Table 2 and ref. 15) makes detection of minor effects of understanding of the corrosion process. Other techniques employing electrochemical measurements or thermogravimetry (using thin layers of salt on the specimens) possibly could be quite helpful in this regard. Nevertheless, as discussed below, when the major

14

15

n
W

16

17

18 Table 7. Analysis of salt samples from crucibles (by atomic absorption) Concentration (wt ppm)
I _

Element

2-2cp Al

3-2b 31 4.9 170 130 <9.0

3-3 3.1 <0.2

4-2'
40.0 1.6 ~2.1 54 <4.1

Fe Si

c r
zr

3.1 3.8 <37 <3.7

4.3

<OS
13 <1

Tirst digit = crucible number, second digit = sequence number; cnicibles 2 and 3 contained salt 1. bAtypical salt . %alt 2.

contributions to weight changes are considered and these measurements are combined with thermodynamic information, salt analyses, and microstructural observations, a qualitative process by which FeAl type of alloys corrode at a relatively slow rate in high-temperature NaN03(-KN03)-Na202 can be postulated. As demonstrated previously,5-7corrosion in molten nitrate salts can result both from solid-state oxidation of the base metal components and from solubility-drivendissolution reactions. Therefore, the significance of net weight change measurements must always be carefully considered in the analysis of results. The measured weight change, w, can be expressed as

where ws is the absolute value of the weight loss due to dissolution of metal ions into the salt, wo is the gain due to the presence of oxygen in the specimen or its adhering scale, and Wd and wl are the weight changes caused by removal of any (or all) of the surface reaction product when rinsing the salt from the specimen after exposure (descaling, wd) and/or by mechanical scale detachment at temperature or during cooling (spallation, wl). Weight losses (negative w) indicate corrosive attack, but, by themselves, do not distinguish between that caused by dissolution (weight loss during exposure) or scaling (weight gain followed by loss due to descaling and/or spallation). Significant weight gains are indicative of corrosion

suscepfibility that can tx associated with oxidation and scale formation. However, reladvely small weight changes do not necessarily mean a particular material is resistant to corrosion. If both dissolution <andoxidation are occurring at rates such that oxygen uptake is approxirnately offset by metal ion dissolution, the net weight change would be srnall while the actual overall corrosion rate is substantial. However, in the present case of iron aluminides, there was no evidence for residual corrosion product on, or internal oxidation of, specimens exposed to the nitmte salts (see Figs. 7,8, 10, and 11). Therefore, wo must be very srnall, so that, in many cases,

The finding that wu = 0 dws not mean that the iron alunlinides exhibiting weight losses have
not been oxidized. Since weight losses were normally higher when the salt was periodically refreshed with highly oxidizing Na2@, it probably indicates that any corrosion product that

formed dissolved into the salt and/or became detached during or after exposure. Thennodynamic calculations and microstructural analyses have shown that Fe203, Najt;e@, and NaAl@ should or can be stable in one or more of these nitrate salt m i x t i i r e ~ . ~ ~ ~the~ 3 ~ ~ 5 In ~ absence of peroxide, exposure of iron t o nitrate salt (lA, see above) led to weight gain~,9-129~5 thereby indicating that a corrosion product had formed. (Xn contrast, weight losses were measured upon exposure to salt 1 B . q The observation that weight changes for bulk alumina were negative (but relatively small) after exposures to 1B and 2 indicate that NaAlO:! forms but dissolves (albeit rather slowly) into the salt. (There is some indirect rnicrostructural evidence for this product based on work with Fe-Ni-Gr systems.l5) When the aforementioned results for alumina are compared with relevant data from Table 2, it can be noted that the lowest weight losses of the alloys (that is, those near the minima of the respective scamxtmds) agree with those measured for alumina (see Table 8). This correlation, when considered with the other evidence discussed above, would seem to indicate that a slowly dissolving product layer involving aluminum fornis on iron aluminides exposed to the aggressive nitrate salts and produces lower weight losses compared to iron and other iron-based alloys, The decreasing weight losses with increasing aluminum concentration of iron aluminide (see Fig. 3) indicate that the Fe2O3 is either more soluble or less mechanically compatible than AI203 over the basicity range of these experiments. This is consistent with the findings regarding pure iron and A1203 exposures15 discussed above. By being more corrosion resistant than the iron oxide products, this slowly thickening (small wd, wj) and/or dissolving (small vv,.,-) aluniinum-containing layer thereby imparts a benefkkd effect.

20

Table 8. Comparison of weight changes of iron aluminides and bulk alumina sed to rnulten nitrate salt at 650C for approximately 24 h Weight change (glm2) Salt 18
-

Material

Salt 2B

& 3 Q
A1203C

-2,w -19.6 t- 10.8 -5.6 k 5.6 -9.0 1 13.6

FA-76B FA-324 FA-350

-8.2 -0- 2 . 9 - 1 1.0 -70.9 rt 28.3 -45.2 -t- 59.3 -21.6 -t 18.1

Single crystal. %eludes data for gelcast alumina with 0 and 0.05 wt % MgO. C Fine grained (-2 pm) alumina with 0.1 wt % MgO.

When Na2R was added to h e salt at the beginning of an extended exposare period and not replenished, weight losses did not increase after almut 24 h (Table 6). Such observations illustrate the importance of the peroxid:: in reactions associated with the fornation and loss of, prcs~mably,NaAlO2 and NaFeQflez0.j (for lipon aluminide). This is not m-~expected; solubilities of oxides in the nitrate salt should be highly depeaadent on salt basicity,l3?16and it is reasonable that the arfdiition of N a 2 a shculd significantly increase the the inmeas4 basicity due to the introduction of the peroxide can change the stable species (for example, Fe2O3 to NaFeQ2) and lead to increase dissolution and/or growth of a product that is less mechanically compatible with the base material (causing delamination). The observation that pure NaNQ3 is more corrosive than the mixed (Na,K)N(93 salt (see Table 2 and ref. 14) is consistent with a reaction process involving the formation of a sodium-containing product. The transitory effect of the peroxide additions (that is, the higher corrosion rate is only maintained if Na2CI-2 is rcfreahcd) indicates that the additions are consumed in the corrosion process and that they directly participate in, rather than simply accelerate, the corrosion reactjon. solubility of these oxides in the basic dissolution regime. 15-16Alternatively, or additionally,

21 The salt analyses shown in Tablc 7 are also consistent with a model of a slowly dissolvirig NaAlO2 layer that is controlling the overall corrosion process. Note that the relative concentration of aluminum ions was about the s m e for the three normal salt chaxges from which samples were taken; but for the atypical, more corrosive salt, iron was in greater abundance. While the reason for the greater corrosivity of this salt is iiraknown (possibly related to contamination from an O-ring), the end result was the inability o an durninumf containing surface layer to hinder the movement of iron into the salt, and comspndingly higher weight losses were measured (Fig. 2), The increased concentrations 01all the principal components of the exposed iron aluminides for the highest weight losses is what is to be expected; but the finding is very significant in that, assuming no change in corrosion mechanism between the typical and atypicd salts, it is indicative of a process(es) in which solid material is lost into the salt (by dissolution or in-salt spallation) mrher than during the specimen removal from the crucible (by spallation) or during the cleaning process after exposlire (descaling). In terms of Ey. (21, it is thus possible to assume wd = 0 and that the principal contribution to wl {if any) is from loss of scale into the salt. There is a relatively high solubility of chromate and dictuoniate in the nitrate salt5 and
materids with significant amounts of chromium perform poorly in these salts at 6250C and

atPo~e.59~5 Therefore, it is interesting that the addition of chromium to iron aluminides had no large effect on their corrosion resistance (see Fig. 4 and Table 5 and, therefore, this 9 element can be used as an alloying addition without a significant negative impact on corrosion. In fact, the average 18 24-h weight loss for a Fe-35.8A1-5Cr heat (FA-328) was among the lowest of those measured and this same composition did exhibit the lowest average weight losses in the 2B salt environment (see Table 5). Additionally, FA-328 also was the most resistant of the Fe-35.8Al alloys in the atypical sda and showed the least sensitivity to changes in salt corrosivity (see Fig. 2) However, it must also be noted that the FA-328 alloy tended to have less initial surface roughness h a n several other iron aluminides (see Fig. 9) and thus should suffer a slightly less weight loss in ternis o mass per unit f surface area. Nevertheless, while the present data cannot be used to determine whether chromium has a definite beneficial effect on corrosion resistance of iron alunhinide exposed to molten nitrate salt, it can be speculated that this elenient may promote the development of a thinner, more uniform aluminum-containing layer that is more effective in prevenling the iron oxide from extensive reaction. This can possibly b accomplished by initial formation of a e chmmia-rich scale (that preferentially fonns with respect to iron oxide) lhat is then dissolved

22 and rcplaced with the slower growing aluminum surface product. Chromium has been observed to reduce the oxidation rate of Ni3Al at 605C!7 and to affect scale moryhology.!* Under salt conditions where there was continued (refieshed) high concentiatihaas of peroxide that somewhat simulate the MOLTOXTM chemical air sep~ation r o ~ e s s , ~ weight p 7*~ losses wcrc linearly dependent on time (Fig. 6 ) ;thus, it is valid (and conservative) to use 24-h weight changr: data to detenniile conosioaa rates. Such rates arc listed in Table 9 for the various iron aluminides. Note that, for this aggressive type of environnnent, the best alloys have very low corrosion rates ( ~ 3 0 0 pirdycx), which are substantially better :hm typical nickcl-based alloys and stainless steel.15 (Rates less than 880 p d y e a r are probably MOUIOXrM process sirnce ehcy art:within the range controllable by acccptahk for economical. process changes.) 'Iherc are scverd implications of this study for development of iron aluminides that arc corrosion resistant in such nitrate salts. Based on a model of a thin, slowly dissolving Table 9. Average corrosion rales based on linear weight loss kinetics
Corrosion rate (PdYear>

Heat No. (FA-)

A1 concentrationa (at. 5%) 35 30

- ........__

1B
120 2ooo 680 500 1800

2R
4300

'I 6B

300 30 1 303 307 308 310 311 312 324 325 326 328 350 353 6040
_ _ _

40
40

38 36.5 36.5 36.5 36.5 35.8 35.8 35.8 35.8 35.8 35.8 40
_ _ I

340 210 70 260 540 160 830

___

4780 1500 4300 1600 2700 360 320 150 1300 380
_ _

usee Table 1 for other comLitucnt5 of alloy, if any.

23
NA1@ that controls the corrosion process at a rate lower than that associated with iron species, minimum corrosion losses would be obtained when the surface coverage by this layer is rnaxin-rized. This possibly could be accomplished by adding Tnme aluminum ur including an element (perhaps chromium) that promotes a faster or more uniform n uclexion and growth of NaAI@ and/or improves the adherence of this layer to the underlying metal. A high-temperature preoxidation treatment in an oxidizing gaseous environment that results in the formation of an adherent A1203 scale on the iron aluminide should aid corrosion resistance under such conditions. However, alumina scales on FejAl tend to spall19 and alloying additions that promote sound, compact, more adherent oxide scales under hightemperature environments should also help in improving the corrosion resistance of iron aluminides in nitrate salt. Although the current results indicate that aluminum concentrations over 30 at. % do not result in greater corrosion resistance, it does appear prudent for an excess of aluminum to be available in case of localized breakdown of the NaAl02. Indeed, it would seem that the relatively large strpndxd deviations associated with the determination of average weight changes may be associated with a tendency for nonuniform attack promoted by incornpletc surface coverage of NaA102. (Some pitting was observed on certain wire used to stisperid the specimens in the salts. This may be 9 cause of the large standard deviations, but there was no strong correlation between the occurrence of pits on a specimen and its net weight loss.) specimens and seemed to be related to galvanic effects due to the presence of the zirconium

SUMMARY
The corrosion of iron-aluminum alloys by molten nitrate salt as a function of aluminum, chromium, and other minor elements was studied as part of an alloy design effort aimed at the development of a strong, ductile, corrosion-resistant FeAl type of aluxninide. Short-term weight change data were used to examine the compositional dependence of corrosion upon exposure of iron duninides to highly oxidizing nitsate salts at 650C
Corrosion resistance was found to increase with increasing aluminum concentxition of the

alloy up to approximately 30 at. % AI. Chromium additions to the alutninide were not detrimental and may actually improve the corrosion behavior for certain aluminum concentrations. No effects of minor allaying additions (C, 3, Ti, and Zr) C W I ~ be determined. The best weight change results were obtained for a Fe-35.8 at, % Pal aluminide

24

containing some chromium. Based on linear weight loss kinetics, the weight change ~ I C ~ S X ~ K ~ Ifor the~most resistant coxnpsitions predict 650C corrosion rates of ~X-I ~

308 pndycar or less, which arc substantially better that1 typical nickel-bdsd aIIoys arrd staiinlcss steels. Whilc weight change rcsults are valuable in assessing relative corrosion ie.esistmc@ of different materials, such data do not directly lead to a niechanistic understanding of the corrosion grsscss(es). Nevertheless, from a consideration of the weight changes; the microsmcturaal, thern-mdynamic, and X-ray diffraction data; and the salt analyses, it appeared that the corrosion of iron aluminides by the: molten nitrate salt proceeded by oxidation aad a slow release of an aluminum-rich product into the salt. ?'his sate is lower than that previously associated with iron and iron-based alloys. Such a corntrolling process would imply that C ~ I - I - O S ~losscs of iron aluminides could lp@ minimized by nmixinzizing the surfaec Q~ coverags of this layer by alloying additions or by a preoxidadon trcatmcnt,

1. W. W. Carling and R. W. M a , Industrid Use of Molren NitrarelNitrite Snits, S A N D 8 1-8820,Sandia National Laboratory report, December I98 1. 2. R. W. Mar and R. W. Carling, " ' h e Application of Molten Salts to Solar Large

Power Systems," pp. 473-84in Proc. Third Int'l. Symp. Molten Salts, eds. G. Marnantov, M. Blander, arid G. P. Smith, Proceedings Volume 81-9, The Electrochmiical Swiety, 1981. 3. 13, W. Dunbobbin and W. R. 13rowr1,Pilot Plant Developmenr o u Ch~rnicak f nit-

Sepezvadon Process, Report for Period ~f October 1, 1984 - September 30, 1986, DOE/CE/40544- 1, February 1987. 4. R. W. Bradd-iaw, Corrosiorm of 304SS by Molten NaN03-KN03 in a Themnl

Conveciion B ~ o pSAND80-8856, Sandia National Labrafory report, December 1980. , 5. W. W. Rradshaw, Oxidation and Chromium Depletion of Alloy 800 and 3 16SS by Molten NaV03-KN83 at Temperatures Above SOOOC',SAND86-9W9, Sandia National Laborarmy report, January 1987. 6. R, W. Bradshaw, "Thermal Convection Lxmp Stidy of the Corrosion of Incoloy 800 ic Molten NaN03-MN03," Corrosion 43, 173-78 (1983). 7. P. F. 'I'oProrelli and J. I-I. DcVan, Th~rmaE Corrvection Loop Siudy of the Corrosion OfFe-Ni-Cr Alloys by Molten Pd&03-,YN03, OFUVL/I'N-8298, Oak Ridgc Naticnal Labratory rcprt, December 1982.

8. A. J. Amfa, J. J. P stB, and W. C. V. Biatti, ' ~ of l[rcm Passivation and ~ ~ ~ Corrosion in Molten. Alkali Nirates," chim. Acta 17,3344(1972). - Diagarns and Passiva Alkali Nitrates," pp. 215-27in Pmc. Diagrtms: Ikrcalized Corrosion, hrceeditags Volume 84-9,171e E ctrochennical Society, 1984. a IO. P. Spieeri et al., "Etude B Corrosion de DifErents Aciers par le MtBange Fondu de Nitrate-Nitrie Alcalim," ter. Sci. Eng. 87,369-78 (2987), 11. A. Baraka, A. I. A ~ e ~ - ~ o hand~ a A. E ~ A. n 7 S V , "@SpSSSiOPn of Mild Steel oraosim J . 11,4446 (1976). in Molteri Sodium Nitrate-Potassium Nitrate Eutectic," ~ ~ Acid ~ , 12. A. A. ElHosary, A. Baraka, and A. I. A ~ - ~ o"'Effect of a ~ and Base osion of Mild Stee in Molten N ~ ~ ~Eutectic," ~ ~ ~ 3 3 Additions OB1 the
J . 11, 143-67 (1 13. G . S. Picard, M.M. Lefebwc, and B. I,, Tr6mi180n9'"I'Renn Corrosion of Iron in NaW03-Na2NQ2 Mixtures," J . EEectrcxhem. Sou.
published. 15. P. F. Tonorelli. P. S. Bishop, and J. R. DiStefano, Selection of CorrosioraNLJIM- 11162, Oak Ridge National Resistant Materialsfor Use in Molten Nitrate Salts,
14. APCI Corrosion Studies I n Support of MOLTOX-'", DOE/CE report, ta be

Labratory report, October 1989. 16. R. A. Rapp, "Chemistry and ~

~of Hot Corrosion of Metals," ~ ~ h ~ ~

s ~

Mater. Sri. Eng. 87, 319-27 (1987). 17. J. A. Horton, J. V, Catkcart, and C. T. Liu, "Effect of ~ TIt' Met. 2 347-65 (1988). Oxid. of Oxidation of Ni3A1 Alloy at
1s.

~ Early Stages ow r

Ni3A1 Exposed to High Temperature Air," Paoc. Cot$. ~ ~ c ~o Oxidation,~ ~M.~ y f ~ s c eds. J. I3ennett and C.W. Lorimer, The Institute of Metals, London, accepted for p ~ b (1990). 19. J. FI. DeVan, "Oxidation Behavior of Fe3Al and Derivativs Allloys,"pp- 107-115 in Qxidution of High-Temperature i ~ ~ t e r ~ ~ T.Grobstein and~ Doychak, TitIS eds. ~ ~ ~ ~ l ~ 9.. ~ , Warrendale, Penn., 1990.

J. tI. DeVan, J. A. DespoPt, and H. E, Bishop, "Morphology of Oxide Scales on

27

Central Research L i k ~ x y k u m e n t Refererice Scction 4-5.. Laboratory Records r)eparmieart I,abratory Records, ORNL RC 6. 7. ORNL Patent Section 8- 10. M&C Rmc3rds Office D. J. Alexander 11. 12-16, P. Angeliiai 17. T. N. Besmnnn 18-22. P. s. Bishop 23, w. D. Bond 24, R. A. Bradley 25. P. T. Cxlson L. G. Christophorou 26. 27. D. p. Craig 28. S, A, David 29. J. R. DiStefano 30. L. L. Horton 31. J, A. Harton, Jr. 32. C R. Hubbard 33. R. R. Judkins 34. M. A. Karnitz 35. J. R. Keiser 35. 0. 1. Kimball ; 36. E. H. Lee

1-2. 3,

37. 38,

42

43.
*

46. 47

44 45.
s

49. 58-54.

48

58. 59.
61. 62" 63. 64
*

5.5. 56. 57.

65.

I. Baker Thayer School of Engineering Dartmouth College IIanover,WI-I 03755

68.

T. J. Devine eonsin Centrifugal E. St. Paul Aye.

66.

M. M. Behravesh Nuclear Piant Corrosion Cuntml Electric Power Research Institute 34 12 Hillview Avenue
Palo Alto, CA 94303
W. R. Brown Air Yroducts and Chemicals, Inc. P.O. Box 538 Allentown, PA 18105

69.

67.

764.

28 71.

N. Fiore 79. Vice Chairman, G&E Board AICD Materids Piogran3 Carpenter Technology Corporation 101 West Bern Street P.O. Box 14662 Reading, PA 19612-466

G. I,. Houze. Jr. Director, Reseaxch and Analytical Latmatories Allegheny Ludlum Corporation lechnical Center Alabama Ct% Pacific Avenue Brackenridge, PA 150 13-1597
li. R. Isaacson Director, Advanced Xechnolcgy Hoescbst-Celanese Advanced Technology Group 1 Main Street 51 John F. Kennedy Parkway Shorthills, New Jersey 07928
D. Kang Air Products and Chemicals, Inc. P.O. Box 538 Allentown, PA 18105

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E. Givens 80. Air Products and Chemicals, In@. F.O. Box 538 Allentown, PA 18105
M. Glicksman Rensselear Polytechnic Institute Department of Materials Enginecnrng 8 1. Materials Research Center - 104 8th Street Troy, New York 12180-3690

73.

74.

M. E. Gunn, Jr. U.S. Department of Energy Forrestal Building, CE-232 1000 Independence Avenue, S W Washington, DC 20585 E. 9. Harbison Air Products and Chemicals, Ice, P.O. Box 538 720 1 Hamilton Boulevard Allentown, PA 18195-1501
A. J. Heckler

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R. N. Katz Worcester Polytechnical Institute Department of Mechanical Engineering 100 Institute RJ Worcester, MA 01609
D. L. Mlarsmom Ha ynes Intemationa1 1020 West Bark Avenue P.O. Box 9813 Kokomo, Indiana 46904-9013 P. W. Lee Research Scientist The Timken Company 1835 Dueber Avenue, SW Canton, OH 44705

75.

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7 6.

Amico, Inc. Manager, New Materials 703 Curtis Street Middletown, OH 45043

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E, E. Hoffman National Materials Programs 85. U.S. Department of Energy Oak Ridge Operations P.O. Box 2008 Oak Ridge, Tennessee 37831-6295
J. @. HOlzwarih 2628 Saturn Drive Lake Orion, Michigan 48035 86.

K. McDonald

h e siden t MeraUamics P.O. Box 1539

Traverse City, MI 49685-1539

78.

D. 1%. Muzyka Special Metals Corporation Middle Settlement Road New Hartford, NY 13413

29
87.

J. c. Murza The Timken Company 1835 Duekr Avenue, S.W. Canton, OK 44706-2798
A. Neupaver

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C. R. Vander Linden Vander Lindes m Assmiaees d 5 Brassie \?Jay Iitileton, Ccalmado 80123

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Anietek Operations Headquarters Specialty Metals Division Route 519 84,PA 1533

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B. 3. Rilth Associate Director of Research Materials Science Component Technology Naval Research Laboratory Code 6 0 0 Building 43, Room 2 12 Washington, DC 20375-5000 R. E. Ricker National Iristitute of Standards and Technology Metallurgy Division Bldg. 223, Room B248 Gaithersburg, MD 20899 E. Samuelsson Speckd Metals Coqxmtion Middle Settlznient Road New Wartford, NE" 13413 F. Sczerzeiiie Special Metals Corporaifion Middle Settlenient Road New IIartford, NY 13413
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98.

E. D. Verink, Jr. h p m i e n t of ~ ~ ~ ~ Science and Ermginecring University of Florida Gainesville, FL 3261 1

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s. M. Wolf U.S. Department of ESriergy Code CE- 12 1000 Independence Ave., S.W. Washington, D43 20585
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Deputy Assistant Mariager for Energy Research and Development kpartment of Energ7 Oak Ridge Operations C)fficc

180.

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