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AVESTA CORROSION MANAGMENT

All rights reserved. Comments and correspondence can be directed to Dr Sten Nordin, Avesta Projects AB, P.O. Box 557,S-651 09 Karlstad, Sweden. Tel. +46 (0)54-10 27 70 Telex 66108 apab s. Telefax +46(0)54-18 82 54.

No 2-1985

Oxidation Kinetics of Heat Resistant Alloys Part I

by Gene R. Rundell, Manager of Technical Services Rolled Alloys, 125 West Sterns Rd., Box 310, Temperance, Mich. 48182, USA Alloys based on the Fe-Cr-Ni system include the austenitic stainless steels and a group of higher chromium and nickel alloys having useful oxidation resistance at temperatures above 900 C (1650 F). These heat resistant alloys include AISI types 309 and 310, RA 330, Hastelloy alloy X, RA 333, and Inconel alloys 600 and 601. All of these materials, in common with the austenitic stainlesses, have face centered cubic structures, undergo no phase change from ambient temperature to the melting point, and are not hardenable by heat treatment. Although types 309 and 310 are used largely because of their oxidation resistance, this property has not been determined by any standardized test. Indeed, a materials engineer would have difficulty finding data obtained by the same test for more than a few alloys. This problem does not exist for the cast heat resistant alloys: the Alloy Casting Institute has developed oxidation data for 14 cast alloys obtained via the same procedure. (These data can be found in Vol 1 of the Eighth Edition of the ASM Metals Handbook.) In an effort to remedy the situation for wrought heat resistant steels, oxidation testing has been conducted at Rolled Alloys for the past three years. This project still in progress - is the subject of this article. Oxidation Kinetics - In the early 1920s Pilling and Bedworth discovered that oxidation of alloy steels increased parabolically with exposure time. The discovery of what is now called "parabolic oxidation" stimulated interest in oxidation kinetics to the extent that books on oxidation contained at least one chapter devoted to the subject. (Examples: see Ref 1 and 2.)

2 Unfortunately, this interest in oxidation kinetics was expressed primarily by fundamental researchers knowledge gained has generally not been used to predict long time oxidation rates of commercial alloys. For example, the data for cast heat resistant alloys are given in mils/yr, and are based largely on weight loss measured at the end of a 100 h exposure. These data do not necessarily agree with those for long time exposure predicted on the basis of our understanding of kinetic behavior. A better approach: extend the exposure period to way beyond 100 h, and determine the amount of oxidation at frequent intervals during the extended exposure time. 2. Contamination of cups from furnace refractories or the metal tray. (An alloy for the tray was selected that develops virtually no spall on cooling to room temperature.) 3. Reaction of the specimen or its oxide with porcelain, and area of contact of specimen with the cup. (Examination of both specimen and cup suggests that the cup does not contribute to or reduce oxidation rate.) 4. Effect of reduced surface area as the sample oxidizes. (A mathematical treatment has been suggested that would account for the effect of reduced specimen dimensions on apparent weight loss per unit area. This effect, however, is small for most of the alloys tested. Thus, original specimen dimensions are used throughout.) 5. Spalling of oxide in open cups upon heating.

Cyclic Exposure Method Used to Develop Oxidation Data

Static oxidation testing at Rolled Alloys has been done within the guidelines established by ASTM in Standard Recommended Practice G54-77. Tests are performed by exposing samples in still air using an electrically heated box furnace capable of handling eight samples within a zone having no more than an 8 C (14 F) thermal gradient. Test temperature is determined by a thermocouple placed close to the specimens and which is independent of the furnace control couple. Air is not intentionally passed into the furnace. Specimens consist of right circular cylinders which have been surface ground to a true right cylinder and finished on 400 grit silicon carbide paper. After final grinding, they're measured to the nearest 0.0001 in. (2.5 m), cleaned and dried with acetone, and weighed to the nearest 0.1 mg. Specimens have a common diameter of 11.43 mm (0.45 in.) and usually range in length from about 14 to 18 mm (0.55 to 0.71 in.). Samples are placed in porcelain cups and reweighed along with the cup prior to exposure. They're handled by metal tongs between cleaning and exposure. Methodology - Specimens of eight alloys are exposed simultaneously in individual porcelain cups. At the end of 20 h the metal tray holding the cups is withdrawn and cooled in air. Heat resistant alloys begin to spall oxide usually within several minutes after the onset of rapid cooling. To obtain accurate weight increase data, all of the spalled oxide must be retained. For this reason, each cup has a close fitting porcelain cover that's added before cooling and kept on until the cup is returned to the furnace. Specimen and cup are weighed at the end of each 20 h exposure to determine weight gain per unit area. Note that the weight gain includes that derived from both adherent and nonadherent oxide. After the usual exposure time of 500 h, each specimen has been weighed 25 times. These data are used to plot an oxidation curve. Possible sources of error in addition to weighing and measuring, and our comments about them, follow. 1. Weight change of porcelain cups. (Initial work exposing empty cups indicated that cup weight is not affected by exposure to the test temperatures of interest.)

Linear Regression Analysis: Its Role in Data Reduction

At the end of the eight alloys' 500 h exposure, each has been weighed 25 times for a total of 200 data points relating weight gain to exposure time. These data are plotted to determine each alloy's general oxidation characteristics. Plotting is followed by a linear regression analysis using a programmable calculator such as the Tl-59. Analysis of heat resistant alloys oxidized at 980 C (1800 F) through 1150 C (2100 F) indicates that oxidation may be either parabolic or linear. Parabolic data become linear when weight gain is squared. In both cases a linear regression analysis is performed using 25 pairs of data for each alloy and test temperature. Linear regression analysis using the program we selected provides.: 1. Best relationship between the dependent and independent variable - a best fit curve. (Also provided are the slope of this line and its intercept, and the calculated value of weight gain for any particular exposure time.) 2. Statistical quality of the data expressed as the coefficient of determination. (The coefficient should ideally approach unity for good correlation. Values above 0.99 are common using this approach for weight gain data.) Oxidation Rate - Regression analysis is particularly useful for calculating (rather than determining graphically) the oxidation rate constant. The rate constant for linear oxidation is the slope of the line defined by: W/A=kL t+C, where kL is rate constant, t is oxidation exposure time, and W/A is the weight gain per unit area. In most cases oxidation is not linear during the early stages of exposure, thus the intercept may not pass through the origin. This results in small positive values for the constant, C. Oxidation rate constants are fundamentally related to temperature in the Arrhenius equation. Rate constants also provide a way to determine weight gain at any given time, such as 1000 h.

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Assessing the Effect of Oxidation on Metal Loss

Use of weight gain data is a simple and direct way to determine the relationship between oxidation and time. Only one sample for each test temperature is needed. The technique does not, however, indicate the effect of oxidation on metal loss. In corrosion testing it is common to determine weight loss which, when converted to volume loss, indicates surface recession. This quantity is also of great value in selecting alloys for elevated temperature service. Depth of metal loss can often be applied directly in design because oxidation of many heat resistant alloys in air is uniform rather than intergranular. Determining useful weight loss values from oxidation test data is complicated by the fact that a portion of the total oxide is thin and tightly adherent. This adherent oxide has to be removed without changing the weight of the unoxidized portion of the specimen. Cathodic descaling has been used for this purpose by others, and is the method we chose. The sample is immersed in a 40 % solution of sodium carbonate in sodium hydroxide heated to 550 C (1020 F). Direct current is passed through the solution with the specimen as the cathode for a time sufficient to remove all surface oxide (several minutes are needed). Oxide removal by cathodic descaling usually involves successive immersions, each followed by a measurement of weight change. In the first stage - typically three or four 1 min treatments - oxide removal, confirmed by visual inspection, is rapid. Continued exposure beyond this stage results in decreased weight loss. A plot of weight change vs immersion time in both stages (Fig. 1) gives two intersecting straight lines which can be assumed to represent the best value for weight loss from scale removal (ASTM Standard Practice Gl-81).

Derived Data - This procedure appears to give satisfactory weight loss data. The ability to remove adherent surface oxide after extended elevated temperature exposure increases the amount of information available from a single sample. In addition to finding an oxidation rate in terms of surface recession, you also obtain: 1. Total weight gain, reflecting the amount of oxygen reacting with the metal (equal to the final weight in cup minus the starting weight in cup). 2. Total weight loss, reflecting the amount of metal oxidized (original specimen weight minus cathodically descaled weight). 3. Total oxide produced (1 plus 2, weight gain plus loss). 4. Weight of adherent oxide (weight change upon cathodic descaling). 5. Adherency factor, or relative amount of adherent oxide to total oxide (4 divided by 3). 6. Average weight ratio of oxygen ions to metal ions in the oxide(s) (1 divided by 2). Additional weight change measurements are needed to account for both total weight gain and total weight loss of the same oxidation test specimen. One specimen exposed for 25 cycles and cathodically descaled is typically weighed 36 times to the nearest 0.1 mg. Benefits - An advantage of determining weight loss is the ability to account for the reduced dimensions of heat resistant alloys in service. Also, weight gain data do not permit valid comparisons between alloys when their oxides differ. Regarding the latter, consider the case of two Fe-Cr-Ni heat resistant alloys - Ra 330 and Incoloy alloy DS having similar nickel and chromium contents but different silicon contents. Weight gain data indicate that the alloys have similar oxidation resistance. On the other hand, metal loss data favor the Incoloy alloy with its 2.45 % Si. Gain 2 g/cm 0.009 0.0093 Loss mils (m) 0.91 (23) 0.72 (18)

Alloy RA 330 (19Cr-36Ni-1.4Si) Incoloy DS (17Cr-35Ni-2.45Si)

Silicon may be present in the Alloy DS scale, helping to inhibit oxidation. (Data are for oxidation after 330 h at 1150 C (2100 F).) Another illustration of the same point is a comparison between two nickel base heat resistant alloys, one of which contains aluminum. Aluminum (or silicon) is present in the scale and affects the relative weight of oxygen ions to metal ions. Metal loss calculated from the weight loss of descaled samples eliminates this effect and is thus an effective way to express oxidation data. However, metal loss isn't practical to use when a large number of samples are involved - 25 cycles of eight alloys in one 500 h run would involve 200 specimens. On the other hand, weight gain measurements every 20 h are not hard to perform routinely, and do provide useful data relating oxidation to exposure time. Both of these criteria are used in the data that follow.
Fig. 1. Weight change of heat resistant alloy samples during cathodic descaling. Data are for RA 330 oxidized at 1095 C (2000 F), RA 333 oxidized at 980 C (1800 F), and RA 253MA oxidized at 980 C (1800 F). Point of intersection of each pair of lines represents weight of adherent oxide produced during oxidation test.

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Observations on Oxidation Using Weight Gain Data

The alloys included in this phase of the test program are listed in Table I. All but one are face centered cubic and contain chromium, nickel, and iron. Several are modified with strengthening elements or elements that enhance. oxidation resistance. Four of the alloys - RA 253MA, type 309, type 310, and RA 330 - were tested for 20 cycles, each lasting 20 h at 980 C (1800 F). All four exhibit parabolic oxidation (see data for RA 253MA plotted in Fig. 2). Parabolic oxidation rate constants are indicated from the slope of the weight gain squared vs time graph (Fig. 2, bottom). Figure 2 indicates that oxidation testing of one sample results in reproducible data over an extended exposure period. Computer derived values for weight gain vs time are shown in Table II. To express these data in terms of metal loss, actual loss determined at 400 h is multiplied by the ratio of weight gain at 1000 h to that at 400 h. (We've assumed that the scaling mechanism is the same at both 400 and 1000 h.) Metal loss data for 1000 h are given in the far right column of Table II. Six alloys - including the same four exposed at 980 C (1800 F) - were exposed for 25 cycles at 1095 C (2000 F). A set of eight specimens was completed by including a lower chromium heat of 309 and a higher chromium heat of RA 330. Both weight gain and metal loss values are included in the tabulation of oxidation data (Table III). Five hundred hour data for weight gain are the best values derived using linear regression analysis data out to 500 h, and 1000 h weight gain values are computer extrapolations.

Five of the alloys exposed at 1095 C (2000 F) for 500 h were included in a cyclic exposure test at 1150 C (2100 F) for 500 h. Two alloys not previously tested were included to complete a set of eight specimens. Oxidation data are given in Table IV. Most of these materials displayed unstable oxidation curves and no effort has been made to extrapolate data from 500 to 1000 h. The single exception is RA 333 tested to 620 h. This is the only alloy exhibiting parabolic oxidation during cyclic exposure at 1150 C (2100 F).

Fig. 2. At top is a plot of weight gain vs oxidation time for RA 253MA oxidized at 980 C (1800 F). This alloy exhibits parabolic oxidation behavior as demonstrated by the straight line plot of weight gain squared vs time at bottom.

Table I: Compositions of Alloys in Cyclic Oxidation Test Program

Alloy (UNS No.) RA 253MA (S30815) Type 309 (S30900) Type 310 (S31000) RA330 (N08330) RA333 (N06333) Type 446 (S44600) Inconel 6012 (N06601) Incoloy 800 (N08800) Composition, % Cr W 20.7 23.5 22.3 24.5 18.2 19.0 24.9 26.0 (23) 20.8 2.8 1

C 0.09 0.06 0.05 0.07 0.06 0.07 0.06 0.09 0.08

Si 1.5 0.4 0.5 0.8 1.3 1.4 1.0 0.7 0.3

Mn 0.7 1.8 1.7 1.5 1.5 1.7 1.4 1.3 0.9

Ni 10.8 13.1 13.1 19.4 35.0 36.4 45.9 (60) 30.8

Mo 2.7 -

Co 2.9 -

Other 0.05Ce, 0.18N 0.18N 1.3AI -

1. Balance iron. 2. Nominal composition.

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5 Table II: Oxidation at 980 C (1800 F) Alloy (UNS No.) RA 253MA (S30815) Type 309 (S30900) Type 310 (S31000) RA 330 (N08330) Coefficient of 1 Determination 0.994 0.997 0.994 0.984 Weight Gain, g/cm 2 500 h 0.0018 0.0027 0.0023 0.0027
2 2

400h 0.0017 0.0024 0.0021 0.0024

1000 h 0.0026 0.0038 0.0033 0.0037

Metal Loss mils (m)/1000 h 0.31 (7.9) 0.39 (9.9) 0.37 (9.4) 0.44 (11.2)

1. From regression analysis 2 Extrapolated.

Table III: Oxidation at 1095 C (2000 F) Alloy (UNS No.) RA 253MA (S30815) Type 309 (S30900) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333) Inconel 601 (N06601) Weight Gain, g/cm 500 h 1000 h 0.0038 0.0065 0.0077 >0.03 0.0096 0.0098 0.0078 0.0066 0.0053 0.0131 0.0135 0.0179 0.0109 0.0091 0.0073
2

% Ni 10.8 13.1 13.1 19.4 35.0 36.4 45.9 (60)

% Cr 20.7 23.5 22.3 24.5 18.2 19.0 24.9 (23)

Metal Loss mils (m)/1000 h 0.60 (15) 1.50 (38) 1.45 (37) 1.77 (45) 1.09 (28) 1.01 (26) 0.51 (13)

Table IV: Oxidation at 1150 C (2100 F)

Alloy (UNS No.) RA 253MA (S30815) Type 309 (S30900) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333) Type 446 (S44600) Incoloy 800 (N08800)
1

% Ni 10.8 13.1 19.4 35.0 36.4 45.9 30.8

% Cr 20.7 23.5 24.5 18.2 19.0 24.9 26.0 20.8

Weight Gain, g/cm2/500 h 0.0884 0.0596 0.0561 0.0711 0.0573 0.0100 0.0368 0.1384

Metal Loss Mils (m)/500 h 10.5 (267) 7.47 (215) 7.07 (180) 9.14 (232) 7.90 (201) 1.23 (31) 4.60 (117) 18.0 (457)

Deviations from Parabolic Oxidation Behavior Noted

Oxidation data - weight gain for each 20 h exposure indicate that most of the alloys tested deviate from parabolic oxidation behavior under conditions of cyclic exposure at 1150 C (2100 F). The shape of the oxidation curve varies from one alloy to another. Lower nickel alloys including RA 253MA and type 309 display marked instabilities, typically followed by a recovery period and then another instability. Inspection of the spalled oxide reveals that two different oxides are produced. Initial stages of oxidation result in a fine type that tends to dust the walls of the porcelain cup. "Breakaway oxidation" is characterized by heavy flakes of spalled oxide. In periods of recovery, the fine type again predominates. The presence of different oxides has been confirmed by X-ray diffraction studies of five alloys exposed at 1150 C (2100 F). In addition, breakaway oxidation of types 304 and 446 stainless steels has been described in the literature.

1. RA 333 exhibited parabolic oxidation. Data for 1000 h (extrapolated) are: weight gain, 0.014 g/cm2; metal loss, 1.73 mils (44 m).

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6 Examples - In the case of RA 253MA (Fig. 3, top), the periods preceding and following breakaway oxidation have been found to be linear by regression analysis. Type 309 (Fig. 3, bottom) displays an initial parabolic period of 200 h, a period of rapid oxidation that increases less abruptly than that of RA 253MA, and, finally, alternating short periods of rapid oxidation and recovery. Type 446 displays five periods of alternating increasing and decreasing oxidation rate. However, the overall effect is slight, and linear regression analysis of all data sets indicates a close fit to linear oxidation. RA 330 (18Cr-35Ni) exhibits alternating breakaway and recovery in the first 200 h, followed by an extended linear segment. RA 333 exhibits parabolic oxidation out to 620 h. The occurrence and extent of instabilities are probably not reproducible from one specimen to another and prohibit extrapolation of data to exposure times beyond 500 h for cyclic oxidation at 1150 C (2100 F). It is reasonable to assume that unstable oxidation of an alloy after exposure at 1150 C (2100 F) for several hundred hours will be eventually reflected in cyclic tests at 1095 C (2000 F). At this time, cyclic oxidation has not been performed above 1150 C (2100 F), and the ability to extrapolate data beyond 500 h is uncertain. Possibly, oxidation curves for higher temperatures such as 1205 C (2200 F) wilt indicate a breakaway oxidation mode. The cyclic oxidation data presented here have been supplemented with isothermal oxidation data at 980, 1095,1150, and 1205 C (1800, 2000, 2100, and 2200 F). These data will be discussed in Part II of this article. The relationship between weight gain and weight loss will also be addressed in terms of the oxides that develop on Fe-Cr-Ni alloys.

References
1. Oxidation of Metals and Alloys, by 0. Kubaschewski and B.E. Hopkins: 2nd Ed, Butterworth Press 1962. 2. Gas Corrosion of Metals, by S. Mrowec and T. Werber: National Bureau of Standards and National Science Foundation, Washington, D.C., 1978. 3. "Resistance of Iron-Nickel-Chromium Alloys to Corrosion in Air at 1600 to 2200 F," by A. deS. Brasunas, J.T. Gow, and O.E. Harder: Proceedings ASTM, Vol 46, 1946.

Part II
The oxidation resistance of Fe-Cr-Ni alloys as determined by cyclic exposure tests in still air was reported in Part I of this two part article. Summary - Weight gain data are convenient for determining oxidation kinetics during cyclic exposure. Exposing a sample for twenty-five, 20 h cycles provides an oxidation vs time relationship that may be useful for estimating longer time behavior. Extrapolation to times as long as 1000 h, for example, is valid for temperatures in which the oxidation kinetic mode has been established, and does not deviate for the exposure times of interest. Part I also pointed out that parabolic oxidation is generally observed at temperatures of 980 C (1800 F) and 1095 C (2000 F) when samples are tested for 500 h. Here, the oxidation vs time relationship is given by: (W/A) = kp t + C, where kp is the rate constant, t is oxidation exposure time, and W/A is the weight gain per unit area. Deviations from parabolic oxidation are common at 1150 C (2100 F) and are assumed to occur at somewhat lower temperatures for extended exposures. Weight loss, expressed in terms of surface recession, can be put to use in selecting alloys for elevated temperature service. Each oxidized sample is cathodically treated to remove the adherent scale and surface recession is then measured. Cyclic exposure at 1150 C (2100 F) results in marked variation within the composition range of alloys tested. Heat resistant alloys containing up to 20 % Ni exhibit oxidation resistance in direct proportion to the amount of chromium present. A similar dependency on chromium is observed for higher nickel alloys such as RA 330 and RA 333. Data are plotted in Fig. 1. Different heats of a given alloy may exhibit very different oxidation rates depending upon the actual amounts of chromium within the specification range. For example, oxidation rate of AISI type 309 may vary by a factor of four when chromium is increased from 22 to 23+%.
2

Fig. 3. Examples of breakaway oxidation behavior in alloys tested under cyclic conditions at 1150 C (2100 F). Top, RA 253MA; bottom, type 309 stainless steel.

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7
Oxidation, mils (m) per 500 h

Table II: Isothermal Oxidation Data

Alloy (UNS No.) 980 C (1800 F) RA 253MA (S30815) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333) 1095 C (2000 F) RA 253MA (S30815) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333) 1150 C (2100 F) RA 253MA (S30815) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333) 1205 C (2200 F) RA 253MA (S30815) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333) Weight Gain, g/cm2 1000 h 3000 h 0.0018 0.0026 0.0033 0.0037 0.0031 0,0044 0.0057 0.0062 Metal Loss, mils (m) 1000 h 3000 h 0.23 (5.8) 0.37 (9.4)

0.30 (7.6) 0.48 (12.2) 0.40 (10.2) 0.66 (16.8) 0.43 (10.9) 0.71 (18.0)

0.0052 0.0091 0.0125 0.0059

0.0134 0.0153 0.0218 0.0098

0.37 (9.4) 0.88 (22.4) 0.95 (24.1) 1.52 (38.6) 1.00 (25.4) 1.69 (42.9) 0.66 (16.8) 1.09 (27.7)

Fig. 1. Effect of chromium content on oxidation resistance of Fe-CrNi alloys tested under cyclic conditions at 1150 C (2100 F). Alloys on upper line contain no more than 20 % Ni; those along the bottom line have more than 34 % Ni.

0.0130 0.0140 0.0160 0.0101

0.0359 0.0242 0.0275 0.0172

1.17 (29.7) 3.14 (79.8) 1.41 (35.8) 2.34 (59.4) 1.94 (49.3) 3.39 (86.1) 0.96 (24.4) 1.62 (41.1)

Isothermal - In this concluding part of the article, isothermal (noncyclic) oxidation rate data for four alloys containing from 11 to 46 % Ni (see Table I) are reported. Data were developed using the procedures described in Part I. Four samples of each alloy were exposed for times ranging from 100 to 600 h to temperatures of 980, 1095,1150, and 1205 C (1800, 2000, 2100, and 2200 F). Each sample for a given temperature-time combination was heated to the test temperature and cooled after exposure in its porcelain cup. Total weight gain and metal loss data were obtained, and the best relationship between oxidation and time was determined by regression analysis.

0.2179 0.0175 0.0238 0.0126

0.0676 0.0295 0.0407 0.0208

26 (660) 1.77 (45)

82 (2083) 2.85 (72.4)

2.26 (57.4) 3.85 (97.8) 1.3 (33.3) 2.23 (56.6)

Isothermal Oxidation Tests: Data Development/Analysis

Isothermal oxidation rates are not only lower than cyclic oxidation rates, but do not deviate from parabolic behavior at 1150 and 1205 C (2100 and 2200 F). Extrapolated data for oxidation after 1000 and 3000 h at each exposure temperature are given in Table II. Note that surface recession for all four alloys at 980 C

(1800 F) is well below 1 mil (25 m) at 3000 h. At 1095 C (2000 F) recession increases to more than 1 mil (25 m) at 3000 h for all but RA 253MA. Isothermal oxidation at 1150 C (2100 F) results in increases to more than 3 mils (75 m) for 253MA and RA 330. The higher chromium alloys AISI type 310 and RA 333 exhibit the best oxidation resistance with values of 2.3 and 1.5 mils (53 and 38 m) respectively. All of the alloys but 253MA, which contains the least chromium and nickel, retain useful oxidation resistance at 1205 C (2200 F). Alloy 333 has an oxidation rate of 2.2 mils (56 m) in 3000 h at this temperature, for example.

Table I: Compositions of Alloys in Isothermal Oxidation Test Program

Alloy (UNS No.) RA 253MA (S30815) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333)
1. Balance Iron

C 0.09 0.07 0.06 0.06

Si 1.5 0.8 1.3 1.0

Mn 0.7 1.5 1.5 1.4

Ni 10.8 19.4 35.0 45.9

Composition, %1 Cr 20.7 24.5 18.2 24.9

W 2.8

Mo 2.7

Co 2.9

Other 0.05Ce, 0.18N -

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8 The addition of cerium to 253MA improves its oxidation resistance at the lower test temperatures. At 1150 C (2100 F) cerium is less beneficial, and at 1205 C (2200 F) oxidation is probably controlled more by base composition than by the rare earth. Alloy 333 has useful oxidation resistance to at least 1205 C (2200 F). Although superior to other tested alloys at this temperature, 333 exhibits slightly higher oxidation at the lowest temperature, 980 C (1800 F). This behavior for highly oxidation 1 resistant alloys has been previously observed.( ) Plots of the effect of oxidation temperature on metal loss are shown in Fig. 2. Both cyclic and isothermal oxidation data are given. Note that alloys 310 and 330 exhibit unusual behavior: isothermal oxidation (lower plot) does not increase as rapidly with temperature above 1150 C (2100 F) as it does between 980 and 1095 C (1800 and 2000 F). Oxidation for cyclic exposure above 1095 C (2000 F) increases much more rapidly with temperature. Alloy 253MA, on the other hand, is less sensitive to temperature change than any of the alloys between 980 and 1095 C (1800 and 2000 F) but is the most sensitive of the four at temperatures above 1095 C (2000 F). Alloy 333 tested isothermally shows the same effect of temperature throughout the test range. In more theoretical treatments of the effect of temperature on oxidation, it is common to plot the parabolic rate constant vs the reciprocal of absolute temperature. The slope of such a plot is the activation energy, which will be discussed later. The data in Fig. 2 are not meant to be used to determine activation energy, but simply to illustrate change in oxidation rate with temperature. The plots are useful, however, for interpolation - extrapolation of 50 C (90 F) is a reasonable extension beyond the test temperature range. As indicated in Fig. 2, cyclic exposure increases oxidation for all alloys at all test temperatures. The difference is most pronounced at temperatures above 1095 C (2000 F). Of the four alloys, 333 is the most oxidation resistant under cyclic exposure at 1150 C (2100 F). Table III: Oxygen to Metal Weight Ratios
Oxide Cr2O3 Fe2O3 Fe3O4 Ratio 0.462 0.430 0.382 Occurrence Forms a protective oxide on Fe-Cr, Fe-Cr-Ni, and Ni-Cr alloys. May form a series of solid solutions with Cr2O3 on alloys containing sufficient iron. Less protective, forming on Fe-Cr alloys of marginal oxidation resistance. May dissolve some Cr3O4. Forms a thin layer on heat resistant Fe-CrNi alloys containing silicon. Beneficial. Forms a protective oxide on Fe-Cr-Ni and Cr-Ni alloys containing aluminum.

SiO2 Al2O3

1.14 0.89

Cu2O - Copper oxidizes in air at ambient pressure to Cu2O. The atomic weight ratio of oxygen to copper is 16.00/2(63.54), or 0.1259. Six samples of electrolytic tough pitch copper (99.9 % Cu) were prepared for oxidation testing as described in Part I and exposed at temperatures of 900 C (1652 F) or 1000 C (1832 F) for various times ranging from 20 to 120 min. The ratios obtained from these tests are close to the "ideal": 0.1271, 0.1276, 0.1259, 0.1277, 0.1261, and 0.1274. NiO - Nickel forms NiO when oxidized in air above 300 C (570 F). The atomic weight ratio of oxygen to nickel is 0.273. The ratios obtained by oxidizing commercially pure nickel (99.6 % Ni) at 850 C (1560 F) and 1150 C (1920 F) for times ranging from 2 to 142 h are: 0.271, 0.260, 0.279, and 0.271. NiO, unlike Cu2O, is tightly adherent, and its accurate removal is more difficult. Nevertheless, the average oxygen to metal ratio agrees with the stoichiometric ratio within 1 %. Alloys' Oxides - The ratio of oxygen to metal, obtained from total weight gain and metal loss test data, for each alloy oxidation specimen has also been determined and found to correlate well with our knowledge of alloy oxidation. Iron-chromium-nickel alloys derive their useful oxidation resistance from the formation of a protective oxide, Cr2O3. The occurrence of breakaway oxidation is interpreted in terms of changes to this oxide. In addition, the modification of the oxide by Fe2O3 and NiO is a major contributor to the excellent oxidation resistance of aus2 tenitic Fe-Cr-Ni alloys.( ) Assuming that Cr2O3 forms on the four alloys tested here, the ratio of weight gain to metal loss is 0.462. (This may be reduced slightly by substitution of iron for chromium in the oxide M2O3.) The ratio of weight gain to metal loss is given in Table IV for isothermal test samples. At test temperatures of 1095 C (2000 F) and above the ratios for 310, 330, and 333 are close to that observed for oxygen to chromium in Cr2O3 (0.462): nine of ten fall in the 0.45 to 0.50 range. At 980 C (1800 F) the ratios for these three alloys are lower, falling between 0.38 and 0.41. The reason for this is not known. Three of the alloys in Table IV exhibit ratios well above 0.46 at 1095 C (2000 F) or 1150 C (2100 F). All three are modified with silicon which forms SiO2 (ratio of 1.14) in Fe-Cr alloys and, apparently, also in Fe-Cr-Ni alloys. Inconel alloy 601 (23Cr-60Ni-1.3AI) has a ratio of 0.63, reflecting the presence of AI2O3 (ratio of 0.89). The weight gain to metal loss ratio is not suggested as a way to identify oxides. X-ray diffraction is a far better technique. The relationship is, however, useful for estimating metal loss from weight gain. Because, as shown

Oxides and Their Effect on Weight Gain and Metal Loss

The primary reason for gathering total weight gain (adherent plus spalled oxide) data is to develop information regarding oxidation kinetics, defined as the relationship among oxidation, time, and temperature. Metal loss values express oxidation in terms of surface recession and are obtained by converting weight loss to volume loss. These data may also be used to calculate the relationship between total weight gain and metal loss. The ratio of the relative amount of oxygen absorbed to the amount of metal oxidized should agree with the weight relationships of oxygen to metal in the oxides present (Table III). This supposition has been tested by oxidation testing of pure metals using the same procedures and equipment. Certain pure metals form only one oxide in air. Assuming that these oxides do not deviate from stoichiometry and form only at the surface, then experimental values should agree with the relative atomic weights of the oxide.

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Fig. 2. Effect of temperature on oxidation of heat resistant alloys. Alloy 253MA exhibits one type of behavior; 310 and 330, a second type; and 333, a third. These data indicate that cyclic exposure increases oxidation for all alloys at all test temperatures.

Table IV: Weight Gain to Metal Loss Ratios

Test Temperature, C (F) 980 1095 1150 1205 (1800) (2000) (2100) (2200) 0.35 0.41 0.38 0.40 0.64 0.46 0.59 0.46 0.50 0.46 0.49 0.50 0.65 0.63 0.41 0.45 0.49 0.48 -

Alloy (UNS No.) RA 253MA (S30815) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333) Incoloy DS Inconel 601 (N06601)

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10 above, silicon and aluminum change the relationship between these criteria, weight loss is the preferred way of expressing oxidation rate. (A comparison of weight gain and metal loss was made in Part I.) Oxide Adherency - We've assumed that the sum of weight gain and metal loss is equal to the total amount of oxide. The amount of adherent oxide is the difference in weight after cathodic descaling. The ratio of adherent to total oxide (in percent) is a useful measure of the oxide's "adherency", and is a more satisfactory description, than "free-flaking", "adherent", or "semiadherent". Adherency values have been determined for each oxidation test specimen (both cyclic and isothermal tests). Values range from 2 to 100 % adherent oxide. Cyclic exposure at 1150 C (2100 F) results in the lowest values (greatest spalling). Isothermal exposure at 980 C (1800 F) results in the highest values. The cerium in 253MA improves oxide adherency. After 500 h of cyclic exposure at 1095 C (2000 F) this alloy retains 82 % of its total oxide compared with values of 40 to 50 % for unmodified Fe-Cr-Ni alloys. It is not surprising that good oxide adhesion and oxidation resistance go hand in hand. The relationship is shown in Fig. 3 for 32 cyclic tests of ten alloys at three temperatures. Activation - This final note relates to the Arrhenius equation, a relationship commonly referenced in oxidation studies. It relates reaction rate (oxidation rate in this case) to temperature: k = Ae
-(Q/RT)

Fig. 3. Relationship between adherency (ratio of adherent to total oxide) and oxidation resistance. Conditions that favor adherency also tend to promote oxidation resistance. Ten alloys and three test temperatures are represented.

Table V: Activation Energy for Isothermal Based on Parabolic Weight Gain

Alloy (UNS No.) RA 253MA (S30815) Type 310 (S31000) RA 330 (N08330) RA 333 (N06333) Temperature Range, C (F) 980-1095 (1800-2000) 1095-1205 (2000-2200) 980-1095 (1800-2000) 980-1150 (1800-2100) 980-1205 (1800-2200)

Oxidation

Activation Energy kcal/mol (kJ/mol) 31 (130) 146 (612) 78 (327)2 68 (285) 39 (163)

where k is the rate constant, A is a constant, R is the universal gas constant (1.987 cal/K/mol [8.33 J/K/mol]), T is the absolute temperature (K), and Q is the activation energy in cal/mol or J/mol. Activation energy cannot be determined if the kinetic mode changes with temperature; for example, from parabolic to linear. In addition, it cannot be determined if the scaling mechanism changes over the range of test temperatures. Several values for activation energy have been determined with these limitations in mind (Table V). The deviations from parabolic oxidation during cyclic exposure at 1150 C (2100 F) favor the use of isothermal oxidation which is parabolic for three of four alloys. Since activation energy is the slope of the straight line plot of rate constant vs temperature, it tells us how fast the rate constant is changing with temperature. Alloys having a similar oxidation resistance at a given temperature, however, may have quite different activation energies.

1. Rate constant based on linear oxidation. 2. Activation energy in cyclic oxidation is 88 kcal/mol (369 kJ/mol).

References
1. "Resistance of Iron-Nickel-Chromium Alloys to Corrosion in Air at 1600 to 2200 F," by A. deS. Brasunas, J.T. Gow, and O.E. Harder: Proceedings ASTM, Vol 46, 1946. 2. Gas Corrosion of Metals, by S. Mrowec and T. Werber: National Bureau of Standards and National Science Foundation, Washington, D.C., 1978.

The articles were originally published in the April (Part I) and May (Part II) issues of Metal Progress Magazine 1985. They are reprinted here with the kind permission of the Author.

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