CA2039584C - Iron-, nickel-, chromium base alloy - Google Patents

Abstract

The invention relates to an iron-, nickel-, chromium base alloy having an austenitic structure and good high temperature features, in-cluding a very high resistance against oxidization in oxidizing atmos-phere and against carburizing; in carburizing atmosphere at high tem-peratures, as well as high creep fracture resistance. The alloy has the following composition in weight-%: 0.01 - 0.08 C, 1.2. - 2.0 Si, from traces up to 2 Mn, 22 - 29 Cr, 32 - 38 Ni, 0.01 - 0.15 rare earth metals, 0.08 - 0.25 N, balance essentially only iron and unavoidable impurities and normally occurring accessory elements in normal amounts, said rare earth metals in combination with the said content of silicon im-proving the growth of a protecting; SiO2-layer on the mesal surface, when the metal surface is subjected to high temperatures in oxidiz-ing atmosphere, which counteracts the transportation of metal ions, in the first place chromium, out of the alloy, so that scaling is mini-mized.

Description

2 PCT/SE89/00630 IRON-, NICKEL-, CHROMIUM BASE ALLOY
TECHNICAL FIELD
The present invention relates to an iron-, nickel-, chromium base alloy having an austenitic structure and good high temperature fea-tures, including a very high resistance against oxidization in oxi-dizing atmosphere and against carburizing in carburizing atmosphere at high temperatures, as well as a high creep fracture resistance.
BACKGROUND OF THE INVENTION
High alloyed, stainless, austenitic steels or nickel base alloys con-taining up to 60% nickel conventionally have been used for objects which during a long period of time are subjected to high temperatures in combination with mechanical loading in oxidizing environments.
These alloys usually have a high oxidization resistance and often also a very high creep fracture resistance, but because of the increasingly high demands which are raised upon materials for the present field of use there has arosen a need of materials having still better oxidiza-tion resistance in oxidizing environment in combination with very good creep fracture resistance, a combination of features which has not satisfactorily been achieved with presently known alloys.
Another problem with known alloys of the above mentioned kind is that they have a comparatively great tendency to take up carbon and nitro-gen when exposed in carburizing atmosphere or in environments which involve a risk for the taking up of nitrogen at high temperatures.
This particularity concerns austenitic steels but to an essential degree also nickel base alloys. Also attacks from gaseous halides and metal oxides in certain environments ma;; involve problems.
The above mentioned problems ~,vill be particularity accentuated in those cases when the material is subjected alternatingly to carburi-zing and i;o oxidizing media at high temperatures, or, which sometimes even may occur, in environments which at the same time may act oxidi-zing as well as carburizing. Those situations when the material in hot -~ 26927-71 condition is exposed to ambient air after having been subjected to caburizing in a furnace at a high temperature are examples of alternatingly carburizing and oxidizing exposures. Similar conditions may occur in furnaces where for some reason it is difficult to maintain a balanced atmosphere. Further may be mentioned furnace linings which are subjected to coke depositions. It is conventional to remove such depositions by burning them off, wherein air is supplied for the combustion, which is a further example of exposure to alternatingly carburizing and oxidizing media. Finally, treatment of poorly degreased goods in oxidizing atmosphere at high temperatures is an example of a situation where carburizing and oxidizing may occur at the same time.
SUMMARY OF THE INVENTION
According to the present invention there is provided iron-, nickel, chromium base alloy having an austenitic structure and good high temperature features, including a very high resistance against oxidization in oxidizing atmosphere and against carburizing in carburizing atmosphere at high temperatures, as well as a high creep fracture resistance, characterized in that the alloy has the following composition in weight-%:
0.01 - 0.08 C
1.2 - 2.0 Si from traces up to 2 Mn 22 - 29 Cr 32 - 38 Ni 0.01 - 0.15 rare earth metals 0.08 - 0.25 N

2a balance essentially only iron and unavoidable impurities, said rare earth metals in combination with the said content of silicon improving the growth of a protecting Si02-layer on the metal surface, when the metal surface is subjected to high temperatures in oxidizing atmosphere, which counteracts the transportation of metal ions, in the first place chromium, out of the alloy, so that scaling is minimized.
BRIEF DISCLOSURE OF THE INVENTION
The invention aims at providing an alloy having a composition which brings about an improved resistance at high temperatures against carburizing as well as against oxidizing, and which also gives a good creep fracture resistance. The material according to the invention also has a good resistance against the taking up of nitrogen and also against attacks from gaseous halides and metal oxides. It can advantageously be used in the form of sheets, plates, bars, rods, wires and tubes in various kinds of furnaces, as for example carburizing furnaces, sintering-, annealing-, and tempering stoves, where also non degreased goods is heat-treated, and it can also be used for accessories for furnaces and stoves, for example charging-basket, -grates and -buckets. Further it can be used in burners, combustion chambers, radiant-tubes, reaction rooms in petrochemcial industry and in fluidized beds, exhaust gas filters for motor cars, etc.
The following table shows the broad range for the elements which are included in the alloy according to the invention, and also the preferred, and the suitably chosen ranges. The contents are expressed in weight-~. The balance is iron, unavoidable impurities in normal amounts and normally existing accessory elements. For example there is a negligible amount of aluminum and calcium in the steel as a rest due from the finishing metallurgical operation prior to casting. The con-2039~8~

3 tents of phosphorous and sulphur are very small, max 0.040%, and max 0.008%, respectively.
Table 1 Broad Preferably Preferred ranges chosen ranges composition C 0.01 0.08 0.02 - 0.08 0.035 - 0.065 -Si 1.2 - 2.0 .1.3 - 1.8 1.3 - 1.8 Mn from tracesto max 1.3 - 1.8 Cr 22 - 29 23 - 27 24 - 26 Ni 32 - 38 33 - 37 34 - 36 Rare earth metals 0.01 0.15 0.02 - 0.12 0.03 - 0.10 -N 0.08 0.25 0.1 - 0.2 0.12 - 0.18 -The carbon content has importance for the features of the steel, as far as the strengtt: is concerned, and shall therefore exist in an amount of at least 0.01%, preferably at least'in an amount of 0.02%, and suitanly not lass than 0.035%. If the alloy shall be used for the 2~ production of plates, sheets, rods, wires, and/or tubes, the carbon content, hovrever, should not exceed 0.08%, suitably not exceed 0.065°/.
Silicon. i~ required in an amount of at leas 1.2% in order that a com-bination effect between silicon and the rare earth metals shall be ~ achieved with reference to the oxidization resistance. This will be explained more in detail in connection with the description of the cerium content. Silicon also is favourable for the carburizing resistance. From these reasons, the silicon content should be at least 1.3%. The upper silicon limit, 2.0°/, preferably max 1.8%, is due to 3C circumstances which has to do with technical circumstances relating to the manufactoring and also to the fact that higher silicon contents may cause difficultes in connection with welding.
Manganese generally improves the strength but impaires the oxidization resistance. The content of manganese therefore should not exceed 2°,a and should suitably be 1.3-1.8°~.

'' 4 203984 Phosphorous and sulphur in amounts exceeding the above mentioned maxi-_ mum limits have an unfavourable influence upon the hot workability.
- The chromium content is high and lies within the range 22-29%, pre-y ferably 23-27%. Herethrough there is achieved, in combination with a high nickel content, a high silicon content, and a significant content of rare earth metals, a good resistance against high temperature damages, in the first place against carburizing and oxidization at high temperatures.
Nickel is favourable for the oxidization resistance and also for the carburization resistance and shall exist in an amount between 32 and 38%, preferably in an amount between 33 and 37%. A preferred composi-tion is 34-36%.
Rare earth metal in the form of the lanthanum group of metals in an amount, expressed in the amount of cerium which normally stands for about 50% of the mischmetal, of 0.01-0.15%, preferably at least 0.02%, and suitably at least 0.03% cerium, improves the formation of a thin, elastic ai:d adhering oxide film, when the alloy according to the invention is exposed to an oxidizing environment at high temperatures.
However, there is not obtained any further improvement of the oxidiza-tion resistance in proportion to the addition of rare earth metals, if the content of rare earth metals, in the first place cerium, exceeds 0.12%. The preferred range for the amount of rare earth metal therefor lies between 0.03 and 0.10°/. Possibly the rare earth metals completely or partly may be replaced by earth alkali metals.
Cerium and other lanthanides (rare earth metals) are suitably supplied as mischmetal to the finished molten alloy together with silicon-calcium or possibly lime as a final operation. Through the addition of silicon calcium and/or by covering the melt with a layer of lime it is possible to prevent major losses of cerium and other rare earth metals, so that the rare earth metals, as expressed in amount of cerium, will exist in a sufficient amount in the finished product in order to bring about the desired effect. Through the influence of cerium and other rare earth metals in the mentioned range of composi-tion there will in combination with silicon in the above mentioned range of composition be achieved a favourable impact upon the growth of a Si02-layer on the metal surface, when the metal surface is sub-s jected to high temperatures in an oxidizing environment. This Si02-layer will form a barrier against the transportation of metal ions, in the first place chromium, out of the alloy, so that scaling is minimized.
Nitrogen has a favourable influence upon the creep fracture strength of the alloy and shall therefore exist in an amount of at least 0.08%, preferably at least 0.1°/, and suitably at least 0.12%. Nitrogen, however, at the same time impaires the hot workability of the alloy and shad therefore not exist more than in a maximum amount of 0.25%, preferably max 0.2%, and suitably max 0.18%. Moreover, there may exist traces of other elements, however, not more than as unavoidable amounts of impurities or as accessory elements from the melt metallur-gical treatment of the alloy. Thus the steel may contain a certain amount of calcium and aluminum as a residu~il product from the finish-ing of the steel. Boron is an example of an element that shall be avoided, since that element even in very small amounts may impaire the oxidization resistance of the alloy by locating itself in the grain boundaries, 4Jnere the existence of boron ray prevent oxygen from pene-trating and be deposited in the grain boundaries in a form of oxides.
BRIEF DESCRIPTION OF DRAWINGS
In the following description of the results, reference will be made to the attached drawings, in which Fig. 1 is a graph in which the results after intermittent oxidiza-tion annealing of a number of commercial alloys are compared with the results from a first example of an alloy according to the invention, and 6 2039~8~4 Fig. 2 is a graph which illustrates the oxidization resistance of an alloy according to a second example of the invention by show-ing the increase of weight in a thermo-balance as a function of the annealing temperature up to 1300°C.
OXIDIZATION EXPERIMENTS
In Table 2, alloys 1-7 are examples of the invention. Alloys A, B and C are commercial reference alloys. Alloy 1 was manufactured as a 500 kg test charge. Alloys 2-6 were manufactured as 13 kg laboratory charges. Alloy 7 was manufactured as a 10 ton full scale charge. As far as alloys 1-6 are concerned, the molten alloy was analysed prior to casting as well as the composition of the finished product. The impurity contents in all the examples were low. The balance therefore consisted essentially only of iron. The compositions of alloys A, B
and C were obtained from the specifications for these materials.
Table 2 Alloy Charge/
No product C Si Mn Cr Ni Ce N Remarks 1 052875 0.058 1.27 1.58 25.1 34.7 0.05 0.033 piat~ 0.054 1.19 1.59 " " " 0.032 2 8322 0.045 1.75 1.68 24.7 34.7 0.065 0.126 bar " " 1.67 25.0 34.9 0.03 0.121 3 332; 0.049 1.56 1.55 25.0 34.8 0.086 0.55 bar " 1.54 1.53 " " 0.034 0.56

4 B323 0.047 1.55 1.43 24.7 34.8 0.053 0.146 bar " 1.52 1.42 " 34.9 0.018 0.147 B321 0.047 1.78 1.67 24.7 34.7 0.059 0.077 ba:' 0.046 1.75 1.66 25.0 31.9 0.023 0.078 6 332 0.040 1.87 1.80 24.9 35.3 0.114 not analysed bar " 1.83 1.78 " " 0..034 0.022 2281-'.'_ piat~ 0.048 1.52 1.74 25.7 34.6 0.045 0.130 A max max max 0.08 1.5 2.0 24-26 19-22 B 0.04 0.35 0.75 21 31 0.3 Cu C max 1.5-0.10 2.3 0.5 21 11 O.G5 0.15 ~'O 90/05792 PCT/SE89/00630 The oxidization resistance of alloy. No 1 was examined through oxidiza-tion annealing. Test coupons 25x15x2 mm were taken out from the plate.
The coupons were planed and ground. The test coupons were oxidization annealed during a total annealing time = 45 h and with five alterna-S tions down to room temperatures. The test coupons were annealed at varying temperatures between 1050 and 1200°C. The coupons were weighed by means of a standard balance prior and after the annealing experi-ments. The results are shown in Fig. 1 which also includes the results from corresponding testing of the commercial alloys A, B and C. From these results it can be stated that the scaling temperature may be 1200°C.
Thereafter also the full scale produced alloy No. 7 was oxidization tested in a thermo-balance. The increase of meight was measured as a function of the annealing temperature as in the proceeding experiment but all the way up to 1300°C. The coupons were weighed with a standard balance prior and after the annealing experiments as a complement to the thermo-balance measurements.
2~ The thermo-balance value and the differences between the coupon prior and after the ex.peri~;:en., for each individual sample is shov:~n in Table 3.
The increase of weight in the thermo-balance as a function of the annealing temperature is shown in the graph in Fig. 2. The limits 1.0 and 2.0 gr/m2 h has been indicated by a dashed line in Fig. 2 from the reason that the scaling temperature is defined by the size of the increase of weight in the following way: "The scaling must not exceed ig/mZ h with the additional condition that 50°C higher temperature must not hive more than at the most 2g/mZ h".
T.he result frc,a t~e testing of alloy No. 7 shok~s that the alloy of the invention. resists also a scaling temperature a'~ove 1200°C.

'"~ 8 2039584 Table 3 Table over each individual 17.7 mm plate, sample of alloy No.
7, - charge 2282 -71. Intermittent five alternations annealing; during 45 h.

Test Experiment T-balance Loss of Total take temperature No. values weight up of 02 o C g/ mz g/ mz g/mZ

1100 B451 7.43 6.64 14.08 1150 B452 7.80 21.24 29.04 1200 8453 11.87 23.08 34.95 1200 B454 18.65 19.56 38.21 1250 B455 54.19 32.09 86.28 1250 B458 61.94 27.15 Bg,Og 1300 8456 35.95 47.90 83.85 1300 B457 56.57 42.22 98.78 CREEP FRACTURE STRENGTH EXPERIMENTS
2~- In these experiments the same alloys were used as in the oxidization experiments, Table 2.
i:-re creep frGcture st~ength of a 20 m;~ plate made o: a'~loy No. _ i~o~
a S00 kg test charge was examined at the tempera;.ures 600, 750 and 25 900°C. Table 4 shows obtained Rkm-values and (within brackets) refe-rence date including min/max-data from three full scale charges of the commercial. steel grade C, Table 2. The examir:ed test material with the iov~ vitro~;en content as expected has lower values than alloy C, ~:rhich is kno~:.~n .o have an extremely high creep fractur a str ength.

WO 90/05792 PC?/SE89/00630 ~03s58~
Table 4 Temp Creep fracture limit, Rkm, N/mmz - °C 102h 103h 104h 105h~"

(3G0-315) (235-240) (145-155) ! - 88- = 100) (105-125) (67-73) (38-42) ( - 21- = 24) 900 28 16 ~ 10 5 (36-40) (23) (14-16) ( = 8- = 12) *The values for 105h have been derived through manual (graphical) extrapolation about one 10-pov:~er of time.
The five 13 kg laboratory charges, alloys 2-6, were manufactured in ,5 order to examine the impact of the nitrogen content upon the creep fracture strength of the alloy according to the invention. The ingots from these small laboratory charges were forged to size p 20 mm. The nitrogen conte-its varied from min. 0.022% to max. 0.147%. The measured creep fracture limit values at 900°C are shown in Table 5.
2v T_aale 5 Charge N Ce Creep fracture limit,Rkm, N/mm2 Rkm/100 h Rkm/1000 h Rkm/10 000 h*

p 322 G.12'_ 0.030 33 20 (12) B 325 G.G56 0.034 31 19 (lij B 323 0.147 0.018 34 l.g (lG;
321 6.078 0.023 33 1" r c1 30 B 320 0.022 0.034 28 16 ~ cj G
*The values for 1 G h have been derived ta.rough manual (grap;:vc~i i ext~a-polation abo~it one 10-power of time.
T_n the continued experiments concerning the influence of the content 35 of nitroge:~, the best result was achieved wits alloy No. 2 containing 0.12% id. 'the improvement as far as the value of the creep fracture i~"' l0 20~9~8~
limit at 900°C is concerned was about 20%. The experiments also show - that also the content of cerium appears to have an impact upon the creep fracture strength. The comparatively low values for alloy No. 4 ' - in spite of a nitrogen content of about 0.15% - therefore may depend on the fact that according to the control analyse the content of ceri-um was only 0.018°/. This also indicates the importance of protecting the lanthanides during the manufacturing so that these elementes are not lost in connection with the finishing of the melt and the sub-sequent casting. Also the rod material of alloy No. 5, which contained about 0.08% nitrogen and 0.023°~ cerium, seems to get a larger reduc-tion of the creep fracture values when the testing period is pro-longed, probably depending on the moderate content of cerium, which indicates that the content of cerium should be at least 0.03% in order to bring about an effect not only upon the oxidizatiion resistance but also upon the creep fracture strength. The investigation moreover shows that the creep fracture strength is significantly increased with increased nitr oge:~ content.
CARBURIZATION EX2ERIT~NTS1 G ~' Ti:ese e>:p~r~ments concern studies if six different alloys in a redo-cing, car::,ur:zing atmosphere. The dep~~:s cf carburization were measured :,.nd from these measurements the carburization rates were evaluated. ':he cue~ical compositio.~.s in ~::eight-are shor:r. in Ta'o:e The compositions of alloys D-H relate to analysed compositions, while the composition of alloy I is the nominal composition. Alloys D, E, G
and H are commercial, austenitic steels. Alloy F has a composition according to the invention, and a'_lo;; ~ is a co;n;aercial, well-kno.;n nickel 'oase alloy.

Table 6 Chemical composition, weight-%
Alloy Fe Ni Cr C Si N Mo Mn Other Ni/Fe-elements ratio D 69.6 9.6 18.4 .06 1.3 .15 .26 .53 .04Ce .14 .. 65.5 10.9 20.8 .09 1.7 .16 .24 .59 .04Ce .17 F 36.1 34.6 25.8 .05 1.5 .13 .05 1.74 .05Ce .96 G 53.8 19.1 24.7 .05 .5 .07 .25 1.50 - .36 H 62.7 12.6 22.2 .06 .39 .10 .37 1.51 - .20 I 15.5 60 23 _.5A1 3.87 The materials in all these cases had the shape of plates, and from these plates coupons were taken, size 1Ox10x1-2 mm. The coupons were 1~ ground and carefully cleaned, vrhereafter they were subjected to a reducing, carburizing atmosphere at the temperatures 850°C, 950°C, 1050°C and 1150°C during a period of exposure which lasted from 20 min ~.0 25 h. The reaction gases consisted of 89% H2 and ll~o C3H6, which was flushed through the furnace at a flow rate of 160 m/min.
Lv Tne carburization of the studied samples was analysed me~allograp:~i-cally, and the carburization kinetics was found to be parabolic and could be cescr ibed by the equa Lion xz -2r: ;,, where x=the depths of P
penetration, kp=a rate constant and t=time of exposure. The obtained 25 data was plotted according to this equation, and the graphical rela-tions then could be used to estimate the kD-values, which are listed i n Tabl a 7 and 8.
T ~ vvas : o~:nd through metal iurgical s tudi es that the carburiza Lion 3~' region could be devided into t~.:o zones. First: is the so-called massive carburizat:ion zone which is a zone just beneath the alle: surface. At greater cep~::s there is a second zone o. cari.de precipi~ates along the grain cou:idaries. The carburization rate constants, kp, are shovrn in Table 7 fcr :oral, i.e. massive plus intergranular carbide formation, 3~ and in Tahie ° for massive carburization in the surface zone onl;.

i ~~v yuiV~iyG

12 2039:~~34 Table ?

Values of carburization (10'um2/h) for t rate constants, k t l p o a carbu-rization depths.

Temp Alloy C D E F G H I

850 5.9 1.4 - 3.0 4.0 _ i0 950 12.0 2.8 .1 3.8 8.4 .6 1050 43.1 48.3 10.8 27.5 38.8 1150 - 195.7 54.1 196.8 -'"samples completely carburized Table 2 Values cf carburization constants, (10'um2/h) f rate k or massive car-p burizatioi~.

Temp Alloy C D E F G H I

850 1.4 .05 - .8 2,p _ 95C 4.3 - .3 4.4 7.0 1.7 1050 - 14.7 8.4 9.0 15.8 9.4 1150 - 38.4 11.0 19.5 - 31.2 Table 7 ar,d 8 shcw that ~ of the alio~~ invention had ~h i e s gr.i:icanti;

lowest k -value as far as cerns massive con carburization P ~
r as 'ctal carburization. :
ell as J :7

Claims (17)

CLAIMS:

1. Iron-, nickel, chromium base alloy having an austenitic structure and good high temperature features, including a very high resistance against oxidization in oxidizing atmosphere and against carburizing in carburizing atmosphere at high temperatures, as well as a high creep fracture resistance, characterized in that the alloy has the following composition in weight-%:
0.01 - 0.08 C
1.2 - 2.0 Si from traces up to 2 Mn 22 - 29 Cr 32 - 38 Ni 0.01 - 0.15 rare earth metals 0.08 - 0.25 N
balance essentially only iron and unavoidable impurities, said rare earth metals in combination with the said content of silicon improving the growth of a protecting SiO2-layer on the metal surface, when the metal surface is subjected to high temperatures in oxidizing atmosphere, which counteracts the transportation of metal ions, in the first place chromium, out of the alloy, so that scaling is minimized.

2. Alloy according to claim 1, characterized in that it has a carbon content of between 0.02 and 0.08%.

3. Alloy according to claim 2, characterized in that the carbon content is at least 0.035 and not more than 0.065%.

4. Alloy according to any one of claims 1 to 3, characterized in that it has a silicon content of at least 1.3 and not more than 1.8%.

5. Alloy according to any one of claims 1 to 4, characterized in that it has a nitrogen content of between 0.1 and 0.2%.

6. Alloy according to claim 5, characterized in that the nitrogen content is at least 0.12 and not more than 0.18%.

7. Alloy according to any one of claims 1 to 6, characterized in that it has a content of rare earth metals of at least 0.02%.

8. Alloy according to claim 7, wherein the content of rare earth metals is at least 0.03%.

9. Alloy according to claim 7 or 8, characterized in that it has a cerium content of no greater than 0.1%.

l0. Alloy according to any one of claims 1 to 9, characterized in that it has a chromium content of between 23 and 27%.

11. Alloy according to anyone of claims 1 to 10, characterized in that it has a nickel content of between 33 and 37%.

12. Alloy according to any one of claims 1 to 11, characterized in that it has a manganese content of between 1.3 and 1.8%.

13. Use of an alloy according to any one of claims 1 to 11 in the form of plates, sheets, bars, rods, wires and tubes for objects which are subjected to long time exposures in reactive environments at high temperatures.

14. Use according to claim 12 in oxidizing environments at high temperatures.

15. Use according to claim 12 in carburizing environments at high temperatures.

16. Use according to claim 12 in alternatingly carburizing and oxidizing environments at high temperatures.

17. Use according to claim 12 at high temperatures in environments which at the same time are oxidizing and carburizing.