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AD 396 420L NATIONAL GAS TURBINE ESTABLISHMENT PYESTOCK (ENGLAND) INVESTIGATION INTO THE RESISTANCE OF VARIOUS NICKEL AND COBALT BAS--ETC(U) DEANPA. V. ; MAY 65 GP-1 FLD/GP 11/6, 2 1/5p USGO

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EO' R. 2674

MINISTRY

OF AVIATION

NATIONAL GAS TURBINE ESTABLISHMENT

PYESTOCKI HANTS. N.GTE. REPORT, No, R. 267

INVESTIGATION INTO THE RESISTANCE OF VARIOUS

NICKEL AND COBALT BASE ALLOYS TO SEA-SALT CORROSION

AT ELEVATED TEMPERATURES
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U.D.C. No. 620.19%669.255t669.25

Report No. R.267 NATIONAL GAS TURBIN ggA7~

Investigation into the resistanoc of v arious nickel anr cobalt base alloys to sea-salt corrosion at elevated temperaturas

-byA. V. Dean

Gos turbines operating in salt laden atmospheres (i.e., over the sea) occasionally encounter severe corrosion of the turbine blades. k The

cause of this attack is attributed to ingested mea-salt combining in the uombustion ohamber with the sulphur in the fael to form sodium sulphate which ia deposited on the turbine blades and leads to corrosive attack. Laboratory inveatigaitions at N.G.T. & have involved the passage over heated apeonens of the vapOUr. and asesO (e.g,, sodiumr chloride and

sulphur dio.ide) that were thought most likely to aause corrosion. Tests at 95000 indicated that nickel-base alloys low in chromium were very suseeptible to attack, but that a high chromium content aloil Was insuffi-

cient to eazuxre good ocrrosion rean tan-e

loeyr the W-8eshnce of

adequate amounts of a.luinium in the alloys appeared to be beneficial. The corrosion resistance of 6obalt-base of niokel-bose alloys. A oorrouion iwchanisn is proponed which involves the depletion of chromium from the surface of the alloy through sulphide formation 80 leading to a loosely-adherent nickel oxide film. Adequte percentages alloys was no better than that

of aluminium in nickel-bpase alloys a"e thought to have a beneficial effect

bocawie aluminium does not fotima stable hulphide and is thaeoreaas

available in the surface layers of the alloy to form protective aluminium t oxide,

M.X.A.5.2.65

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22CONTMTS

Report No. R.267

1.0 2.0

Introduction Review of corrosion experience in British engines

4. 4

3.0
4.0 5.0 6.0
7.0

Laboratory investigations of sea-salt corrosion Laboratory investigations at N.G.T.E. Laboratory test results Discussion o. mechanism of attack
Fvrther work

7
8

9
11
14

8.0

Conclusion

15 15

Acknowledgement References
Distribution Detachable Abstract Ccards

18

-TABLES No.
I

Title
Chemical analysis of scale on Ashanti turbine . blades . 19

II
IIrI

Ohemical.ana!yaes of samples of sea water at two loc!alitie Results of simulated laboratory sea-salt teats at 950 C with 5 p.p.m. corrosion salt concentration Results of simulated ls1oratory sea-salt
corrosion tests at 1000 C with 5 p.p.m. salt conoentration 23

20:

21

IV

Comparative performance of various nickel and cobalt alloys in simulateit laboratory corrosion tests at 950 and 100O0

2.

VI

Results of laboratory hal.-i,-

rsion corrosion,
25

;,teats -in slphate/choridd mixtures

SI. ..

. ,

3 -

Report No. R. 267

APPENJDICES No. Title Typical compositions of various alloys tested II Methods applied for descaling of nickel and cobalt alloys after corrosion testing =LUSTRATIONS
Fig. No. Title

Page 26 27

or Sk. No. Rk.

Corroded Nimonio 100 rotor blade removed from Cazelle 101 en.aine after salt water ingestion trials Section througJh corroded area on Nimonio 100 blade View of Nimonia 90 rotor blado removed from Bristol Proteus engine after over 700 hr operation in H.M.8. 'Brave Borderer'
Section th~rough surface pitting on Nimonic 90

Rep.

10/65

blade clearly revealing sulphide penetration into the alloy

lPirst stage Nimonic 90 stator segment removed from Marino Proteus engine after severe sea water inLrestion

Rep. 12/65

Effect of temperature on the corrosion resistance of various niokel-base alloys to sodium sulphate, Rep. 13/65 0.5 per cent sodium chloride mixtures Effect of temperature on the corrosion resistance of various nickel-base alloys, to sodium. sulphate, Rep, 14/65 25 per cent sodium chloride mixtures Apparatus for producing simulated sea-salt corrosion conditions in the laboratory vapour pressure with temperature VariaLion chloride for sodium of Sections through various nickel and cobalt base alloys showing nat'e of corrosion attack after 100 hr test at 950 C with a salt concentration of 5 p.p.m. 11 Sections through alloy specins after 100 hr corr6sion test at 950 C with a salt conoentration of 50 p.p.m. 85074

"7
a 9 10

85,075
15/65 Rop 16/65

Rep. 17/65

. -

Zeport Ito. R.267

I.0

Introduction

Alloys oased on iron, nickel or cobalt Eae weI known for their good resistance to oxidation at teaperaturos of 1200 0 or more. However,

in media other than air are frequently encountered and canservice, lead to corrosive catastrophic component failure. The three types of fuel comnionly used in turbines are coal, fuel oil and diesel oil and their cormustion products are found to contain particularly reaotive elements such as sulphur, vanadium, chlorine and 1 sodium . Vanadium, as the pentoxide, collects in the ashes resulting from the combustion of fuels such as residual oil and coal and corrodes
those parts with which it

into conbination with oxygen and sodium to form sulphur dioxide, sulphur trioxide and sodium sulphate. Corrosion in boilers has been encountered for many years and results from the use of fuels containing relatively large percentages of vanadium, sulphur eto. Coal, for example, can contain as-much as 5 per cent sulphur, In ooseeprison, fuel oils for gas turbines have sulphur contents of I per cent or lesa nd can be as low as 0.1 per cent for aircraft gas turbine applicationsr,. (The specified maximum for aviation kerosine is 0.2 per cent but invariably the content is less than 0.1 per. cent.) In recent years, however, severe -orrosion pf gas 'turbine rotor and stator blades has odcasionally been reported and is '.ving cause for concern. This corrosion has occurred on the blades of turbines operating iz, salt laden atmospheres (i.e., operating over the sea) and appears to be associated with salt ingested into the engine. The N.G.T.E. Materials Department became interested in this problem following a report by the United States Navy that turbine blade corrosiol could be eliminated by the use of cobalt alloys instead of nickel alloys4. Following discussions between the Admiralty and the Bureau of Ships in Washington, it transpired that this claim was not based on any experimental evidence. It was therefore decided to examine the problem and determine the laboratory corrosion resistance of blade alloys and of compositions potentially resistant to sea-salt corrosion. 2.0 Review of orroaosion cxncrLcncr in British enainon

comes into contact.

Sulphur readily enters

Some of the earliest engine tests under simulated sea-air conditions were carried out by Bristol Siddeley Engines Limited in 1955 using their Marine Proteus engine 2,p,6. This turbine has wide usage in powering fast Naval craft and was particularly susceptible to sea-salt ingestion due to the air intake being positioned near to the level of the uea. Engine testing lasted 225 hr using a diesel fuel containing 0.57 per cent silphur and sea water injection to give a salt concentration of 1.07 p.p.n. in the intake air. xbcamination, after completion of the test, revealed that the Nimonio 90 noszle guide vanes had experienced considerable corrosion. Laboratory investigations of the deposits on the stator segments showed that 8.3 per cent was water soluble and was chiefly composed of sodium No chloride was sulphate plus a little calcium and bagnesium sulphate. The non-solubles consisted of the oxides of nickel, cobalt, present. titanium, iron, chromium, aluminium and silicon. A small amount of carbonaceous material (thought to be carbonised fuel) was also present. X-ray diffraction studies shoied the outer corrosion layer to be largely nickel oxide (NiO) with cobalt sulphide (Co384) present. The intermediate

S mnn amum

[i.

- 5R

eport No. R.267

layer contained nickel and nickel sulphide (NiIS4) and was substantially The magnctic state indicated a loss of chromium metallic and matnetic. from this layeri The important feature of the test was the presence of 8 per cen', It is sodium sulphate in the deposits found on the nozzle guide vanes. probable that this sulphate was formed in the combustion chamber as a result of interaction of sodium chloride from the sea-salt with sulphur The absence dioxide (or trioxide) derived from the sulphur in the fuel. of attack on the first stage and subsequent rotor blades is siaiifioant, In the Proteus engine test the stator blades, operating at 900 to 9300C,' were considerably more susceptible to corrosive attack han the subsequent rotor and stator blades that were operating at least 80 C lower, thus inuicating the influence that temperature may play in promoting; attack. Other early exy.eriments were carried out by Metropolitan Viokers with their Gatric engine in hB. 2009, the first gas turbine-powered sea The purpose of these trials was to determine the problems resultcraft. Deaite air inlet design ing through salt ingestion into such engines. modification, considerable amounts of sea-salt entered the engine and some slight corrosion of the nozzle guide vanes (manufactured from Nimonio 80) Analysis of the corrosion products showed that they was encountered. consisted of approximately 95 per cent nickel sulphate (NiSO4 7H 2 0), 4 per cent sodium chloride, and about I per cent carbonaceous matter. Trials were also carried out with a Metropolitan Vickers G2 engine Particularly severe conditions were in H.M.S. 'Bold Pathfinder'. encountered in this test, and melting of the nozzse guide vanes (Nimogic BOA) was encountered due to overheating to tewiperatures of about 1450o0 Blades that had not been heated above 850 to 870 0 for short periods. blades that had reached temuperatures in excess of 850 were unattaoked. to 87000 showd very marked corrosion, oharacterised by a green deposit. Analysis of the deposits ruvealed a predcminenico of sodium sulphate with traces of nickel and chromium.
2 2

7 More recently (1961), Napier Acre Engines Limited , carried out 150 hr hovering, After engine. 101 Gazelle their using helicopter trials showed Olades of which 30 hr was actually over the sea, the Nimonic 109 Further teats '9 with connibblqd edges and slight greenish soale, The initial running .trolled sea water ingestion were also oarriea out. used ingestion equivalent to 25.4 p.p.m. of salt, but, due to drop in engine power, the ingestion was subsequently reduced to less than I p.p.M. After cent. The fuel used had a sulphur content of approximately I per blades, rotor stage first 100 Nimonic the of 30 hr, severe corrosion particularly along the trailing edges, had occurred (see bigure I). of an outer Microscopic study revealed that the corroded areas consisted Beneath loosely-adhering oxide scale over a metal plus oxide layer. sulphide) (prob*coly layer dispersed finely a layer intermediate this

Thfenal 2) embedded in the matrix could be seen (see i~i, which helicopters in current service ere powered by Nimbus engines

The use of low sulphur apparently have not encountered corrosion. engine (-0.1 per cent) Avoat fuel, short flying durations and frequent effects. corrosion any minimise may replacement inspection and component Similar corrosion was reported by Bristol SiddOeley Llgines Proteus engine Installed Limited,iO after more recent trials with their ranning, pitting on the hr 700 over Alter Borderer'. in H.M.S. 'Brave Co . , .. , . ,-:,'

6-

Re-ort

o. R.267

surface of the Nimonic 90 rotor blades waas detected and led to a full ijiure 3 shows a typical blade reroved from the laboratory examination. A section through a corroded area, about 0.03 in. diameter and engine. The outermost layer consisted 0.004 in. deep, is shown in Figure 4. entirely of oxide whereas the innermost was found to be chromium sulphide intermediate layer was darker The which had a typical grey appearance. in colour and was thought to be a mixture of sulphide and oxide. The eceo with which corrosion attack can unexpectedly occur in serIn this case omission to vice is well illustrated in Vigures 5 and 6. being ingested replace a hatch resulted in substantial amounts of sea water 4 A segnent of into a Proteus engine installed in I.,.S. 'Dravo B3orderer' . a first stage stator showing severe corrosion of the Nimonic 90 blades is illustrated in Fizure 5. in an The most recently encountered catastrophic failure occurred 11 Allen turbine alternator installed in an Ashanti class frigate ,12. The Microscopic examination agein shoited typical sea-salt corrosion. Analysis of the scale deposits were found to contain sulphur and sodium. is shown in Table I and may be compared with the normal alloy composition. The probability of excessive tenmperatures being incurred during the operation of this engine is of particular significanoe, again indicating the effect that high temperatures may have in assisting corrosive attack. All the co-rosion examples cited above occurred in gas turbine engines installed in sea craft which understandably ingost air heavily No turbine blade corrosion has been experienced in airladen %rithsalt. 2 Because deck running time is quite craft engines of the Pleet Air Arm . falls off rapidly with height above sea ccncentration sea-salt limited and level cn,,ine running will be mostly in unpolluted sir. om the engine experience certain conclusions can be drawn concern, Those are summerised below:ing the nature of this corrosion. (a) l,'els used in gas turbines imstalled in sea-faring craft can contain as much as 0.6 per cent sul hur but under normal conditions (i.e., no salt ingostion) this does not result in corrosion of the turbine blades. Ingestion of even very small amounts of sea-salt (i.e. 1 I p.p.n.) can result in severe corrosion of turbine blading. 'Typical This has become known as 'sea-salt corrosion'. sea-salt may contain as much as 80 per cent sodium chloride with small quantities of other salts (see Table II). Analysis of deposits found on corroded blades reveals substantial amounts of sodium sulphate but usually no sodium

(b)

(c)

chloride.

the ingested sea-salt combines writh the sulphur in the fuel to form" sodium sulphate which is finally deposited on the stator and rotor blades. (d) Corrosion appears as a heavy outer oxide scale over an The innermost intermediate layer of oxide plus sulphide. layer is comprised of chromium sulphide which is formed The presence of sulprefereentially to nickel sulphide. phide in the corrosion products indioates the significant part sodium sulphate may play in promoting attack.

It appearA that the sodium chloride present in

Report No. 11.267

(e)

Sea-salt corrosion of blades that do not roach particularly 0 high temperatures (4850 C) (i.e., second and subsequent stages of rotorz and stators) has not been reported, whereas engines which have overheated often showed very severe corrosion of the nozzle guide vanes and first stage rotors. Therefore temperature may have a marked influence in the initiation and degree of corrosion. of nickel-base Turbine blades manufactured from a rare alloys (i.e., Nimonios 80, 8OA, 90 ,cnd 100) have been This corroded in engine trials in salt laden atmospheres, suggests that no current rotor blade alloy possesses outstandingly good resistance to this type of corrosion.

(f)

3.0

Laboratory investivations of sea-salt corrosion

Although sodium sulphate is quite innocuous, the presence of certain impurities, especially sodium chloride, could load to corrosion Aocepting this hypothesis, many investigaof gas turbine blades. 1 3 14 1 5 have studied the corrosive effects of sodium sulphate/ tors , , Tdsting sodium chloride mixtures on various turbine blade materials. has involved the half-immersion 8 f cylindrical specimens in salt mixSalt tures at temperatures up to 1000 0 for durations of I to 88 hr.

mixtures ranging in composition from pure sodium sulphate to 50 per cent 15 by eigkht sodium chloride have been used, although it has been augested
that salt mixtures containing 0.5 to 1.0 per cent chloride have a corrosive effect similar to the deposits found on blades in service.

The most comprehensive corrosion study with salt mixtures was 1 carried out by Lewis and Smith 5 in which they dotermined the effect of salt mixtures containing 0 to 50 per cent sodium ohloride on various Results obtained niokel-base alloys at temperatures from 700 to 1000 C. with salt mixtures low in chloride bore no relation to rsuJlts obtained True alloy oomwith mixtures containing high percentages of chloride. This is weli illustratod by comparing parison waa therefore impossible. the data shove in Figures 6 and '. Comparison between the various invesIt is clear from the tigators also yields widely differing conolusions.

available data that the Nimonic type alloys (no' data available for
Nimonic 115) are vulnerable to attack in salt mixtures.

to combine with sulphur from the fuel, its absence from analysod deposits It has been recently suLgested that seaor. blades is not unexpected. 4 salt particles present in the secondary air supplied to the combustion chamber may still exist as particles upon reaching the first blade stages . salt particles successful However, this still remains to be verified. in reaoiiina the turbine would aLso have to penetrate the sulphate deposit in order to trigger reaction between blade alloy and sulphate deposit. Therefore, although sodium chloride readily initiates the corrosion of nickel alloy specimens half-imzmersed in salt mixtures it is far from conclusive that a similar phenomenon occurs in service. Simple laboratory tests show that carbon, like sodium chloride, It is is able to initiate corrosion of nickel alloys by sodium sulphate. possible, therefore, for carbon to have a similar effect in the gas turbine where incariids.ont particles of carbon p"ssing through the engine are

Due to the high volatility of sodium chloride and its readiness

Report No. R.267

deposited on the first row stators and rotors available to reduce the sodium. sulphate. 4.0 Laboratory investifations at N.G.T.E.

16

, and are therefore readily

A research programme was initiated to determine the relative resistance of various nickel and cobalt base alloys to sea-salt oorrosion and The 'halfalso to shed further light on the mechanism of attack. and sodium immersion' type of test, using mixtures of sodium sulphate 4 chloride, was not oonsidered to be sufficiently real stic and attempts have been made at N.J.i*.E. to produce corrosion conditions in the laboraTests have involved the tory more sizilar to those occurring in service. passage over heated test specimens of gases and vapoure thought most A suitable rig was designed sand built and is likely to cause corrosion. shown diag'ammatically in Figure 8. The apparatus consists essentially of a long alumina tube passing through two independently controlled furnaces with a means for introducing gaseous sulphur dioxide, sodium chloride vapour, and water vanour into the Sodium chloride iae Introduced into the gas stream by passing airetream. air throuob and over lumps of sodium chloride dispersed in alumina, heated Reasonable temto a known temperature in the first furnace (Tube A).

perature control (t7 C) was attained over much of the length (14 in.) of The each furnace by using three separately-wound. furnace elements. second furnace (Tube B) was used for heating t,;) oylinaricsl spesmensn (generally i cm diameter x 2 em long) to the test temperature (V1 0).

A gas flow rate of 4 litrss/min saturated with water vapour was By selecting a suitable temperature, the vapour used for all teats. pressure of sodium chloride, and therefore the amount of vapour taken up A graph relating by the air, could be adjusted to the requisite amouj. vapour pressure and temperature Vor sodium chloride'' is shown in Temperatures of 618 and 692 C gave salt contents of 5 and Figure 9. In service the amount of salt ingested into 50 p.p.m. in the gas stream. an engine is quite variable, depending on proximity to sea, and severity Under widely differing conditions the amount of wind and sea turbulence. For this of salt ingested can vary between I and upwards of 25 p.p,m. reason laboratory tests have been carried out using salt contents of Analytical cheeks on the salt content 5 and 50 p.p.s, in the gas stream.
verified these concentrations.

Gaseous sulphur dioxide is introduced into the gas stream between The lowest flow rate used gave a Tubes A and B as shown in Figure 8. sulphur dioxide content of about 0.045 per cent which is equivalent to about ten times that likely to be found in the combustion chamber of an The gas stream containing sodium ohloride vapour, aircraft ,as turbine. sulphur dioxide, and water vapour now passes along Tube 13 and over the Using this apparatus corrosion tests have been heated alloy specimens. up to 10000C for duration of 100 hr or more temperatures at out carried and the results obtained are reported below. Comparative laboratory half-immersion tests (using a 75 per cent sodium sulphate, 25 per cent sodium chloride mixture) were also carried out on various nichel and cobalt bgse alloys in the form of cylindrical speoimens immersed for I hr at 950 C.

9 -

Report No. R.267

5.0

Laborator

test results

A preliminary series of tests were carried out at 9500C using a sodium chloride concentration of 5 p.p.s. and a sulphur dioxide concen'These concentrations are approximately ten tration of 0.0 4 5 per cent. times those likely to be encountered in a gas turbine operating in normal These initial tests on some typical turconditions just above the sea. Carbon was therefore bine blade alloys resulted in negligible corrosion. introduced into the experiment to determine whether its presence had a Cylindrical specimens ware triggering effect on the corrosion reaction. given dip coatinge of graphitic carbon suspended in ethyl alooh8 l ('Dag') Prolonged exposure at 950 C resulted and then exposed to the gas stream. in substantial attack on the same alloys. Metallographio examination revealed that alloy specimens corroded in these laboratory tests had experienced corrosion very similar, in This is appearance to that encountered in service on simiilar alloys. Beneath well illustrated by comparing Figures 10 and 11 wdith Figure 2. the outer loosely-adherent oxide scale a layer consisting of a mixture of "Fingers" of grey black oxide and grey sulphido can be clearly seen. sulphido penetrating into the underlying alloy matrix form the innermost The presence of sulphate in the outermost scale was chemically layer. identified. The results obtained for a number of nickel and cobalt base alloys at 950 0 for durations up to '100 hr or more are summarised in Table III. Typical compositions of the various alloys tested are given in.Appendix I. Nimonice 75, 80A and 90 wore found to have good resistance to attack under Nimonic 100 with a chromium content of 10 to 12 per the test conditions. cent (compared with about 20 per cent for Nimonios 75, 80A and 90) has Thu casting alloy, Nimooaut 258, of simiparticularly poor resistance. lar composition to Nimonio 100, was also found to hove poor resistance to Evidently the hiah alhuminium content (5 to 6 por cent) of corrosion. Nimonic 100 and Nimocast 258 does not compensate for low chrcmium content. In comparison Nirmonics 105 and 115, having intermediate chromium contents (-15 per centS but similar aluminium contents (-- per cent), showed very good corrosion resistance. Several other nickel-base alloys (i.e., 026, Alloy C, E474,.EPDi3 and chromium-nickel (60/40)), were included in the tests although they are unlikely to be considered for turbine blade applications because of their Of these alloys, C26 has the lowest brittleness or inadequate strength. chromium content (10 per cent) but possesses an unusually high aluminium content (11 per cent) which may account for its extremely good resistance In comparison, alloys 'C' and E474, possessing hith chromium to attack. contents (17 and 27 per cent respectively) but no aluminium, ahow only Similarly the simple 60 per cent chromium fair corrosion resistance. 40 per cent nickel alloy had very poor resisLance and was characteristed Hlowever, EPD13 having similar composition by a loosely-adherent scale. to Nimonic 80A but with additional chromium (30 per cent total) generally The first batch (A) of MD13 alloy suphad good corrosion resistance. plied by the manufacturer (Henry Yliggin and Company Limited) was found to have inferior corrosion resistance to material subsequently supplied However analysis indicated that both batches were from the (Batch B). saeme melt.

10-

Re)ort No. R. 267

A.)pa rently a high chromium content alone is insufficient to ensure Alloys with low clu-ojidurm cortonts i-ood resistance to sea-salt corrosion. It arc very susceptible to attack (c.g., Nimonic 100 and Nimocaost 258). may be inferred that alloys low in chromium (e.g., Alloy U26) require higher aluminium contents than that present in Nimonia 100 to ensure equivalent corrosion resistance to those containing moderate or high chromium contents (e.g., 15 to 20 per cent in Nimonics 75, 80A, 90, 105 and 115). Niwronio 75 contains negligible aluminium or titanium but the absence of molybdenum and tungsten which are found in substantial aaimots in several of the alloys tested may account Vor its good corrosion resistance. The presence of 6 per cent molybdenum and 7 per oent.timgsten respectively in the cobalt-base alloys 422/19 and X40 may account for their poor resisIn comparison, another cobalt alloy Umoo 50, tance to corrosion attack. Under Nvhich contains no molybdenum or tungsten, showed good resistance. normal oxidising conditions, however, moderate additions of tungsten and molybdenum are-not generally considered to have an adverse effect on the However, their oxidation resistance of either nickel cr cotalt alloys. ability at elevated temperatures (above 800 C) to promote catastrophic oxidation is well known. Two theories have been proposed to account for this effect ,ith One theoryl proalloys containing at least 4 per cent of mmolybdenum. Molybdenum poses the formation og low melting point oxide euteotics. trioxide molts at 790 C and theomolybdenum trioxide/iron oxide eutectic, The presence of a liquid phase on the for example, melts at about 730 C. surface of an alloy has a most deleteripus effect on oxidation reseRtance. air above 800 C has also been attributed"v to Severe oxidation in still the possible dissociation of molybdenum trioxide into molybdenum dioxide The largo amount and very reactive nascent oxygen (KoO, 1 Mo00 + 10'). of oxygen available in moving air effoctively prevents the formation of Any inability or difficulty to form a truly the lower molybdenum oxide. protective scale in simulated sea-salt conditions might well be accentuated by the formation of, for inntance, molybdenum trioxide. A 8erios of tests vas carried out at a higher testing temperature viz. 1000 C using similar salt and sulphur dioxide contents (i.e., A slight increase in the 5 p.p.m, and 0.045 per cent respectively). corrosion rate was apparent (see Table IV) but no alteration in the order of merit resulted for the limited number of alloys available for comIparison. * oPerhaps of more signifioance vere the results of tests carried out at 950 C vrith a considerably incressed sodium chloride and sulphur dioxide .hose concentracontents viz. 50 p.p.m. and 0.4,5 per cent respectively. tions are about xlO0 grctcr than those likely to be encountered by airInspection of the results craft gas turbines cpecv-ting over the zoa. given in Table V, where comparison can also be made with similar laboratory tests at lower vapour concentrations, immediately reveals a very Under such extreme condisevere increase in corrosion for most alloys. significant experienced EPD13, alloy, resistant most the even tions 3 Even more noteworthy is the poor attack (weight loss of 6.9 mg/cm ). resistance to corrosion exhibited by alloys such as Nimonic 105, the earlier Nimonic 115 and C26. which had shown up very favourably in conountrationEs. dioxide sulphur and salt lowver with tests

i.~

~~~~~ ~

.[ ...... .L_ .. .

~~~

..

...

11 -

Report No. R.267

The results of half-immersion tests using a salt mixture of 75 per cent sodium 2ulphate, and 25 per cent sodium chloride are given in Table VI. Alloys tested for I hr at 950-C were either unattacked or severely corroded. The results bear little relationship to those obtained in the simulated laboratory tests at the same temperatures, as seen by the markedly different orders of merit (see Table VI). Considering the long durations of testing (up to 100 hr or more), results obtained at 950 0 C ;ith 5 p.p.m. concentration show reasonable reproducibility for specimens experiencing relativelyr srmall amounts of corrosion (i.e., less than about 5 mg/cmo weight loss after descaling). However alloys experiencing quite severe attack i.e., E474 and chromium/ nickel (60/40) showed fa.rly large scatter in the few tests carried out. Generally only a few samnplen of each alloy were tested and accurate assessment o- the reproducibility of this type of test can only be achieved by testing, say, 10 samples of each alloy at a given test temperature and vapour concentration. 6.o Discussion of mechanism of attack

Both laboratory and engine tests have shown that the presence of sodium sulphate in the -,as turbine resulting from sea-salt ingestion can lead to a oharacteristic attack known as 'sea-salt' oorrosion. It has been demonstrated at N.G.T.E., and by other investigators, that sodium sulphate alone is quite unreactive when in contact with nickel alloy specimens, but, the presence of a suitable triggering agent can result in A mechanism has bean proposed by severe corrogion of alloy specimens. Simons at ala for the corrosion of alloy steels in the presence of sodium sulphate. It is thought thrt a similar mochanism of attack may apply in the corrosion of rotor and utator blades of gas turbines operating over the sea and is developud below. Interaction between sodium chloride (from the sea-salt) and sulphur (from the fuel) occurs in the combustion chamber of the gas turbine, and can be written in the following simplified form.

S2NaCt

+ 'St

+ 21H1 + 20,g ....

-Vag S0 4 + 2HC1

(I)

The sulphur and hydrogen are available from the combusting fuel either in the nascent form as in Equation (1) or in combination with oxySen as sulFree energy (a.) considerations predict phur dioxide and water var:our. that this reaction is thermodynamically possible but, of course, do not give any rcal indicetion of the re-action kinetics. The combustion products containing sodium sulphate vapour, hydrochloric acid va. our, water vapour, sulphur dioxide, sulphur trioxide, and chamber into the incandescent carbon particles pass from the combustion the sodium sulphate ad. carbon first stages of the turbine -ihere some of The initial are deposited on the relatively cool ulade surfaces. triggering action involves reduction of the sodium sulphate by a reducthe d-posit and m be reprsented t ing agent, such as carbon, prcscnt as follows:-

12

Report No. R.267

2Na 2 S04

+ 6C + 30,-+-a.O + 6C02

+ 2'S'

....

(2)

0 At a blade temperature of about 1000 C thermodynamic considerations The free energy change show that this reacts ion should readily occur. (WG) is about -80 Kcal/mole.

The sulphur product formed in Equation (2) is immediately free to combine vrith the unarlylng blcado alloy to form metal sulphides, thusl-

Crg8 2 Or + 3 'IS -+
and poesibly Ni + '. -' Ni S

....

(3)

Chr n~vun sulphide forms more readily than nickel sulphide because of the considerably greater reactivity of chromium (and therefore greater free However, if the chromium content of the alloy is low energy of reaction). the abundance of nickel available for reaction enables nickel sulphide to A similar situation may also arise where chrof: rm (Law of Mass Action). mium may be depleted at the surface layer by oxidation or at grain bounwhere locally iaries by carbide precipitation, or during severe corrosion the ohromium content may be reduced to a low level due to excessive chroHowever, loss of chromium from the alloy matrix mium sulphido formation. through sulphide formation produces a concentration gradient between the Because of this, chromium corroded zone and the bulk of the alloy. diffusion into the areas denuded of chromium occurs and becomes available tciy nickel sulphide so formed is therefor further sulphide formation. fore likely to be reduced by newly available chromiumi-

3 liS + 2 Cr -*Cr 2 S3 + 3 N1.

(4)

This explanation of sulphide attack is borne out in service where nickel sulphidi is not usually foundL in the corrosion products, The metal s.iphide formed in the above viny is now available to combins with either free sodium sulphate or free oxygen in the combustion The reaction between chromium sulphide and products of the gas turbine. sodium sulphate,

Na2 So 4

+ Cr2 S 5 - Cr 5 03

+ NaO + 4S

....

(5)

However, free energy conhas been proposed by other investigators siderations give no support to this theury since the reaction would More correctly, involve a large and positive energy change (+AG). A Equation (5) should be written with reactants and products reversed. similar situation occurs with nickel substituted for chromium.
It is more likely t.hnt the relatively simple reaction mium sulphide and oxygen

22

betwden

chro-

13

Report No. R.267

2CrsSa

+ 902

2Zra03 + 6S0 2

....

(6)

will occur.
This reaction is strongly possible from thermodynamic consideration and has also been reported in the literature 1 . The formation of chroHowever, a limited supply of oxygen may mium sulphate is also possible. be es'sential for sulphate forrAtion,

CrgSs + 60s --t Cr2 (s0 4 )a Nickel oxide, with chromic oxide in the outer loosely-adherent scale may be readily formed by combination of nickel from the blade alloy (which has been heavily impoverished of protective chromium) with oxygen in the following ways-

2Ni

-+ 2NiO

This proposed mechanism, based on thermodynamic considerations has not included the many side reactions Which are quite likely to occur. It does, however, give a reasonable outline of the corrosion attack involving formation of a reactive sulphur species through reduction of It in this sulphur sodium sulphate deposits on the blade surface. species which readily combines with the underlying blade alloy to form sulphide fingers that penetrate into the matrix and eventually become available for enhanced oxidation. The fornation of nick.1/nickel sulphide eutectic with a particularly low melting point (644 C) hae b ni roposed by investigators as The theory suggests that being the cause of enhanced oxidation'',28.* metal dissolved in the euteotio mixture would be highly reactive towards oxygen especially as a truly protective film seldom forms on a liquid. The two stage oxidation process may be written as followat(i) (ii) Solution of metal Oxidation Ni + NiS -#Ni/AiS euteotio Ni/MiS + -202 -+ NiO + NiS

This mechanism postulates oxidation of the nickel dissolved in the eutectin rather than the nickel sulphide, Generally, nr evidenne is found hat a liquid phase has formed This is not unreasonable ifduring corrosion in service at say, 850 C. Chromium chromium sulphide is formed preferentially to nickel sulphide. sulphide (melting point 155000) doeu form a metal/metal sulphide eutectio which melts at 13500c, a temperature considerably higher than that The formation of a encountered by rotor or stator blades in service. C) is often identified low melting nickel/nickel sulphide phase (6" half-immersion tests using sodium sulphate/sodium chloride in laboratory 1 mixtures 1 4 ,i, and especially when attack is severe.

14 -

Report No. R.267

Experimental data indicates that the aluminium content of typical nickel-base alloys appears to have a significant influence on resistance The to sea-salt corrosion, especially with alloys low in chromium. oxidation resistance of typical nickel-base alloys (i.e., the Nimonic series) is known to be accounted for by the physical characteristics of With the chromic oxide/nickel oxide layer formed on the alloy surface. chromium contents of 10 per cent or more a 'spinel' typo structure is formed between the nickel oxide and chromic oxide which is extremely Addiimpervious to oxygen and is tenaciously held to the alloy surface. tions of aluminium to nickel-chromium alloys result in a further spinel being formed between the nickel oxide and aluminium oxide which is consiA nondoted to Live even gr-ater protoction to the underlying alloy. spinel type structure is also formed between the chromic oxide and aluminium oxide which ip less protective. Alloys of low or zero aluminium content depend entirely on the nickel oxide/chromic oxide spinel for protection of the substrate against Damage to this protective spinel does n(t result in rapid oxidation. oxidation of the alloy because fresh imporvioue spinel is immediately However, the absence of formed through oxidation of the alloy surface. chromium in the surface layers of the alloy through sulphide formation results in the nickel matrix being exposed to sevego oxidation, because nickel oxide alone affords no protection above 800 0. Laboratory tests have indicated that adequate percentages of aluminium have a beneficial effect on the resistance of nickel alloys to seaIt is sugented that aluminium may do this by being salt corrosion. Alumiunable to form a stable sulphide under the prevailing conditions. nium would, therefore, always be available in the surface layers of the alloy to form aluminium oxide which alone, or in combination with nickel oxide as a spinel, would act as a protcotive barrier against the corrosive Evidence as to the ability of aluminium to form a stable environment. no useful thermodynamic sulphide is rather scanty and there is certainly 22 have reported that aluminium Several investigators data available. sulphide readily decomposes in air and is reduced by iron and copper. It appears therefore that aluminium sulphide is unlikely to be found in corrosion products but may break down to form protective aluminium oxide. Several investigators have experimented with aluminised and chromised blade alloyr (e.g., Nimonic 90 and coatings on typioal gas turbine rotor 23 and laboratory hvlf-immersion Nimonic 115) in both full scale rig 24 1 Pack cementation techniques are preferred for applying the . tests i, In half-immereion tests using the most reactive salt mixture coating. coatings (75 per cent sodium sulphate, 25 par cent sodium chloride) In rig tests, aluminised generally had lives of from I to16 hr at 900Oc. A single laboratory test coatings remained protective for up to 20 hr. at 14.G.T.E. uning a pack aludnisod Nit:onic 90 spccimen under simulated conditions with a salt concentration of 25 p.p.m. (sulphur dioxide at 0,225 per cent) indicated that the coating gave satisfactory protection 95000 for the test duration (100 hr). 7.0 Further work

Investigatory worke at N.G.T.E. into the resistance of high temperature alloys to sea-salt corrosion was promptod by the need to substantiate the claim of the United States Navy that cobalt alloys had superior resisResearch has gone further than this and attempts tance to nickel alleys. have been made to shod further light on the rechanism of attack and the

15

Report No. R.267

factors influencing the corrosion resistance of the various alloys tusted. Three lines of further research are possible. (a) rore accurate determination of the influence of alloy com-

position on corrosion resistanoe using alloys with controlled additions. (b) More comprehensive reseirch into the influence of atmosphere composition and concentration in promotinS corrosion at elevated temperatures in simulated laboratory tests. The development and evaluation of coatings that are resistant to sea-salt corrosion.

(a)

8.0

Conclusion

A laboratory tett in which air, .sodium chloride vapour, etc., are passed over various high temperature alloys has been shown to reproduce corrosion in the laboratory similar tc that vhioh occurs in bas turbines The results obtained do not substantiate the operating over the sea. original United States Navy contention that cobalt-base alloys have The susceptibility superior corrosion resistance to nickel-base alloys. of nickel alloys to corrosion under simulated laboratory conditions generally appears to be influenced by the aluminium and chromium contents of the alloys and is in areement with the corrosion mechanism proposed.

Aoi!qOaLMGaENM
The author gratefully acknowledges the assistance given by Mr. J. E. Northwood in the preparation of the photomiorographs.

16

Report No. R. 267

Rid' Eztq CES

NO.
I

Author(s)
L. "I.Johnson Bradbury E. 01.

Title, etc,
Corrosion-resistant materials in Marine Engineering. The International Nickel Company (Mond) Limited Publication No. 588C pajges 8-9 Solt water corrosion of hizh temperature blading in marine gas turoines. N.G.T.E. Correspondence 17th May, 1960 Corrosion of gas turbine blades in marine conditions. February 1962 ISIQ-T 2797 HR 555 Private communications with Naval Ma-ine Wing, N.G.T.E. Laboratory Initiation No. 8630A. Report No. 18 11th July, 1955 Corrosion of turbine: muterisls tunder marine conditions. Report No. B3I0739 27th May, 1960

Cdr.' W. T. Look

A. Musoott

Cdr. M. S. Drewett

Bristol Siddeley Engines Limited Briutol Siddeley Engines Limited

Frivato conaudiation with T. I.. Pullin Resident fechnical Officer, Dr. '1.A. Taylor, N.G.T.E. 17th October, 1961 Napier Aero Engines Limited Napier Acre Engines Limited Napier Aero 'Engines Limited (Development Department) Laboratory Report No. Reference JK;4A/iE3 12th July, 1961 6871

Report on condition of GA.101 following salt ingestion with reference to later sand ingestion tests. Report No. FPJVGazelle 101A~/.1045 7th November, 1961 Laboratory Report No. L.E. 62/109 25th April, 1962 Private communication, N.G.T.E. October 1963 Private communication, N.G.T.E. November 1963

10 11 12

Bristol Siddeley Engines Limited J. E. Northwood F. H. Holderress

17-

Report No. R.267

REFEWCES (cont'd) No. 13 Author(s) H. T, Shirley Title, eta. Effects of sulphate-ohloride mixtures in fuel-ash corrosion of steels and high nickel alloys. Journal of the Iron and Steel Institute Ifebruary 1956 Vol. 182, pages 144-153 The corrosion of gas turbine blades under marine operating conditions. Bristol Siddeley Engines Limited IaSK 2805 HR 558B 23rd November, 1961 Corrosion of high-temperature nickelbase alloys by sulphate-chloride mixtures. First International Congress of

14

R. WJ.Arohdale

15

H. Lewis R. A. Smith

Metallic Corrosion
Published by Butterworths, pages 202-214, 1Oth to 15th April, 1961 16 17 R. S. Smith C. J. Smithells Private communioation, N.G.T.E, Metals Reference Book. Published by 3atterworths,

November 1961
page 657,

1962

18

J. L. Meijaring

Rapid oxidation of metals and alloys

Rathernau G. V1.

in the presence of molybdenum trioxide. Nature, Vol. 165, pa&es 240-241

lth February, 1950 Meohanjim of the rapid oxidation of high teriperature, high strength alloys containing molybdenum. Transactions of American Society for 1949 Metals, Vol. '41, pages 1213-1247 Sodium sulphate in gas turbines.

19

W. C. Leslie 4M.G. Fontana

20

E. L. 5inons

G. V. Browning
H. A. Liebhafsky 21 J. 4. Mellor

Corrosion, 11, 505t-514t

1955

A comprehensive treatise on inorganic and organic chemistry. Vol. XI, Published by Longmans, 1948 Green and Company, page 431

22

J. W. Mellor

Ibid. Vol. 5, page 331

18

Report No. R.267

REFERECES (cont'd) No. 23 Author(s) Bristol Siddeley Engines Limited Title, etc.

Salt water injection test on 1st stage turbine blade materials to Admiralty requirements. Report No. P.T.R. 21st May, 1963 76

24

E. G. Richards

A review of laboratory high temperature corrosion tests on coated sam~ples of nickel-base heat resistant alloys. The International Nickel Company (Mond) Limited G.T.C.C. Materials Sub-Committee Report

No. R.C. 561

25 L. Vt. Johnson S. J. Bradbury

-October 1963

Corrosion resistant materials in marine engineering. The International Nickel Company (Mond) Limited Publication No. 5880/5911 Smithsonian Physical Tables. Vol. 88 page 651, Published by Smithsonian Inotitution

26

V,'. E. Fowle

1934

ADVANCE DISTRIBflJUION BY N.G.T.E. The Chief Scientist, M.O.A.

ACr.1(a), (Mr. A. Anscombe) AD/Eng.RD. 1 AD/Eng. RD. 2 rOA(RD) DFP DG(Eng.)

D.Eng. 1 D.Eng. 2 DWAGS (1 copy)

DGR(A)

D.Mat. Pats.1(a)3, N.G.T.E. Staff Officer (Naval) Eng.RD TIL.I(b) (180 copies)

AVD/65A$)LK/305/27/1ii

19

Report No. R.267

TALLE I Chemioal analysis of soole on Ashanti turbine blades

Per oent by wei-ht of elements in scale First-stage rotor blades

Eleont

Firit-stage blades o stator

(Nimooaet 90)

(Nimonio 90) ........... ... ....

SOomposition 90 o N
Nimocast 9

No. 2

No. 4

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

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

C.C.I. Woolwioh spoctrographio analyses At 10.0 8.0 11.5 9.5 i 1.2

B
Od

1.0
SLIGHT

1.0 4.5
15.5 1.0 8.0 11

<0.5
TUACE

<0.5 3.0 7.5

1.5 19.5

Co
Or Cu Fe

6,0
20.0 1.5 10.0

3.5
9.0 1.5 23.0

16,0
20.0 0.5 5.0

11

I Ni
Pb

<<.5 0.5
2.0
1.5 <1.0 0.5 24.0
1.0

I<0.5
17,5
2.5

<0.5
14.5
2.0

0.3 BilL
-

Ti V
Si

<1 0 05

2,5 0,5
4.0

2.0 o,5

2.4
-

!~~
N(,.T.E ,: i 12.5 (0.7)" *I 9.0 Analyses

~~ . ........ . ......... 3.O .. iI:

0.4

,,

iso,

24.1

24.3

KNa

0.5

5.1

3.1+

iI

N.B, Frtm analysis of a portion of scale taken from another first-stage stator

bltde (No.

6)

-20

Report No. R.267

TABLE II Chemical analyses of samples of sea water at two looeJlitiea

Concentration in parts per million

Constituent

Locality of sampling

Kure deaoh 25
North Carolina Sodium Chlorine

North Pacific2 26

10,590
19,200

10,722 19,337

Magneaium Calcium Potassium Sulphate, So 4 Bromine

Iron

1,292 404 4-03 2,664 67

negligible

1,207
417 382 2,705

66

Carbonate, C03

negligible

7
-

p77

21

Report No.

R.267

TABLE III Results of simulated laboratory sea-salt corrosion tests at 950QC with r p.p.n,. salt concentration Gas flow rates and conditions:Air saturated with water vapour Sulphur dioxide Sodium chloride

4 litres/min 0.045 per cent by volume 5 p.p.m. by weight

A graphi+.e coating was applied to all specimens prior to testing.

i IAIoi
Ni-base Nimonic 75 Nimonic 80A

~ duration ~~hours Test

loon* \oight =o-

72

3.7

0o ': "!
Nimonic 90
72 100 -I co 250

2.5
6.9 3.3 6.0o 8.1

.
A

72
100 100

4.6
3.8 "44 36.3

Nimonio 100 Nimonio 105

72

100 150

i0o

1.6 1.7
1.3
1.6 4.3

Nimonic 115

100 100

Nickel/Chromium (80/20)
IHimocast 258 ED13 (Batch A) * EID13 (Batch B)

100
100

1.1
2.9

72 72 72 100
116 116

101.0 8.7

15.8
3.7
0.9 3.6

1
r.

100 0E47

100

29.1

4.9

22 -

Report No.

R.267

TABLE III (cont'd)

All/J

Test duration hours 76 76 1.0o 100 100

,ht

loss /cmo

Alloy C ChrondunA/Nickel (60/40)

8.5 20.8 8.5 22.7 51.0

Umao 50 (Cast) Umoo 50 (foreea) X40(cat)

100 100 100 24 72 100 o17.4 24 100

0.0 2.3 3.5 4.5 16.3 3.3 17.6

422/19 i:

?See Appendix I for compositions used *Soo Appendix ii for methodu for scale removal after testing

23

Report No. R.267

TABLE IV Results of simulated laboratory sea-salt

corrosion testis at IOO0CC with

5 P.n.m, salt concentration Gas flow rates and conditions:.. Air zaturated with water vapour Sulphur dioxide Sodium chloride 4 litres/mmn 0.045 per cent by volume 5 p.p.m. by weight

A Lraphite coating was applied to all speoimens prior to testing.

Test duration hours

freight loss mg/oien

Nimonio 75

1OO

2,6

Nimono 715
1TDI 3 (Batch 13)

100

2,6
2.7

10o

2),

5.5

Cobalt-baso2 Umoo 50 (forged) 214

6.0

1100

9.0L
000

x~.o,100

21

Report No.

R.267

TOLE V Comparative performance of various nickcel and cobalt alloya in simulated laboratory corrosion tests at 950 and 100000

Gas flow ratea and conditions:Air saturated with water vapour Sulphur dioxide Sodium chloride Test duration 4 litros/min 0.45 per cent by volume 50 p.p.m. by weight 100 hours

A graphite coating was applied to all specimens prior to testing.

& HWeight loss mgAom

Alloy 50 p.p.m. salt concentration 9500C 5 .p-m. salt oncenP*M saltconPen. tration 1000 C |

tration 950 0

'I i-baue
Nimonio 75 Nimonlic 90 INimonic 105 12.2 59.4 91.4 2,5 3.0;4.41.6;1.7 4.2
-

i,

oiio 115

1i6.0;211. 7
6.9

1. 6,"3
3.7;"0.9

2.6
5.5

SEPD13 (Datch n) FAU Alloy C Chrorrtum/Nickel (60o/)

42.3
111.1 44.3 95.3 26.0

3.6 4.9;29.11

>8.5 8.5; 22. 7;51. 0 0.3 0.0; 2

l Alloy C26
1! Co-base j- Umco 50 (cast)

I. Umoo 50 (forged)
422/19.
Oobalt/Chromium (80/20)

3.0
5.0 0 2L,0

3.5 17.6
-

9.0
-

*Results rrom 'fable III #'Results from Table IV

tI
-25TABLE VI Resul-ts of lab-oratory, h alfT.:Immersion corrosion tests in sulphate/chloride mixtures Report No. R. 267

Test conditions

Composition of salt mixture sodium sulphate 75 per cant sodium chloride 25 par cent

Test ten.orature Duration

95000 I hour

Wei6ht loss Alloy Half-immersion test:i

.teit

-/OMG

Simulated laborat~ryI1, utes 100or/950Al 100 h/5

Ni-bpaee
Nimonia 90
.

211

3,80.4

Fiokel/Chrwomium (80/20)

O1i4

1.1i2.9

S474o
Alloy C ii Chromjum/nIickel (60/40) Alloy 026
.

.7
126.8 0.6 126 ......

,.9; 29. 1
>8.5 8.5;22.7;51-0 0.3

Co-base
Umoo 50 (cast) !i Umco 50 (forged) I X40 422/19

145;155
2.2;3.1 <1.0 <1.0

0O.;2.3 3.5 17.4 17.6

*Results from Table III

-26

Report No. R.267

AI'DIDIX I

\DC1 '
c

104 0~C)

4)

.ii

N'

CU

~ ..... . ... O .. ... .... ....... .. ..........

0I

. . . . . . . .

ll RI

ON '-- 1_
's

I
N

9 ri

V)

' I'
I

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

I'1

M0
N -u.

'-

-%
0

)i

OO OU

0 N0

00

co x

RESTRICTED - 27 AflPENDIX II Methods applied for descaling of nickel and coalt alloys after corrosion testing.

Report No. R. 267

(a)

Electrolytic desoaling in molten sodium hydroxide, sodium carbonate

mixture (50/50) at 4150C0. The corroded specimen was made the cathode, end its nickel container used as the anode. Reduction of the metal oxides to the metal by sodium ions occurred, the r- duced metal being removed by brushing. ,etal sulphides were similarly reduce,.

Na0H Na
4 Ni0 + 2Na

+ (OH)
+ Na 2 O

At cathode

-+ Ni

Na2O + H20

2NaOH

However this method was not found entirely satisfactory for cobalt alloys as they were susceptible to greater uncorroded metal lose. Other techniques were therefore used for these alloys. (b) Immersion in a warm (60/700c) acidified sodium fluoride solution, made by discolving 4 grms of sodium fluoride in a mixture of 10 mls cone. W103 and 86 mlo 'ater. This technique was very effective for cobalt Umco 50 alloy but additional abrasion was ncce:s'u'y with other cobalt alloys. (a) Electrolytic descaling in diluted 5 per cent sulliuric acid solution was found to be quite effective for- scale removal with The most specimens corroded in sulphate-chloride salt mixtures. specimen is made the cathode and the presence of an inhibitor, diortho-thiotolylurea, further minimised uncorroded metal loss Scale removal results from the prising throug9h acid attack. effect of hydrogen evolved at the metal/scale interface.

RE&TICTED

FIGS. I & 2
-0

SFIG. I

um

CORRODED REMOVED AFTER FIG. 2

NIMONIC

100

ROTOR

BLADE

FROM !IGAZELLE_ 101 --ENGINE WATER INGESTION TRIALS.

SALT

-LOOSELY SCALE.

ADH4ERENT

-INTEMEDIATE
S..

PARTLY

""--FINELY

OOUDISED LAYER.

DISPERSED
'AHEAD' LAYER

SECTION ON

THROUGH NIMONIC

CORRODED BLADE.

AREA

100

FIGS. 3 &4
SFIG. 3

VIEW OF NIMONIC REMOVED AFTER IN FIG. 4 FROM OVER H.M.S.

90

ROTOR

BLADE

BRISTOL PROTEUS ENGINE 700 HRS BRAVE OPERATION BORDERER.

SECTION ON NIMONIC SULPHIDE.

THROUGH 90

SURFACE

PITTING REVEALING ALLOY.

BLADE

CLEARLY INTO THE

PENETRATION

FIG. 5

In

ae

FIRST

STAGE

NIMONIC 90 STATOR

SEGMENT

REMOVED AFTER

FROM MARINE SEVERE SEA

-

PROTEUS ENGINE INGESTION

WATER

FIG. 6

In coloy DS

100
Nirnonic o

10

Ni rnon ic g

SNirnonic

Te00era0re

1,000

oc1 EFFECT OF TEMPF-.pTR~E O 0.VA ROU O NIKE BS ON THE COR0JNRSSAC ALLOYS TO SODIUM SULPHATEr,!

PRCENT SODIUM

CHLORIDE MIXTUR~s

FIG.7

01,000

Nimonic 0+

)x

cl70Z
Nimonic BOA

In

E n
In:
V 0 N

ncl

imonic 1001.

Nimonic 105..-, S Nlm~nic 75

80 A.

.s

..

--

...

A..

0.1 700 8oo

Temperature

,10 900

1000
oC

(BROKEN

UNES

SHOW

OXIDATION

IN AIR.)

EFFECT OF TEMPERATURE ON THE CORROSION RESISTANCE OF VARIOUS NICKEL BASE ALLOYS TO SODIUM SULPHATE, 25 PER CENT SODIUM CHLORIDE MIXTURES

FIG. B

o-o
00 0
I

0
o0 o

I0

0'

Io

00
0 0

0
0

0N

0.

0 \
0

\o nOA00\ On 0 \z
0

0 Q 00
50

0
0 0

0
1

iizii

FIG. 9
780

700

ii

S/I,

600

Iii

Ii
550

'I

3:

-,'0 LOO.

-3"0 VAPOUR PRESSURE

-2-0

-1.0

VARIATION

OF

VAPOUR FOR

PRESSURE CHLORIDE

WITH TEMPERATURE

SODIUM

FIG. I0

Lfl

K
- IW ,;ld

SOUTER ~LAYER
Ol

CORROSION

CONSISTING
OXIDE
*

SULPHIDI I

'

uIs

NICKEL

EPD 13 ALLOY (BATCH A)X

OUTER CORROSION LAYER CONISISTING S ."1 07J OXIDE * SULP x 00

9
ALLOY BTHA NCOBAL 1 X40 'w . COC
4.4

SEVERE PENETRATIOC
MARI - ,. _ I1I

,.... .

,,

OF *

.
*

PEN.RI' .; *: . ..
. 1 ..

,r-

.TAI

ALLOY
SETOSTRUHVROSNCE

SHOING ATUR

OF

ORRO
COALT K 400

ION

ATCKIIaN
ASDZ

COBALT

X40

AL.LOY

SECTIONS THROUGH VARIOUS NICKEL & COBALT ALLOYS SHOWING AFTER 100 HR CONCENTRATION NATURE OF CORROSION

BASED", ATTACKI

TEST AT 950C WITH A SALT OF 5 PARTS, PER MILLION.

FIG. 10 (cont).

ul

-METAL STRIP SUPPOIMNO SPECIMEN SURFACE

SULPHIDE OXIDE

rI

PENETRATION

IT

COBALT

UMCO

50

ALLOY (FORGED)

InI
CL. ic LAYER

FIG. II

OUTER

OXIDE

INTERMEDIATE OXIDE , SULPHIDE LAYER

--

NIMONIC
f ,

115

ALLOY
SUFC

NICK.E
SIONS
..

AL OY SPACIMEEN
___.

THROUGHH
;,,,==..*.

SURF'ACE

'. . *;

.. JAo, .

AFTER

100 HR CORROSION

AC

TEST AT 950

WITH A SALT CONCENTRATION OF 50 PARTS PER MLLION

p/ACHAILa &?ACeTFC CARM ?hAOs abstract cards are Inserted In H.G.T.C. Reports and Memoranda for the OOIWODISUCO

of Librarians and others who need to maintain an Informatlon index.

DeOaMOed O&arM e sUbjeot to the sM 8ecurity Regulations as the parent dooU-ftp and &reord of their location should be mSde on the inside of the bok cover of the parent doCu-

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