CORROSION OF REACTOR MATERIALS

The two most "modern" fields of technology, Much operational experience and many experi-
nuclear and space engineering, are placing drastic- mental results have accumulated in recent years re-
ally increased demands on numerous materials; they garding corrosion of reactor materials, particularly
have to conform to extremely rigorous specifications, since the 1958 Geneva Conference on the Peaceful
in which new physical and chemical properties have Uses of Atomic Energy, where these problems were
been added to the old ones. One of the necessary also discussed. It was, therefore, felt that a survey
characteristics is increased corrosion resistance. In and critical appraisal of the results obtained during
fact, corrosion resistance has often been described this period had become necessary and, in response
as the foremost problem in the choice of reactor to this need, IAEA organized a Conference on the
materials. Corrosion of Reactor Materials at Salzburg, Austria
(4-9 June 1962). It covered many of the theoretical,
Reactor materials include nuclear fuels (mainly
experimental and engineering problems relating to
uranium, but also plutonium and thorium), the clad-
the corrosion phenomena which occur in nuclear r e -
ding in which the fuel is contained and pipes and ves-
sels in which coolants circulate (a large variety of actors as well as in the adjacent circuits. Some 200
steel, aluminium, zirconium and other alloys), mod- experts from 23 countries took part in this meeting.
erators (graphite, beryllium, etc.), shielding (con-
Behaviour of Steel
crete of varying composition), and metals used for
mechanical reactor components. All these are sub- Several of the papers presented at the confer-
ject to particularly heavy corrosion owing to the fact ence dealt with the behaviour of steel. H. Inouye
that they are exposed to coolants at high temperatures (USA) reported on studies on high temperature reac-
and p r e s s u r e s and to irradiation, and the fact that tions of certain types of stainless steel in helium with
radiation increases the susceptibility of certain mate-
low concentrations of carbon dioxide and carbon mon-
rials to corrosion.
oxide. This research was part of the fuel develop-
Heavy corrosion may impair the functioning of ment programme for the Experimental Gas-Cooled
reactor parts and reduce their lifetime. This, in Reactor.
turn, would increase the shut-down periods of r e -
actors for maintenance and repair work, with a cor- R. Darras, D. Lecleroq and H. Loriers
responding rise in operating cost. This factor is of (France) described corrosion effects of carbon di-
considerable importance in view of the large capital oxide on structural steel at average temperatures of
between 450°C and 550°C under pressure. The vary-
outlay on reactors.
ing compositions of both the steel and the gases used
A second consideration in this connection is the gave revealing but often very widely varying results.
possibility of hazards, which may arise from the pol-
H. E. McCoy J r . (USA) discussed various
lution of the primary cooling system with highly radio-
types of gas-metal interactions and their effect upon
active fission products resulting from severe dam-
the service performance of metal. These investi-
age to fuel element claddings. On the other hand, a gations were undertaken to render possible an in-
corrosion-induced leak in the primary circuit may crease in the operating temperature of gas-cooled
lead to heavy contamination of the adjacent installa- reactors by selecting suitable structural materials
tions or even of the surroundings. Products of such and fuel element claddings. The experiments were
corrosion may not only impair the flow of cooling liq- carried out over a temperature range of 700°"90O"C
uids within the heat exchanger and cooling systems with stainless steels, nickel-based alloys and r e -
of reactors; they may also become radioactive them- fractory metals in environments of argon, hydrogen,
selves and contaminate the whole system. This carbon monoxide, carbon dioxide, nitrogen, air and
could give rise to considerable radiation hazards. In oxygen. Studies on the kinetics of electrode pro-
addition, radioactive contamination may necessitate cesses of low-alloy chrome and chrome-nickel stain-
a prolonged decontamination shut-down of a reactor, less steels and aluminium alloys at temperatures of
with corresponding financial loss. up to 300°C and pressures of up to 87 atmospheres
Since, broadly speaking, the efficiency of a re- were described by V. V. Gerasimov (USSR). The
actor increases with precisely those factors which data obtained from these studies made it possible to
also increase corrosion (primarily rise of tempera- forecast the corrosion behaviour of structural ma-
ture), corrosion resistance assumes considerable terials at critical temperatures in water of any com-
economic importance. position.

29

B. considerable diffusion of the oxygen in the underlying ing simultaneously. Humidity and the presence of hydrogen . metal . was discussed by a number of experts. tions. content. M. Alloys with extremely low silicon content influenced by temperatures. pressurized-water reactors . Asher (UK). Grail. the temperature and on the nature of the neutron flux. into the formation of oxide layers on high the kinetics of oxidation of non-alloyed zirconium in purity aluminium and its alloys. Coriou. The authors showed that a changes in corrosion rate. It was observed that the growth of thin oxide films could be attributed to irradiation with gamma r a y s . nickel and niobium have a high rials. He said that because of was incorporated into graphite and the gasification of the improved mechanical qualities which this alloy the graphite was studied by measuring the carbon-14 showed after appropriate heat treatment. Olkhovnikov and A. Draley and W. L. P . K". Ruther (USA). The corrosion of Zircaloy in various alkaline Corrosion of aluminium alloys in high temper. They showed that the formation which opens the circuit at certain pre-set voltages of and growth of a surface oxide film is accompanied by the electric current and of an electronic timer work. the silicon con.a phenomenon which makes the metal more brittle. it was in- activity. Carbon-14 S. I. exist in the formation of oxide films. Yu. A. Cox and R. addition to the one per cent nickel normally incorpor. "critical threshold" exists in regard to lithium hy- tent of aluminium-nickel-iron alloys was found to droxide concentrations. certain other graphites of widely different origins was practically ions. M. E.V. Cope stake and F. Also. (USSR) reported on experimental work on the resist. The effect of reactor irradiation on the oxida- On the other hand. J. According to study by H. one of the most important nuclear materials used in producing corrosion-resistant al. The effect of hydrogen on metals which a r e loys. On the other hand. Lang and P . Brabers (Belgium) described investiga- tions. also with lead. p r e s s u r e s . made by means of a so-called "transito. Sudarikova. S. Studies on corrosion resistance of a zir- carbon dioxide-cooled reactor was described by conium-niobium alloy were also dealt with by T. corrosion and H. resistant than the ordinary ones. Zotov and V. Alloys of zirconium with niobium and cant influence on corrosion resistance of these mate. Zirconium. Various impurities had a signifi. zirconium alloys at the temperatures in question. The presence of insignificant concentra- F. have practically no effect on the corrosion of showed a very definite influence. rosion takes place. on the effects of the composition of water on corro- ples in a stream of liquid sodium at temperatures of sion of zirconium alloys at high temperatures and 600°C and 700°C. carbon and carbon dioxide in a graphite-moderated. Dalgaard (Canada). considerable variations ated in aluminium for high temperature performance.was the object of a ditions under which the tests are run. C. J. in- by coolant gases. J. iron. Magnier (France) gave an tions of certain ions in the water. The purpose of using rates largely vary when there is a high rate of flow these media is to make the corrosion products more of water past metal surface. corrosion resistance in pure distilled water at 360° C. media at high temperature . B. Videm (Norway) dis. which activate reactions under normal condi- the same. S. They pointed out that filterable and so to reduce considerably the contam- seemingly minor variations in conditions cause large ination of the circuits. Lyashenko. E. Lehr (France) discussed meter". the speed of oxi. Neunier. The "transitometer" a dry oxygen atmosphere at temperatures of between comprises a constant current source and a switch 600°C and 850°C. M. reported ance to corrosion of various construction steel sam. Feates (UK). It was found that the corrosion duces intensified corrosion of zirconium alloys at effect on numerous highly purified carbons and high temperatures.Pelras J. dependent on These alloys were found to be more corrosion. normally covered and more o r less protected by an 30 . Willermoz (France). Debuigne and P . tended to use it for the fabrication of pressure tubes in Canadian power reactors. V. Ivanov A group of Soviet scientists. V. According to their findings. which under nor- account of experiments on the corrosion of graphite mal conditions would be absolutely harmless. tion of zirconium alloys in steam was the subject of cussed alloys containing about ten per cent silicon in a paper presented by B. A. The varying nature of the effect of the ions was stat- ed to be connected with their influence on the char- The use of carbon-14 for the study of carbon acteristics of the protective films formed on the transport in the radiation-induced reaction between surface of zirconium alloys. Rosenfeld. in place of the Zircaloy Aluminium and Zirconium Alloys used at present.which is of interest in ature water (260°-315°C) depends partly on the con. above which very rapid cor- have an important influence on their corrosion be. For ammonia no such behaved better than those with a more typical silicon threshold was noted. dation depended on the temperature. either increasing or lowering it. and that this threshold is greatly haviour. L.

C. One ic energy within several years. Cestmfr Simrfne. 31 . eral tests to demonstrate the excellent corrosion re. The theoretical aspect of corrosion by liquid metals was discussed by J. Weeks and C. quoted. Kemme nation itself is essentially a controlled corrosion (USA) pointed out that molten plutonium alloys may process in which the film is removed along with a combine some of the advantages of fluid fuels with small amount of the underlying metal. Nehru (UK). particular importance being removed for inspection. but this very realization was a factor of sive compounds. Bid well. Zirconium alloys also Lithium has been regarded as a promising show some improvements. C. Hoffman (USA) reported ful whether. M. "In general. We have heard about the coolant for power reactors for some time. in this case. actor materials. The results showed that all the materials With irradiation as well. results from different countries For the Molten Salt Reactor Experiment at the Oak agreed rather satisfactorily or complemented one Ridge National Laboratory. Director of IAEA's Division verely in the presence of small amounts of water. but also by an en- tainer material. Leach and Other Procedures and Summing Up A. said that the papers dealing with technological corrosion rate due to the presence of radiation was aspects had been more impressive than the theoreti- noted. had free hydrogen as well as certain organics which are shown how little we actually knew regarding cor- then capable of reacting with oxygen to form corro. The precondition for their inhibitors. J. J. content will further improve the corrosion resistance tainer materials with molten lithium. by organic coolants when used with common materi- but I am sure that later on still much higher temper- als and with metallic nuclear fuels. In that described by W. as somebody remarked. It is doubt- J. Ayres (USA). Di Stefano and E. alloys. reactors or of parts of the primary system was dealt tonium fuel. representing an increase of 200 degrees which is quite considerable. corrosion occurs only as a r e - sult of certain impurities. B. E. Magnesium corroded se. This point may al- of these properties is the low corrosion rate shown ready have been reached in the case of aluminium. Decontamination of attaches to corrosion effects caused by molten plu. 150°C was considered the maximum temperature for sistance of this material to molten fluorides at high aluminium alloys. a high-strength another very well. De Van in the improvement of corrosion resistance to r e - and R. as compared to water. for example. magnesium and some of their radiation is already difficult enough to understand. Corrosion is caused not only directly utilization is the development of the appropriate con. of Technical Supplies. J. R. cooled and -moderated reactors because of certain it may well be less the corrosion than mechanical superior physical and chemical properties which or- aspects which will be the determining factor in atom- ganic liquids possess. S. some years ago. " in their pure form. zirconium. speaking at the closing s e s - hydrogen attacked zirconium. but it was pointed out that radiation produces cal contributions. A. R. in a summing-up of the discussions. hanced rate of attack during subsequent operation as a result of the removal of the protective film. Brabers. Burwell and J. who gave the re. L. E. atures will be given. If the improvements in corrosion resist- Special interest attaches to the use of organic- ance continue at the rate achieved over recent years. increasing the niobium on experiments on the compatibility of various con. chairman of the last session. J. USA. with in a paper by J. Y. he said. Excessive the high breeding ratios that are possible with fast corrosion is suppressed by the addition of suitable Plutonium r e a c t o r s . Thamer. etc. beneficial effects of niobium and copper. P. by the decontamination process. Gellings (Netherlands) suggested a pro- Problems in A d v a n c e d Reactors cedure which would make it possible to follow the Since the prospect of economic nuclear power corrosion of test pieces inside a reactor or even of depends to a considerable extent on the possibility of the reactor material itself without the need of their developing breeder reactors. This week the figure 350°C was temperatures. H. R. Evans (USA) described the results of sev. B. Hammond. but sults of tests carried out on different types of steel. E. Parkins (USA). Irradiation may have many Corrosion effects with organic coolants were effects like face changes.oxide layer was discussed by J. dislocations. The conference. corrosion without any ir- aluminium. Great progress has been made nickel-base alloy has been developed. No increase in the sion. progress. in view of the enormous effects of the heat treat- ments. M. P . respect the material presented was still limited. said: A reactor with the fuel material homogeneously distributed in molten fluoride salts is considered to be a promising concept for future power reactors. J. Decontami- R. rosion. Klamut (USA). a whole series of compli- tested a r e essentially inert to the organic coolants cations is added to the problems.