Sunday, May 30, 2010

Superalloys: the choice for GenIV?

My previous post (Metallurgy: Austenite vs. ferrite) generated some great comments. There's a lot of interest in the possibility of using nickel-based superalloys (such as the Hastelloys) for major components in GenIV fast reactors. In between the day job and some business travel, I did as much reading as I could along these lines. First, I summarize some of what I've learned from my reading, and then go out on a limb with my crystal ball regarding the use of superalloys in next-gen reactors.

But before even the first item, let's take a quick aside. One of the "new things" in the superalloy literature are cobalt-based alloys for applications such as fossil-fired turbines. We can dismiss this possibility for the simple reason that cobalt and neutrons don't mix -- 59Co activates to 60Co, and becomes a significant radiological hazard to the reactor personnel. We can rest assured than cobalt-based superalloys, and even nickel-based superalloys containing more than a trace quantity of cobalt, are ruled out.

Superalloys are the ne plus ultra for high-temperature, high-corrosion applications in non-nuclear environments. Jet engines and stationary gas turbines, as we know them today, would be utterly impossible without superalloys. Because any thermodynamic system becomes more efficient as the temperature increases, superalloys are constantly creeping up to higher and higher operating temperatures. (American Airlines, for example, would fork over big cash to a jet engine company that can cut their fuel cost per mile even a small amount.)

The fast reactor research programs in the 70s produced quite a lot of irradiation data for superalloys. The Rowcliffe et al. paper summarizes them quite readably [1]. Murty and Charit [2] and Nanstad et al. [3] also cover on the topic.

Superalloys gain their spectacular high-temperature behavior due to the presence of "gamma-prime" and "gamma-double-prime" precipitates in their structure. These are tiny particles in the nickel-based matrix that pin "dislocations" (the basis of ductile deformation) up to very high temperatures. The main problems with using nickel in a reactor environment are twofold: (1) superalloys contain large numbers of alloying elements. Not quite half the periodic table, but it seems that way. These solutes move around under the gradients of defects produced during irradiation which destroys the gamma-prime and gamma-double-prime, produces new precipitates (with names like "eta" or "laves") which can embrittle the grain boundaries, and radiation induced segregation which can induce both brittle failure and corrosion at the grain boundaries. (2) Nickel is highly susceptible to (n,alpha) reactions, in which a neutron is absorbed by a nickel nucleus, causing it to kick off an alpha particle. This transmutes the nickel into a different element, and results in the alpha becoming a helium atom in the metal. Since helium has (effectively) zero solubility in metals, helium bubbles begin to form almost immediately. (Figure)

These helium bubbles are the primary cause of the swelling and shape-change seen in irradiated superalloys, which can affect the tight tolerances needed for precision machinery as well as weakening the material. Superalloys always contain some amount of carbon; radiation can induce the formation of M6C and M23C6 precipitates, where "M" denotes "metal", mostly Cr but with some fraction of the rest of the cations. These are blamed for destroying the swelling resistance of the material and allowing the helium bubbles to begin their dirty work. Murty and Charit suggest that superalloys should certainly be useful in regions of the reactor with lower radiation flux (i.e., steam generators) but more data is needed, as well as new alloys, to truly understand to what degree the radiation damage, particularly helium and swelling, can be ameliorated.

Nanstad et al. studied a series of alloys: Nickel-chrome-iron "800H", nickel-cobalt "617", and a series of steels. The 617 was interesting from a fundamental point of view, but its cobalt content (~12%) will make it uninteresting for real applications. The 800H showed appealing properties, especially when processed differently to improve its grain boundaries, but swelling due to transmutant helium is still a threat.

OK, so that's a quick once-over of some literature. Now comes opinion. GenIV reactors are going to show spectacular temperature / dose combinations, which will result in huge amounts of nickel transmutation to helium in any alloy. My guess -- and I emphasize that this is a guess -- is that any in-core metal parts are going to have to be nickel-free in these new reactor concepts. Rowcliffe et al. discussed concepts such as mechanical alloying to produce nanoclusters in the nickel superalloy matrix to vacuum up the point defects and helium, but this approach has really only been successful for ferritic steels. The problems of GenIV materials are simply extraordinary, and as a taxpayer and voter I say we need to pursue multiple parallel tracks of research towards the goal of clean energy via GenIV, including superalloys. But my personal crystal ball says that the oxide-dispersion-strengthened iron-chrome steels are the most likely solution.

(Figure is hotlinked and may go away, change, etc.)

[1] A. F. Rowcliffe, L. K. Mansur, D. T. Hoelzer and R. K. Nanstad: Perspectives on radiation effects in nickel-base alloys for applications in advanced reactors. Journal of Nuclear Materials V392, (2009), P.341-332.

[2] K. L. Murty and I. Charit: Structural materials for Gen-IV nuclear reactors: Challenges and opportunities. Journal of Nuclear Materials V383, (2008), P.189-195.

[3] R.K. Nanstad, D.A. McClintock, D.T. Hoelzer, L. Tan and T.R. Allen: High temperature irradiation effects in selected Generation IV structural alloys. Journal of Nuclear Materials V392, (2009), P. 331-340.

4 comments:

  1. The thing is Superalloys were developed for aviation and gas turbine applications and any that have reasonable performance in the nuclear field like Hastelloy N were developed for that purpose. Frankly I think that the hunt for high-performance nuclear materials along this route is going to run into diminishing returns very fast.

    I suspect that the future here belongs to high performance nano-composite non-oxide ceramics, as outright structural materials, for things like reactor pots, for MSR type designs.

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  2. My concern is those dpas:displacements per atom. In metals at high temp, you can expect the dpa-induced structural problems to anneal out, at least to some extent. Will they anneal out in the non-oxide ceramics?

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  3. Meredith, it's my understanding that there is some work being done with SiC, AlN and Si3N4 based fibres that looks promising and suggests that a composite tailored for high neutron damage resistance can be developed from these compounds. There is some evidence that there is some recovery via annealing in SiC systems, but it's too early to tell if it's useful from an engineering perspective.

    Too, these may need some sort of mechanical support depending on their structural properties.

    There is a way to go with ceramics no doubt, but I have a sinking feeling that we just might have reached a point with alloys where the cost is going to become prohibitive, both for the material itself, and the fabrication processes needed.

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  4. ok, quick question here from someone who doesn't know a great deal of structural engineering..

    Isn't one of the advantages of the MSR designs the fact that they are not 'fast' reactors but thermal ones, which hence implies that the neutrons are themselves slower when they hit the containment material than their fast reactor cousins?

    And hence that the helium bubbling that is described here is much less of a factor than it would otherwise be in, say an LFMBR?

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