Tag Archives: tritium

Isotopic effects in hydrogen diffusion in metals

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For most people, there is a fundamental difference between solids and fluids. Solids have long-term permanence with no apparent diffusion; liquids diffuse and lack permanence. Put a penny on top of a dime, and 20 years later the two coins are as distinct as ever. Put a layer of colored water on top of plain water, and within a few minutes you’ll see that the coloring diffuse into the plain water, or (if you think the other way) you’ll see the plain water diffuse into the colored.

Now consider the transport of hydrogen in metals, the technology behind REB Research’s metallic  membranes and getters. The metals are clearly solid, keeping their shapes and properties for centuries. Still, hydrogen flows into and through the metals at a rate of a light breeze, about 40 cm/minute. Another way of saying this is we transfer 30 to 50 cc/min of hydrogen through each cm2 of membrane at 200 psi and 400°C; divide the volume by the area, and you’ll see that the hydrogen really moves through the metal at a nice clip. It’s like a normal filter, but it’s 100% selective to hydrogen. No other gas goes through.

To explain why hydrogen passes through the solid metal membrane this way, we have to start talking about quantum behavior. It was the quantum behavior of hydrogen that first interested me in hydrogen, some 42 years ago. I used it to explain why water was wet. Below, you will find something a bit more mathematical, a quantum explanation of hydrogen motion in metals. At REB we recently put these ideas towards building a membrane system for concentration of heavy hydrogen isotopes. If you like what follows, you might want to look up my thesis. This is from my 3rd appendix.

Although no-one quite understands why nature should work this way, it seems that nature works by quantum mechanics (and entropy). The basic idea of quantum mechanics you will know that confined atoms can only occupy specific, quantized energy levels as shown below. The energy difference between the lowest energy state and the next level is typically high. Thus, most of the hydrogen atoms in an atom will occupy only the lower state, the so-called zero-point-energy state.

A hydrogen atom, shown occupying an interstitial position between metal atoms (above), is also occupying quantum states (below). The lowest state, ZPE is above the bottom of the well. Higher energy states are degenerate: they appear in pairs. The rate of diffusive motion is related to ∆E* and this degeneracy.

A hydrogen atom, shown occupying an interstitial position between metal atoms (above), is also occupying quantum states (below). The lowest state, ZPE is above the bottom of the well. Higher energy states are degenerate: they appear in pairs. The rate of diffusive motion is related to ∆E* and this degeneracy.

The fraction occupying a higher energy state is calculated as c*/c = exp (-∆E*/RT). where ∆E* is the molar energy difference between the higher energy state and the ground state, R is the gas constant and T is temperature. When thinking about diffusion it is worthwhile to note that this energy is likely temperature dependent. Thus ∆E* = ∆G* = ∆H* – T∆S* where asterisk indicates the key energy level where diffusion takes place — the activated state. If ∆E* is mostly elastic strain energy, we can assume that ∆S* is related to the temperature dependence of the elastic strain.

Thus,

∆S* = -∆E*/Y dY/dT

where Y is the Young’s modulus of elasticity of the metal. For hydrogen diffusion in metals, I find that ∆S* is typically small, while it is often typically significant for the diffusion of other atoms: carbon, nitrogen, oxygen, sulfur…

The rate of diffusion is now calculated assuming a three-dimensional drunkards walk where the step lengths are constant = a. Rayleigh showed that, for a simple cubic lattice, this becomes:

D = a2/6τ

a is the distance between interstitial sites and t is the average time for crossing. For hydrogen in a BCC metal like niobium or iron, D=

a2/9τ; for a FCC metal, like palladium or copper, it’s

a2/3τ. A nice way to think about τ, is to note that it is only at high-energy can a hydrogen atom cross from one interstitial site to another, and as we noted most hydrogen atoms will be at lower energies. Thus,

τ = ω c*/c = ω exp (-∆E*/RT)

where ω is the approach frequency, or the amount of time it takes to go from the left interstitial position to the right one. When I was doing my PhD (and still likely today) the standard approach of physics writers was to use a classical formulation for this time-scale based on the average speed of the interstitial. Thus, ω = 1/2a√(kT/m), and

τ = 1/2a√(kT/m) exp (-∆E*/RT).

In the above, m is the mass of the hydrogen atom, 1.66 x 10-24 g for protium, and twice that for deuterium, etc., a is the distance between interstitial sites, measured in cm, T is temperature, Kelvin, and k is the Boltzmann constant, 1.38 x 10-16 erg/°K. This formulation correctly predicts that heavier isotopes will diffuse slower than light isotopes, but it predicts incorrectly that, at all temperatures, the diffusivity of deuterium is 1/√2 that for protium, and that the diffusivity of tritium is 1/√3 that of protium. It also suggests that the activation energy of diffusion will not depend on isotope mass. I noticed that neither of these predictions is borne out by experiment, and came to wonder if it would not be more correct to assume ω represent the motion of the lattice, breathing, and not the motion of a highly activated hydrogen atom breaking through an immobile lattice. This thought is borne out by experimental diffusion data where you describe hydrogen diffusion as D = D° exp (-∆E*/RT).

Screen Shot 2018-06-21 at 12.08.20 AM

You’ll notice from the above that D° hardly changes with isotope mass, in complete contradiction to the above classical model. Also note that ∆E* is very isotope dependent. This too is in contradiction to the classical formulation above. Further, to the extent that D° does change with isotope mass, D° gets larger for heavier mass hydrogen isotopes. I assume that small difference is the entropy effect of ∆E* mentioned above. There is no simple square-root of mass behavior in contrast to most of the books we had in grad school.

As for why ∆E* varies with isotope mass, I found that I could get a decent explanation of my observations if I assumed that the isotope dependence arose from the zero point energy. Heavier isotopes of hydrogen will have lower zero-point energies, and thus ∆E* will be higher for heavier isotopes of hydrogen. This seems like a far better approach than the semi-classical one, where ∆E* is isotope independent.

I will now go a bit further than I did in my PhD thesis. I’ll make the general assumption that the energy well is sinusoidal, or rather that it consists of two parabolas one opposite the other. The ZPE is easily calculated for parabolic energy surfaces (harmonic oscillators). I find that ZPE = h/aπ √(∆E/m) where m is the mass of the particular hydrogen atom, h is Plank’s constant, 6.63 x 10-27 erg-sec,  and ∆E is ∆E* + ZPE, the zero point energy. For my PhD thesis, I didn’t think to calculate ZPE and thus the isotope effect on the activation energy. I now see how I could have done it relatively easily e.g. by trial and error, and a quick estimate shows it would have worked nicely. Instead, for my PhD, Appendix 3, I only looked at D°, and found that the values of D° were consistent with the idea that ω is about 0.55 times the Debye frequency, ω ≈ .55 ωD. The slight tendency for D° to be larger for heavier isotopes was explained by the temperature dependence of the metal’s elasticity.

Two more comments based on the diagram I presented above. First, notice that there is middle split level of energies. This was an explanation I’d put forward for quantum tunneling atomic migration that some people had seen at energies below the activation energy. I don’t know if this observation was a reality or an optical illusion, but present I the energy picture so that you’ll have the beginnings of a description. The other thing I’d like to address is the question you may have had — why is there no zero-energy effect at the activated energy state. Such a zero energy difference would cancel the one at the ground state and leave you with no isotope effect on activation energy. The simple answer is that all the data showing the isotope effect on activation energy, table A3-2, was for BCC metals. BCC metals have an activation energy barrier, but it is not caused by physical squeezing between atoms, as for a FCC metal, but by a lack of electrons. In a BCC metal there is no physical squeezing, at the activated state so you’d expect to have no ZPE there. This is not be the case for FCC metals, like palladium, copper, or most stainless steels. For these metals there is a much smaller, on non-existent isotope effect on ∆E*.

Robert Buxbaum, June 21, 2018. I should probably try to answer the original question about solids and fluids, too: why solids appear solid, and fluids not. My answer has to do with quantum mechanics: Energies are quantized, and always have a ∆E* for motion. Solid materials are those where ω exp (-∆E*/RT) has unit of centuries. Thus, our ability to understand the world is based on the least understandable bit of physics.

Nuclear fusion

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I got my PhD at Princeton University 33 years ago (1981) working on the engineering of nuclear fusion reactors, and I thought I’d use this blog to rethink through the issues. I find I’m still of the opinion that developing fusion is important as the it seems the best, long-range power option. Civilization will still need significant electric power 300 to 3000 years from now, it seems, when most other fuel sources are gone. Fusion is also one of the few options for long-range space exploration; needed if we ever decide to send colonies to Alpha Centauri or Saturn. I thought fusion would be ready by now, but it is not, and commercial use seems unlikely for the next ten years at least — an indication of the difficulties involved, and a certain lack of urgency.

Oil, gas, and uranium didn’t run out like we’d predicted in the mid 70s. Instead, population growth slowed, new supplies were found, and better methods were developed to recover and use them. Shale oil and fracking unlocked hydrocarbons we thought were unusable, and nuclear fission reactors got better –safer and more efficient. At the same time, the more we studied, the clearer it came that fusion’s technical problems are much harder to tame than uranium fission’s.

Uranium fission was/is frighteningly simple — far simpler than even the most basic fusion reactor. The first nuclear fission reactor (1940) involved nothing more than uranium pellets in a pile of carbon bricks stacked in a converted squash court at the University of Chicago. No outside effort was needed to get the large, unstable uranium atoms split to smaller, more stable ones. Water circulating through the pile removed the heat released, and control was maintained by people lifting and lowering cadmium control rods while standing on the pile.

A fusion reactor requires high temperature or energy to make anything happen. Fusion energy is produced by combining small, unstable heavy hydrogen atoms into helium, a bigger more stable one, see figure. To do this reaction you need to operate at the equivalent of about 500,000,000 degrees C, and containing it requires (typically) a magnetic bottle — something far more complex than a pile of graphic bricks. The reward was smaller too: “only” about 1/13th as much energy per event as fission. We knew the magnetic bottles were going to be tricky, e.g. there was no obvious heat transfer and control method, but fusion seemed important enough, and the problems seemed manageable enough that fusion power seemed worth pursuing — with just enough difficulties to make it a challenge.

Basic fusion reaction: deuterium + tritium react to give helium, a neutron and energy.

Basic fusion reaction: deuterium + tritium react to give helium, a neutron and energy.

The plan at Princeton, and most everywhere, was to use a TOKAMAK, a doughnut-shaped reactor like the one shown below, but roughly twice as big; TOKAMAK was a Russian acronym. The doughnut served as one side of an enormous transformer. Hydrogen fuel was ionized into a plasma (a neutral soup of protons and electrons) and heated to 300,000,000°C by a current in the TOKOMAK generated by varying the current in the other side of the transformer. Plasma containment was provided by enormous magnets on the top and bottom, and by ring-shaped magnets arranged around the torus.

As development went on, we found we kept needing bigger and bigger doughnuts and stronger and stronger magnets in an effort to balance heat loss with fusion heating. The number density of hydrogen atoms per volume, n, is proportional to the magnetic strength. This is important because the fusion heat rate per volume is proportional to n-squared, n2, while heat loss is proportional to n divided by the residence time, something we called tau, τ. The main heat loss was from the hot plasma going to the reactor surface. Because of the above, a heat balance ratio was seen to be important, heat in divided by heat out, and that was seen to be more-or-less proportional to nτ. As the target temperatures increased, we found we needed larger and larger nτ reactors to make a positive heat balance. And this translated to ever larger reactors and ever stronger magnetic fields, but even here there was a limit, 1 billion Kelvin, a thermodynamic temperature where the fusion reaction went backward and no energy was produced. The Princeton design was huge, with super strong, super magnets, and was operated at 300 million°C, near the top of the reaction curve. If the temperature went above or below this temperature, the fire would go out. There was no room for error, but relatively little energy output per volume — compared to fission.

Fusion reaction options and reaction rates.

Fusion reaction options and reaction rates.

The most likely reaction involved deuterium and tritium, referred to as D and T. This was the reaction of the two heavy isotopes of hydrogen shown in the figure above — the same reaction used in hydrogen bombs, a point we rarely made to the public. For each reaction D + T –> He + n, you get 17.6 million electron volts (17.6 MeV). This is 17.6 million times the energy you get for an electron moving over one Volt, but only 1/13 the energy of a fission reaction. By comparison, the energy of water-forming, H2 + 1/2 O2 –> H2O, is the equivalent of two electrons moving over 1.2 Volts, or 2.4 electron volts (eV), some 8 million times less than fusion.

The Princeton design involved reacting 40 gm/hr of heavy hydrogen to produce 8 mol/hr of helium and 4000 MW of heat. The heat was converted to electricity at 38% efficiency using a topping cycle, a modern (relatively untried) design. Of the 1500 MWh/hr of electricity that was supposed to be produced, all but about 400 MW was to be delivered to the power grid — if everything worked right. Sorry to say, the value of the electricity did not rise anywhere as fast as the cost of the reactor and turbines. Another problem: 1100 MW was more than could be easily absorbed by any electrical grid. The output was high and steady, and could not be easily adjusted to match fluctuating customer demand. By contrast a coal plant’s or fuel cell’s output could be easily adjusted (and a nuclear plant with a little more difficulty).

Because of the need for heat balance, it turned out that at least 9% of the hydrogen had to be burnt per pass through the reactor. The heat lost per mol by conduction to the wall was, to good approximation, the heat capacity of each mol of hydrogen ions, 82 J/°C mol, times the temperature of the ions, 300 million °C divided by the containment time, τ. The Princeton design was supposed to have a containment of about 4 seconds. As a result, the heat loss by conduction was 6.2 GW per mol. This must be matched by the molar heat of reaction that stayed in the plasma. This was 17.6 MeV times Faraday’s constant, 96,800 divided by 4 seconds (= 430 GW/mol reacted) divided by 5. Of the 430 GW/mol produced in fusion reactions only 1/5 remains in the plasma (= 86 GW/mol) the other 4/5 of the energy of reaction leaves with the neutron. To get the heat balance right, at least 9% of the hydrogen must react per pass through the reactor; there were also some heat losses from radiation, so the number is higher. Burn more or less percent of the hydrogen and you had problems. The only other solution was to increase τ > 4 seconds, but this meant ever bigger reactors.

There was also a material handling issue: to get enough fuel hydrogen into the center of the reactor, quite a lot of radioactive gas had to be handled — extracted from the plasma chamber. These were to be frozen into tiny spheres of near-solid hydrogen and injected into the reactor at ultra-sonic velocity. Any slower and the spheres would evaporate before reaching the center. As 40 grams per hour was 9% of the feed, it became clear that we had to be ready to produce and inject 1 pound/hour of tiny spheres. These “snowballs-in-hell” had to be small so they didn’t dampen the fire. The vacuum system had to be able to be big enough to handle the lb/hr or so of unburned hydrogen and ash, keeping the pressure near total vacuum. You then had to purify the hydrogen from the ash-helium and remake the little spheres that would be fed back to the reactor. There were no easy engineering problems here, but I found it enjoyable enough. With a colleague, I came up with a cute, efficient high vacuum pump and recycling system, and published it here.

Yet another engineering challenge concerned the difficulty of finding a material for the first-wall — the inner wall of the doughnut facing the plasma. Of the 4000 MW of heat energy produced, all the conduction and radiation heat, about 1000 MW is deposited in the first wall and has to be conducted away. Conducting this heat means that the wall must have an enormous coolant flow and must withstand an enormous amount of thermal stress. One possible approach was to use a liquid wall, but I’ve recently come up with a rather nicer solid wall solution (I think) and have filed a patent; more on that later, perhaps after/if the patent is accepted. Another engineering challenge was making T, tritium, for the D-T reaction. Tritium is not found in nature, but has to be made from the neutron created in the reaction and from lithium in a breeder blanket, Li + n –> He + T. I examined all possible options for extracting this tritium from the lithium at low concentrations as part of my PhD thesis, and eventually found a nice solution. The education I got in the process is used in my, REB Research hydrogen engineering business.

Man inside the fusion reactor doughnut at ITER. He'd better leave before the 8,000,000°C plasma turns on.

Man inside the fusion reactor doughnut at ITER. He’d better leave before the 8,000,000°C plasma turns on.

Because of its complexity, and all these engineering challenges, fusion power never reached the maturity of fission power; and then Three-mile Island happened and ruined the enthusiasm for all things nuclear. There were some claims that fusion would be safer than fission, but because of the complexity and improvements in fission, I am not convinced that fusion would ever be even as safe. And the long-term need keeps moving out: we keep finding more uranium, and we’ve developed breeder reactors and a thorium cycle: technologies that make it very unlikely we will run out of fission material any time soon.

The main, near term advantage I see for fusion over fission is that there are fewer radioactive products, see comparison.  A secondary advantage is neutrons. Fusion reactors make excess neutrons that can be used to make tritium, or other unusual elements. A need for one of these could favor the development of fusion power. And finally, there’s the long-term need: space exploration, or basic power when we run out of coal, uranium, and thorium. Fine advantages but unlikely to be important for a hundred years.

Robert E. Buxbaum, March 1, 2014. Here’s a post on land use, on the aesthetics of engineering design, and on the health risks of nuclear power. The sun’s nuclear fusion reactor is unstable too — one possible source of the chaotic behavior of the climate. Here’s a control joke.