Guys, I’m sad to announce that this is the last episode for a while/indefinitely. Thank you all for listening. I’m going to be focusing on school and other projects for most of the next year. I have no idea what Brian and Alex will be doing. Drinking probably. I hope that the podcast entertained people and gave them a glimpse into our weird little world. The facebook and tumblr pages will remain up, and I will leave the voicemail line open, just in case we revive the show.
Anyway, this last episode we talk about a lot of things, including Spider-Woman’s ass, the Golden Girls, and The Neverending Story. Enjoy.
We’re joined once again by Alex. This week we start off by mourning the passing of the Genie from Aladdin. We then spend a good chunk of the show getting deep into how hanging works. We then solve racism in the way that only three white guys can. We then cure ebola and discuss the physics of black holes. What more can one podcast do?
Do you know if deviled eggs are kosher or who the bad boy of volleyball is? Then leave a comment on Facebook, or leave us a voicemail at (609) 741-8837
Sodium Aluminum Hydride (NaAlH4) after high energy ball-milling for 10 min magnified 10,000X with scanning electron microscopy (SEM)
This is the second part of my posts about my the undergraduate physics research I participated in this summer. Check out part 1 here. When we left off I had received a space grant (GRANTS… IN… SPAAAAACE) that would pay me for an internship position at my school. I’m not going to lay out my two months of research as a chronological story because that seems rather boring to me. Instead, I’m going to give some background on the subject of my research, some of the cooler stuff I got to do, and what we found out. So, as I said in part 1, the scientists I was working with specialized in materials science, specifically hydrogen storage.
So, why do we care about storing hydrogen? Well, hydrogen can be used as a fuel for vehicles or for generating power. Basically we can store energy in the form of hydrogen and then burn it without releasing any greenhouse gases, just water. Greenhouse gases are bad. Actually, water vapor is technically a greenhouse gas but not one we’re as worried about as carbon dioxide. Also, we don’t really burn it, we use a hydrogen fuel cell to turn the hydrogen directly into electrical energy.
There’s a problem though. While hydrogen is a great energy carrier with a greater efficiency than gasoline, it has to be stored either under high pressure (5,000 – 10,000 psi) or at extremely low temperatures (lower than -252.8ºC)[1]. That really makes it not ideal as a fuel, especially in vehicle applications. High pressure tanks are heavy and that added weight reduces the overall efficiency of a hydrogen fuel cell vehicle. Plus, people get a little worried about having an explosive gas under high pressure in their car (even though gasoline is probably actually way more dangerous than hydrogen in that respect). Everyone starts thinking about the Hindenburg. Also, a pressurized tank has to be a certain shape, and you can’t just change that shape to fit it in nicely to the car like you can a gasoline tank. Cooling hydrogen down takes a lot of extra cooling equipment and insulation that also isn’t ideal.
So, storing hydrogen by itself has a lot of drawbacks. But, fear not, there are other ways we can store hydrogen. Materials hydrogen storage is a way to take those hydrogen atoms which want to shoot off into the atmosphere or turn into fireballs and bind them to some material in a solid state. Then, you just reverse that process to get the hydrogen back out. I say “just”, but it’s rarely this simple and sometimes the process is not reversible in any practical way.
One type of materials storage for hydrogen is complex chemical storage. This is where hydrogen is bound up in a molecule. This has some advantages in that you have a higher weight percentage of hydrogen in these molecules and many of them are stable at moderate pressures and temperatures (so no crazy heavy pressure or cryo tanks). This storage method has some drawbacks too. One is that because hydrogen is so tightly bound that it might require crazy high temperatures to get the hydrogen out (400ºC or higher) and some of these molecules are highly reactive with things like air and water.
To get a bit more specific, the material I was working with is called sodium alanate or sodium aluminum hydride (NaAlH4). A bunch of research has been done on this stuff since the early 2000’s because it seems promising as a way to store hydrogen and later release it. Now, if you watched the video I linked to in the previous paragraph, you may be asking, “Chris, why don’t you just mix the stuff with water and use that reaction to power your vehicle or power plant?” Good question reader. You actually could do that, and you would generate heat which you could use to boil water and turn a turbine of some kind. Mixing sodium aluminum hydride with water is a very violent reaction that’s extremely hard to control (but then again so is gasoline exploding). Believe me, I cleaned out a mixing vessel that had a light coating of NaAlH4 in it with water and a foot high jet of flame shot out of it. But, remember, we’re talking about hydrogen storage. We want this material to store hydrogen, release it, and then absorb it again over and over. The water and sodium alanate reaction is non-reversible.
The release of hydrogen, called dehydrogenation or desorption begins with the following two reactions:
NaAlH4↔1Na3AlH6+2Al+H2,
Na3AlH6↔3NaH+Al+3H2.
(There’s a third reaction where sodium lets go of hydrogen, but it occurs at temperatures that are too high for us to care about).
So, we want to heat up this material (usually a powder) so that it lets go of its hydrogen atoms and then use those atoms to power a fuel cell. We have two problems here. First, the temperature we have to heat it to is too high. Sodium Aluminum Hydride at atmospheric pressure initially begins to let go of its hydrogen atom at around 180° C. Producing the heat to get this reaction started takes energy, and using this energy reduces the overall efficiency of the system. Second, this hydride releases the hydrogen pretty slowly. At the minimum temperatures to begin releasing hydrogen it can take hours for all of the hydrogen to be released.
Luckily, many scientists have already figured out a way to reduce both the temperature and the time it takes for these dehydrogenation reactions to occur. First, they’ve found out that they can reduce the desorption/dehydrogenation temperature of this (and other) hydride(s) by doping them with catalysts. What the hell does that mean? Well, basically you take another material, like titanium trichloride (TiCl3) and mix a small amount of it (less than 10% by weight). This reduces the temperature at which hydrogen is released. How does it do this? That’s actually an unanswered question. There have been studies that have come to opposite conclusions about how dopants affect the desorption kinetics (how fast and at what temperature the release hydrogen) of hydrides. Science doesn’t always require that you start with a theory and then test it. Sometimes you can just do something and see what happens. In this case the why may be secondary to the what. What type and amount of dopant gives the best outcome (lowest desorption temperature) for sodium aluminum hydride?
What about the second problem of the reaction taking too long? Again, previous scientific studies have shown that if you mill the dry powder form of sodium aluminum hydride you get faster dehydrogenation reactions. Milling is basically taking the dry powder, sealing it in a jar with some ball bearings and then putting it into what is essentially a really high power paint shaker. A science shaker.
By the way, because sodium aluminum hydride reacts with oxygen and the moisture in the atmosphere it has to be kept in a dry nitrogen atmosphere. In my case it was kept in a glove box, which looks cool, but is a major pain to work with. Here’s a glovebox at the Advanced Photon Source at Argonne National Lab.
Science box.
The glovebox at Rowan was mostly metal, which was better for long term storage, but was much harder to work with. Who knew science could be so hard on your back?
So, all of that preceding was background on the subject. My actual research built on the work of those previous studies I mentioned and on the work of my advisor and her previous research students. What we were trying to figure out was; what happens to the structure of sodium aluminum hydride when we add these dopants and/or mill it, and how does this relate to how fast the hydride releases hydrogen.
There’s a few ways we can study the small-scale structure of materials. First we can use scanning electron microscopy (SEM). SEM is a lot like regular microscopy except that we use electrons instead of photons to probe smaller structures of materials. This works because electrons have a smaller wavelength than visible light. Yes, electrons have wavelengths. Quantum physics y’all.
Here’s a gif of a series of SEM images of sodium aluminum hydride.
Orders of magnitude magnifications of NaAlH4.
At the highest magnification, we’re looking at features on the order of nanometers. While this seem really small, it actually only probes the gross structure of this hydride. What did the SEM tell me? Well, the ball milled NaAlH4 is clumpier, an assuredly unscientific word, but if I show you a picture of the milled and un-milled NaAlH4 side-by-side, you can see what I mean.
“Neat” or unmilled, undoped NaAlH4 at 100X magnification.NaAlH4 milled for 10 minutes at 100X magnification.
As far as we know, these are the same materials, at the exact same magnification. The difference is pretty striking, huh? Why would this difference cause the hydrogen to desorb faster from the second powder? Well, that’s an open question, and one that we weren’t able to answer over the summer.
Now, you’ll remember that I said that SEM lets us look at the gross or large-scale structure of materials. Then how do we probe smaller structures? That’s where X-Rays come in. At Rowan we have a laboratory scale X-ray Diffraction machine. I actually used this device before I did any SEM scans. It’s a really neat machine.
Rayons Equis indeed.Crystal structure of sodium aluminum hydride. Yellow balls are sodium, blue balls are aluminum, and red balls are hydrogen.
I’m not going to go deep into the physics of it, but X-rays allow us to probe the atomic crystal lattice structure of materials.
Basically if there’s a regularly ordered crystal structure in your material then at certain angles the X-rays will constructively interfere with each other and produce peaks of high intensity in the detector, like so:
X-ray diffraction peaks for undoped NaAlH4 milled for 10 minutes.
These graphs actually come from data that we gathered at Argonne National Lab at this place,
Swag.
Using this detector,
X-ray detection array at APS to study the structure of matter. Major science biz happening here.
The major difference between our lab scale XRD and the one at APS is that the APS is way, way brighter, meaning it has way higher energies. It also has four different detectors that can measure a wider range of angles of scattering from the beam. This can give us different kinds of information about the structure of the materials. More on that later.
So at Argonne we took our powder and heated it up to 135° C and held it at that temperature for an hour, while scanning it with the X-ray detector periodically. Why that temperature? Well, for one thing it’s below the normal desorption temperature for NaAlH4, and it is also a temperature at which previous studies were conducted, so we could compare the new data directly to old data.
This is the “heating stage” that we put the sample powders in:
It kind of looks like a combo hard-drive and CD player.
So check this out, we heated samples doped with different catalysts and measured the crystal structure of each. Here’s an XRD graph of a doped sample:
Graph of X-ray diffraction peaks taken at room temp. and over time at 135 degrees C.
So, it looks pretty similar to the graph I post further up. The different colored lines represent the intensity of scattered electrons at various “d-spacings”. Basically, if there’s a peak, then that means there’s a repeating structure of atoms that is separated by that much distance in angstroms (0.0000000001 meters). The blue line is the scan taken at room temperature. Then going from the green to the orange, and then to the red line are measurement taken at 135º C over time. Okay, so look at the peaks I’ve marked with a dashed vertical line. See them? Those are known peaks for sodium aluminum hydride. We expect to see them because, as far as we know, our sample is crystalline NaAlH4. We’re interested in how these peaks change as the sample is continually heated. So far, so good. So check out those solid black vertical lines. Those lines indicate the presence of aluminum. That indicates that hydrogen desorption has begun. Now, go back up and look at the first XRD graph above. Do you see it? No aluminum lines! Oh dang. That means that we really have lowered the desorption temperature of our hydride. These lines are only present in the doped samples (there are more graphs of the other doped samples, but they’re very similar to the one above).
The third type of scan we did is called ultra-small angle X-ray scattering (USAXS). It uses the same beam as the XRD above, but with a different detector. This scan provides some more information about the non-crystal structure of the material. It’s based on a pretty complicated mathematical model that contains in it information about the size, shape, and fractality (if that’s a word) of populations of particles in the materials. A graph of USAXS data looks like this:
My humps my hump, my lovely USAXS bumps.
Okay, so that line that goes from upper left to to lower right, with the “hump” or “shoulder” near the lower right is the data obtained from the USAXS scan of our hydride. By applying the mathematical model known as “unified fit”, represented here by the magenta and green lines, and making several assumptions about the shape of the particles we can get an idea about the radius, and porosity of the particles in the material. Why is this important? Like I said before, we think that doping and milling cause structural changes to sodium aluminum hydride that lead to the effects on dehydrogenation that we see. USAXS is another way to look at structure. What did we learn from this data? Honestly, I’m not entirely sure. This model is way more complicated (to me) than XRD or SEM, so I have a bit of trouble wrapping my head around it. All I can say is that we need to do more research.
That’s pretty much it. This may be the longest thing I’ve written in a long time. I hope it held your attention. I even started to zone out writing it about half way through. I hope to put up more posts about my research when I start again in the fall, and about the sorts of things I’m learning in my classes in the fall.
Hey! Bonus episode this week! And we’re going to have another new episode next week! Exclamation points! We saw Guardians of the Galaxy! Only minor spoilers in this episode, so feel free to listen if you haven’t seen it (but do go see it because it’s awesome). Besides talking about Guardians we dedicate this episode to talking about fictional science, including the problem of the missing Ash mass, and the difference between a phaser and a disruptor. Plus, we have two, count ’em two, voicemails! A podcast record!
As always, if you like the show, follow us on Facebook, Tumblr, rate and review us on iTunes. Also, if you have a better idea about how evil Ash appeared outta nowhere, or how phasers work then leave us a voicemail at 609-741-8837 (609-SH1-TTER).
My research poster, presented at Rutgers University on August 1st 2014 (click to embiggen)
I thought it might be interesting to write a post about what I’ve been doing all summer besides making podcasts with my bro-host. To catch anyone up who doesn’t know (and to lay it out and consider it for myself) I’m an undergraduate student majoring in physics at Rowan University in Glassboro, NJ. It’s a very strange thing. I haven’t written much about it, though I’ve mentioned it several times on the aforementioned podcast. Being a 32 year old undergrad surrounded by 19 and 20 year olds is a little bizarre and disconcerting. For some reason I constantly feel the need to announce that I am, in fact, comparatively old. I don’t know why. If I had to guess I’d say it’s some sort of defense mechanism. I tend to, when confronted by something that may be awkward in the future, like having to explain that I am ten to twelve years older than everyone in the room, get nervous and blurt out the thing that is the source of my nervousness or anxiety. I’ve tried to cut back on it, because I think all it serves to do is build a wall between myself and my fellow students. All of that really has nothing to with my research, but I thought I’d get it down in written form because, like I said, I feel the need to blurt out the thing that is the source of my anxiety. Although, I think it might come back into play at the end of this post.
For those who don’t know, STEM fields (Science Technology Engineering and Mathematics) have boss internships. They’re usually paid and you usually get to jump into real life research with real life scientists right away. They’re called REU (Research Experience for Undergraduates) and they pay, on average, $4000 for 10 weeks of research. Now, an important piece of information is that I quit my job at Ace Hardware way back in March so that I could focus 100% on school (after failing my Linear Algebra mid-term and having to drop the class). It paid off actually and I ended up finishing my first year as a physics undergrad with a 4.0. But, I was living entirely on student loans, meaning I would have no income for the summer. My plan for the summer was to apply for a summer REU for both the money and the research experience. I applied to over 30 different internships. By the time most of the acceptance deadlines had happened in May, I had received over 30 rejection emails. Things were looking bleak. I really did not want to get a regular summer job.
Luckily, Rowan’s physics department took applications at the end of April for their summer internships, and I felt I had a pretty good chance to get one of those. Apparently it’s easier to get an internship at your home institution first and then do your next one someplace else. Around the same time, on the advice of the head of the department, I also applied for something called the New Jersey Space Grant. It’s a grant from NASA that supports aerospace research by students in New Jersey. The deadline for announcing the winners of that grant came and went, which was disappointing. However, I got an internship at Rowan, which meant that I didn’t have to get a summer job. Then, strangely enough I got an email saying that I got the NJ Space Grant. See, turns out that when I sent my application (by mail, because they only accepted application by mail for some weird reason) that they lost it and only found it again after they had announced internships. But, because I had a 4.0, they decided that I deserved that grant and so they gave it to me, but my internship position would remain at Rowan. Basically, I got slightly more money for my internship and Rowan got to keep the money they were going to pay me. Plus, I get to say that I won a Space Grant. SPACE! GRANT!
So, that brings me to the research part of my research. My field of interest is astronomy, you know, space stuff. However, my internship was with a researcher whose focus was on materials science. Don’t take that to mean that I don’t find materials science interesting, it’s just not what I plan on doing as a career. In fact, on day one I got to to learn how to use a big scary x-ray machine with the glowing radiation trefoil on it.
So ends part 1 of my summer research. I’m going to do a follow up post that focuses more on the research itself. So, if you want to know about that, come back in a week.
This week Alex again joins us and we talk about Old Boy(s), serial killers, weird mutant trucks, Jamie Foxx’s penis, bananas in pajamas, magnets and how they fuckin’ work, Amazing Spider-Man 2, we answer a listener question about the best remake of a beloved childhood property, and we can’t quite figure out what our phone number is.
As always, if you like the show, follow us on Facebook, Tumblr, rate and review us on iTunes. Also, if you have a better idea about how evil Ash appeared outta nowhere, or how phasers work then leave us a voicemail at 609-741-8837 (609-SH1-TTER).
Alex gets in on the Transformers rage that he missed on the previous episode. We discuss kaiju Kelsey Grammer, forming a Korean/Chinese football teams, the Spaceballs theme, movies about teachers and principals, the Kermit/Gonzo/Miss Piggy love triangle, sexy Bugs Bunny, mud runs, Mark Dacascos, Razor Ramon, Orange is the New Black, Doug, Big Bad Beetleborgs, Power Rangers, our favorite kinds of male porn stars, Tim Curry, and Dreamcatcher.
I have no idea what’s wrong with my mic in the beginning. It sounds muffled.
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Remember how last week we said we were going to see Transformers 4: Age of Extinction? Well, it was a mistake. Listen as we vent our rage for an hour on this piece of shit movie. Seriously, fuck this movie.
This week we talk about writer vampires, MRSA, the benefits of the metric system, dialysis, Brian’s dad Hodor, Game of Thrones, bittorrent, The Core, Rubik’s Cube, Farscape, Voyager, chubsandscrubs.tumblr.com, and of course Brian’s amazing idea for reality TV.
