SMS_F2014_12

Structural Materials Selection Fall 2014 Session · 8 sections 18 cases · Watch on YouTube ↗ all files
Layer 3 — readable edition

§1. Class business and the Hertz fellowship interview [00:00]

§1.p1

Where are we — anybody have any questions? I'm going to pass around the sign-up sheet for presentations. If your name is on here, it's because when I sent around the sign-up sheets you said you were available those days. We have forty people in the class. If your name is not anywhere on the sheet, please let me know, because then we don't know you're part of the course.

§1.p2

If I don't have to go out of town we'll finish before Halloween. If I have to go out of town we'll finish before Veterans Day, November 11th. I think the Armistice was at eleven o'clock — eleven, eleven, eighteen.

§1.p3

Does anybody have any questions? The schedules will come around. You should be signed up for one of the days you said. We'll start presentations next Wednesday. The presentation should be brief, no more than ten overheads, a focused subject. By focused I don't mean the automotive industry or the steel industry. Someone suggested they want to do Venetian glass — that sounds great to me. You can tell everybody what Venetian glass is and why it's different and what's interesting about it. The topic can be anything that's of interest to you.

§1.p4

I could tell you the story of when I interviewed for a Hertz fellowship. Hertz is the Hertz rental car fortune, and he was sort of a right-winger. Edward Teller was on his board of directors. The guy who interviewed me — if I tell someone at Lawrence Livermore National Lab that the guy who interviewed me was Lowell Wood, they say, "So you interviewed with Lowell Wood." Lowell Wood was Edward Teller's right-hand man. Edward Teller was the father of the hydrogen bomb — Hungarian, super right wing, advisor to Eisenhower and Kennedy.

§1.p5

I made the first round, and the second round was when they made the final decision. I was in the dean's conference room one evening interviewing with this guy, and frankly he was sort of a jerk. Everyone I've talked to since says, "Oh, you interviewed with him? Yeah, he was a jerk" — because that's how he ran Lawrence Livermore. He was the number two guy there at the time. He first asked me, who is Count Rumford? Anybody know who Count Rumford was? Neither did I. Count Rumford was a philanderer from Medford, Massachusetts who disproved the phlogiston theory of matter in the 1790s. He was reaming out gun barrels and he showed he could get an infinite amount of heat from friction, and therefore heat was not a constituent of the material — it was generated by the work. That was the early days of thermodynamics. Count Rumford was not actually a count. He went over to France so he could be a philanderer with some of the royal people and call himself Count Rumford. One of the deans here at MIT got really interested and wrote a book about him. I didn't have a clue.

§1.p6

So he asked another question: who unified the Prussian states in the 1870s? I said Metternich. At that time Henry Kissinger was an advisor to Nixon — early '70s. And I said Henry Kissinger did his doctoral thesis on Metternich. He was really impressed that I knew that. Big deal — I read it in some magazine. We got onto those questions because he said, "I've been asking you questions, why don't you pick the topic." I was sort of fed up with this jerk, and I said, well, how about cooking, because I like to cook. He said, "Well, I was thinking something more technical." I said okay, what about history. So we got onto Count Rumford and Metternich. The only thing that impressed him was that I knew Henry Kissinger's doctoral thesis topic. I didn't get the fellowship. I got an NSF fellowship instead.

§1.p7

So this sheet — please sign up if you haven't. We're scheduled through October 23rd. We've got three empty dates on these days and four empty slots on those days. Hopefully you can fit into some of this and we'll finish up early. Do something that's fun and interesting.

§2. Tempered and laminated glass [06:44]

§2.p1

We were talking about glass, and I mentioned that glass manufacturing productivity had improved markedly over the ages. I also mentioned glass is a brittle material, but it is a structural material. It has one very interesting property — it's transparent — and because it's transparent we want to use it in structures. The problem is, it actually corrodes. If you look at annealed glass, which comes out of the float glass process — float glass is produced virtually stress-free — and it breaks, it shatters, and it ends up with long sharp shards that have killed people when they walk through a glass door without realizing it. So now there are codes that you have to either use tempered glass or laminated glass. More often than not they use plastic in screen doors. Since you'd like to have something optically clear, we use glass in a number of different forms.

§2.p2

You have to anneal glass, because glass has low thermal conductivity, is brittle, and has small flaws that can cause it to crack and shatter with hazardous, potentially lethal shards. We have to do something to make it safer. What do they do on windshields, or side windows?

Student: Laminate it on the windshield, temper it on the side.

§2.p3

They laminate it, and on the side windows they temper it. They put a piece of plastic in between, they make a composite. If you've seen an accident where someone impacted their windshield, you'll see it breaks, but the plastic acts as a catcher's mitt and holds the stuff so it doesn't go shattering all over everywhere and cutting people.

§2.p4

Tempering is a process of heating the glass up to a range where it's in a viscous plastic state, and then cooling it rapidly — they're just blowing air on it. As you cool it rapidly, the top surface goes into tension because it's shrinking. With poor thermal conductivity the center is still warm and viscous, but because it's viscous it actually contracts while the outside is also contracting. The outside is going below what we call the strain point — the temperature at which glass will relax within about an hour. If you cool it rapidly in tens of seconds, you basically get the outside to harden up and the core to shrink. When you cool all the way down, the core has shrunk and everything gets back to uniform temperature, and the outside surface is in compression.

§2.p5

One of the rules of residual stresses due to thermal processes is that whatever stress you have at high temperatures will be reversed at low temperatures. At high temperatures you have tension on the surface, but at low temperatures you have compression on the surface, and you have to overcome those compressive stresses. If you look at the tempering plots, this is temperature through the thickness of the glass. You start cooling it down — quenching time in seconds, so this is over tens of seconds. The center cools down more slowly than the surface, and you set up these temperature gradients. When you get down to room temperature, you end up with a residual stress pattern that looks something like this — stress in megapascals. You can end up with compressive residual stresses on the order of 75 megapascals, which is not a whole lot. It's about 10 ksi. But 10 ksi compressive stress on the surface — as long as you don't break through that, you can bend the glass and put stresses of up to 10 ksi on there, whereas untempered glass would have a strength of about 1 ksi due to the notches from the float glass process.

§2.p6

Another thing we can do, since glass is an important material, is ion exchange. You take a glass — in this case they took a sodium aluminosilicate glass — and you do an ion exchange with potassium. You put it in a salt bath with potassium, and just because of entropy effects the sodium exchanges with the potassium. Potassium is a larger atom. You're doing this at relatively low temperatures, below any viscous diffusion, for hours. After four hours you can increase the strength of the glass from 140 megapascals — about 20 ksi — up to 400 megapascals. This is chemically tempered glass, where you get compressive residual stresses by exchanging large ions for small ions.

§3. The John Hancock Building and the depth of ion exchange [13:15]

§3.p1

The John Hancock building over here — when I was a student they were building it, and after they first built it, the winds came along, creating a suction force, and the windows were popping out of the building and falling to the ground.

Student: The Plywood Palace?

§3.p2

Yeah, probably the Plywood Palace. Someone who lived in the same house I was in, two years younger — the day after they put the top I-beam on, he snuck in, climbed up to the top and signed the top I-beam. He was sort of a risk taker. A couple of years later he died skydiving in Colorado when his parachute didn't open. But in any case, it's chemically tempered glass, because they needed a stronger glass — the building was flexing. They now have the building under a slight negative pressure, with big vents. And they took a whole floor and put a big weight in there. The swaying frequency of the building is several seconds, and it's a damper.

Student: Tuned mass damper?

§3.p3

Right, it's a seismic balance — not for earthquakes, but to keep the thing from bowing too much. They're reducing the vibration of the building. Most buildings just sway. About the same time I went to Chicago, went to the top of the Sears building. They have an observation deck, and you go in the restroom and you see the water sloshing in the toilet, because the building is sloshing. The John Hancock, they didn't want it to do that — they wanted to damp it seismically. They have a whole floor with a weight rotating in opposition to the wind motion. They spent a lot of money — hundreds of millions of dollars — to fix that building because they used glass as a structural material and ran into problems. Yes?

Student: [question about ion exchange depth]

§3.p4

No, it doesn't come down the whole profile. It's only the first two or three thousandths of an inch. This is typically a plate glass, a quarter of an inch thick, no thinner than an eighth of an inch. Float glass might be a sixteenth, an eighth, or 3/16. Plate glass is where you pour it on a steel plate and grind it and polish it — quarter inch to half inch or thicker. The ion exchange is relatively thin. You could scratch it with a glass cutter and not be beneath the chemically tempered compressive layer. But if you really got a good gouge in it — took a diamond and gouged — you'd get below that, and this'll shatter on you as you get into the tensile residual stresses on the inside. So they have to make it 50 microns deep, and that's why it takes hours to do. You put it in there, you'll get a very thin layer, but then that slab gets scratched, and now you've created a situation where you've stored energy in it and you release the spring and kapow. It's got to be a thick enough layer. But on a hard material like glass, it's hard to scratch it three thousandths deep. You can, but if you do you're in trouble.

§3.p5

I wish I had it, but Professor Uhlmann, who used to teach glass here when I was a student, had a piece of chemically tempered glass that was probably about eighteen inches long and bowed about three inches high, and he could put it on the table and just flatten it with his hand. He wasn't exceeding the compressive stresses in bending. This only works in bending, doesn't help in tension. But big flat sheets fail in bending. So it works. People have done a lot of things to make glass a useful material in spite of its brittleness. So all those things I said about how wonderful steel is because it has toughness — well, that's true, but people are clever enough to figure out how to make glass into something useful even though it's brittle.

§4. Transparent armor and the RPG problem [17:40]

§4.p1

Now, other stories. This is from protective armor systems. [Tom displays a transparent armor sample.] Three layers of glass with one layer of polycarbonate. Polycarbonate is a very tough plastic in its own right — about 10 ksi strength if you pull it slowly. They used to use it as a bullet stopper. Now there are copolymers — I just bought some Vitamixes for my children last night, and they use Eastman Chemical Tritan, a polyester copolymer. They used to make those out of polycarbonate, which is very tough and transparent. Now they make armor for bullets. This was an inch and a quarter, four layers adhesively bonded together. You can't have any bubbles in the adhesive — this has to go through an autoclave in a very controlled roller process. This will stop a 50 millimeter round. It does it by cracking the glass, absorbing the energy, hitting the next layer, cracking and shattering and absorbing the energy. Eventually it gets to the polycarbonate, and hopefully you've slowed it down enough.

§4.p2

That will not stop a rocket-propelled grenade — an RPG. However, they make things that are just under six inches thick that will stop an RPG. The president's limousine has five and three-quarter inch thick material made by these folks. It looks like a nice big car, but if you get in it, it's pretty scrunched inside. It is a big car, but the doors are about ten inches thick. It looks like a regular old Cadillac or Lincoln, but it's been modified. You can buy one yourself. A lot of sheikhs and other people in the Middle East buy these, because they have some enemies who would just as soon hit them with an RPG. Humvees might have something like that. The big things in Iraq —

Student: MRAPs.

§4.p3

MRAPs. The MRAPs were these sixty-ton personnel carriers that replaced the Humvees, because of the V-shape on the bottom. And it turns out six layers of glass as the armor.

§4.p4

What happened — I can't tell you everything because some of it's classified — but I used to sit on the committee that reviewed the materials and mechanics group at Aberdeen Proving Ground. This used to be the materials group out at Watertown — Watertown Arsenal Mall now. Since the 1860s that was the U.S. Army's materials lab. They used to make cannonballs there in the 1860s, in the mall area. Some of those buildings were almost original. They moved to Aberdeen Proving Ground, where the Army does all their ballistic studies, and built them a beautiful new building.

§4.p5

What happened was, the Secretary of the Army — we were losing a lot of soldiers in Iraq — came and said, look, you're our people who are supposed to be developing armor for us. We want you to solve this problem. Within eighteen months they solved it. Soldiers had been being blown up in their Humvees, but within eighteen months we quit losing soldiers being blown up in their Humvees. One guy on our committee was a captain who'd done two tours in the Middle East, and he said the most important thing was the eyes of the soldier. They go down a road every day, and if they saw anything change on the road, or within fifty yards of the road, they would stop and start looking for some buried whatever it was. These people weren't very sophisticated — they didn't have remote control. They'd be hiding twenty-five yards off the road ready to trigger the device when someone came by. The best thing was the eyes of the soldier. But in fact they developed things — they didn't know what armor was going to be best, so they tried steel, titanium, aluminum, glass. They had reasons to believe glass might be good. They just blew them up down there at Aberdeen, all within a month or two, and they found out glass was the best.

§4.p6

I can't tell you why, because that's classified, but glass worked better than anything else at repelling the rocket. These are shaped charges that send off a stream of molten copper that will just cut through steel and destroy aluminum. Sonic velocities of this massive dense copper that will cut through steel. A shaped charge that shoots out a thirty-six inch piece of copper will penetrate thirty-six inches of steel. I've seen the steel that was penetrated by one of these things. So you can't put thirty-six inches of steel underneath the V-shaped MRAP. You put six sheets of half-inch, three-quarter-inch glass. I can tell you that because any soldier out there can look and see that he's being protected by glass.

§4.p7

So hardness is an important property in armor protection. Glass is harder than steel. It's not stronger, because flaws will make it break. But if you cause it to break, you're absorbing energy. Maybe only one time, but you only need to do it one time. If you get hit by an RPG, you're probably not going to use that MRAP again anyway. Yes?

§5. Shaped charges, IEDs, and the armor-penetration race [24:36]

§5.p1

Student: Same kind of material used for IED protection and the underbelly of the Cougars?

§5.p2

Yeah. Improvised explosive devices are nothing more than shaped charges. Let me give you a little of the history. When they first went into Iraq — President George Bush's time — they would use a four-inch black iron pipe, just a steel pipe four inches in diameter. They'd put a bottom on it — machined or welded. Then you put the explosive in, and you have to have a piece of copper that's sort of dish-shaped, like a saucer. When you set off the charge, the copper folds outward — remember little clickers you had as a kid that you could click and they'd buckle? The copper bows outward, and as it does, the stress causes enough frictional heating that the copper melts. You end up getting what's called a shaped charge.

§5.p3

The U.S. Navy discovered this in the 1880s at the Brooklyn Navy Yard, by mistake, while they were doing some explosives work, and they found it would cut through steel. I wish I had one of Doc Edgerton's pictures of a milk drop splash — you have a drop of water come down in a little dish and it goes out in a wave and comes back as a wave, and when the wave comes back you get this big spike of milk. Basically all the copper melts from the energy of the explosion and the mechanical shape — it's called a shaped charge — and you form a jet of molten copper. That will eat through steel of equal thickness to the length of the jet, approximately.

§5.p4

RPGs have fins on the back so they'll fly. But the reason they have the shape is because they have a V-shaped piece of copper and the explosives down below, and it implodes and makes this big jet that will go right through a Humvee. Four-inch diameter — I think this was 200 kilojoules of energy. They got a little better and went to eight inches. The energy goes as the cube, so they went to 1.6 megajoules. That blew a Humvee into smithereens. People were dying in Humvees, so the Secretary of the Army came and said, you've got to do something.

§5.p5

Within eighteen months they designed and developed armor for the MRAP vehicles. The seats in the MRAP are sort of interesting — I got to sit in one. They're big shock absorbers, because if you get a 1.6 megajoule IED under you, even though it's shaped like a V for the armor to deflect the blast, it will still lift that sixty-thousand-pound vehicle four or five feet in the air, and you're taking off like a rocket too. So you have to be strapped in, with these big springs, so that you don't get a serious spine injury or hit your head on the ceiling and end up dying from a concussion. You don't want to be hit while you're in one of these, but it won't blow the thing to smithereens.

§5.p6

And of course, now that we've moved out of Iraq, what are they doing with the MRAPs? We read in the papers, they're giving them to the local National Guard. Where was it — Missouri — they come in after the riots, after the policeman killed the teenager, with their MRAP. So now the rioters in Missouri better have their eight-inch-diameter improvised explosive devices, and the police will be safe. Isn't it great.

§5.p7

To machine the copper disc you rely on symmetry — you can't just use any old machine shop, and there is no machine shop in Iraq that can make those. I can't tell you what country was giving these to the insurgents, because that's classified, but we know where it came from and who's doing the machining. All you had to do was take a little disc of copper, and pipe — they've got plenty of pipe in Iraq, that's what they use for the oil business. They just went from four inch to eight inch and they could wipe out Humvees.

§5.p8

The technology for weapons is sort of amazing. In 1985, they were first developing some of these really good RPGs. One of my students who was in the Army at the time, over at Watertown Arsenal doing his doctoral thesis, told me a story. They lined up three tanks on a battlefield — probably down at Aberdeen — and they shot an RPG, and it went through six layers of armor, through both sides of all three tanks. Apparently the general tossed his cookies right there on the battlefield. He just got sick.

§5.p9

Within a year they had developed new types of armor that could not be punctured. In 1984 there was no armor that could not be penetrated; by 1986 there was no propellant that could penetrate the modern armor. The modern armor was a composite — layered with metal and ceramic. It's actually a metallurgical reaction that allows the copper to go through steel — it's an embrittlement reaction of copper and steel. You put ceramic in between, you don't embrittle ceramic with copper, so you can stop it.

§5.p10

The other thing you can do is — these penetrators, I talked about depleted uranium. They might be a sabot, thirty-six inches long, half or three-quarter inch diameter depleted uranium rod shot out of a shoulder-mounted weapon or a tank weapon. When it hits, it gets stressed to close to 400,000 pounds per square inch. If you have on the surface of your armor an explosive that ignites and sends a shock wave through that rod, you'll send a stress wave through it that reflects off the other end, and the whole rod will shatter. So they have what they call explosive armor — armor with an explosive on the top surface.

§5.p11

That works great for the first shot. So what did I see in 1985? They were doing supercomputer modeling, and they had sabots with a twelve-inch piece that would set off the shock wave, and another twenty-four-inch piece right behind it that would go through the hole, because they'd already set off the explosive. Modeling this on supercomputers, finding ways to develop armor that couldn't be penetrated and penetrators that couldn't be defeated by armor. It's sort of gory, but it's interesting to see the technology that goes into this stuff. None of what I just told you is classified — you can find it in books. But there's plenty of stuff that is classified that I can't tell you about.

§6. Touchscreens, fusion-drawn glass, and humidity attack [33:42]

§6.p1

I want to tell you about your computer screens. They're glass. They're actually a composite. I showed you LED screens — they might be six or seven layers. You've got a layer of plastic on the very outside — nowadays we actually have glass on the outside because you have indium tin oxide, this transparent semiconductor that allows you to use a touch screen. It's very interesting to have a transparent material that conducts electricity. Ordinarily if it's transparent that means it doesn't absorb photons in the visible range, which is several electron volts. But if it conducts electrons, it's got to have some band gaps — it doesn't have very big band gaps. So how can you be transparent in one case, which means you have to have a band gap in the visible range, and then conduct electrons at the same time? Indium tin oxide is about the only material that can do this. I've never looked into the band gap structure, but it can, and that's why we can use automatic teller machines and touch screens on iPads.

§6.p2

But what about the glass? The glass is 0.3 millimeters thick — twelve thousandths of an inch — and you can get it in sheets 1.8 meters by 1.6 meters wide. You can do big-screen TVs, laminate it with all this other stuff, and that gives it some strength. But glass can become brittle within hours by being attacked by humidity. In the float glass process, the top air surface — where it just uses gravity and air to give you a flat surface — gives you an extremely pure flat surface, and if they use the right composition glass it won't be attacked by moisture. But the side on the tin bath — although they keep the tin bath from oxidizing, you shouldn't have big defects — if you go in there with an atomic force microscope and measure the flatness, the tin side is nowhere near as flat and as perfect as the air side.

§6.p3

So what do they do for these very thin things? They want both sides to be float glass. I've seen the Corning plant that does this, but I had to sign a confidentiality agreement. They basically — I won't tell you how they do it, but they take two sheets of float glass and they weld them together. The outside surface on both sides is float glass, and the bad tin surfaces are buried as they weld the glass together. I can't tell you the details. Interesting technology — about a quarter-million-dollar plant. Yes?

Student: [question about glass structure]

§6.p4

If you look at the structure of glass, you've got silica atoms with tetrahedral bonds in lots of different orientations. They're not perfect tetrahedra because glass is amorphous, not crystalline. You've got silicons with oxygens in between — a silicon-oxygen-silicon bond, which is one of the strongest bonds. It's potentially stronger energetically than even a carbon-carbon bond in diamond. But pure quartz is not as strong, because of fracture properties, as diamond. To break the network up, you have some sodium — you put in some Na₂O and some alumina. Some of those sodium atoms will hit the surface, and when sodium sees moisture it might form sodium hydroxide, might form a little pit. It won't keep forming the pit forever, and depending on the composition and network structure, the silica is fairly immune to moisture corrosion, but the sodium and potassium are not. You form hydroxides.

§6.p5

You might say, that's only a few angstroms deep. Yeah, well, go look at the fracture toughness of glass and the Ashby plot — critical flaw size, 10⁻⁴ millimeters. All you have to have is a few sodiums together and you get a pit a little deeper. Not very deep — you can't see it in a regular microscope. If you go in polished glass, like plate glass, you'll never get the strength you get from float glass in bending, because the whole polishing process leaves little scratches all over the surface, microscopic. You can't see them — they're smaller than the wavelength of light, hundreds of nanometers. But if you go in there with a fine enough microscope, you'll see notches, and moisture can do that. It doesn't take long. Yes?

Student: So if you use ion exchange you don't really change the sensitivity to humidity?

§6.p6

No, you don't. Well, you can, but now you've ended up with a compressive layer that's hundreds of microns deep, not angstroms — maybe 500 or a thousand microns deep. So what do I care about little small flaws? They're still in a compressive state.

§7. Glass strength, the brittleness limit, and Corian countertops [40:00]

§7.p1

[Tom locates a reference handout.] Annealed glass, not a safety glazing material, has very low internal stress, is brittle, and can be easily broken. You get large sharp dangerous shards. Unlaminated glass cannot be used in motor vehicles. Tempered glass has very high internal stresses — over distances of microns or tens of microns, even a hundred microns — that increase impact resistance. Upon breakage, small blunt particles result.

§7.p2

Glass is a brittle material — it fails instantaneously and completely. The ultimate strength of glass is not so much a function of its chemistry, although the potassium and sodium matter. With no residual stresses, like in float glass, I get critical flaw sizes. If I can introduce compressive stresses, or I can protect it by lamination — pristine glass fibers, those without flaws, have exhibited tensile strength of 14 gigapascals, 2000 ksi. That's when they're brand new and haven't been attacked. However, ordinary everyday glass is never in pristine condition. The surfaces of flat glass are cumulatively damaged on a microscopic scale during the initial float glass manufacturing process as well as subsequent operations — handling, cutting, grinding, tempering. You only need flaws on the order of tens of nanometers to significantly weaken that from its 2000 ksi strength level.

§7.p3

That's four times the best steel wire we can come up with. If we get iron single-crystal whiskers with a screw dislocation down the middle, we'll get steel with 2000 ksi strength. The inherent strength of the bonds is fantastic, but we never achieve it in metals because dislocations move before we ever get to those strength levels. In brittle materials like glass, they shatter by fracture mechanics before we ever get there, unless we take nice new fibers and encase them in protective epoxy so they don't get attacked. You can make composites out of glass, and we do have transparent glass structural materials.

§7.p4

Here's a lesson on — eventually I'm going to get to how to pick your kitchen countertops. Transparent structural materials: polycarbonate — that stuff between glass layers in transparent armor — acrylic (stretched acrylic is basically polymethyl methacrylate, Plexiglas), or chemically tempered glass. Tensile strengths are very low for the plastics, very high for the glass. Modulus of elasticity — glass is very stiff. That plastic window, you can flex it, you can lean against it and pop the window out. Design stress for the plastics — they give you three or four ksi, that's nothing compared to a metal. They won't even give you a design stress for glass, because it's brittle — you'd better not put it in tension. It's fine in compression, but don't let it see tension. Just like Portland cement — about 1 ksi tensile strength, but the codes give it zero in tension. You have to put steel in there as reinforcement.

§7.p5

Glass-ceramic compared to marble and granite as building materials. How many of you have a home where your parents have marble or granite countertops? All right. Now, you want to know what's wrong with that? Glass-ceramic versus marble and granite — you can get a bending strength three times as great in the glass-ceramic. Water absorption — glass-ceramic doesn't absorb water; marble and granite do. In fact, you can change the color of granite all the way through by ion exchange, half an inch through. You can take white granite and turn it into red granite. Red granite sells for a lot more. Marble and granite are beautiful. But the water absorption — do you really want to be fixing food on something that's absorbing water?

§7.p6

But that's not the real problem. Acid resistance and alkaline resistance. Marble — acid resistance, one percent sulfuric acid, gets a 10.3 rating, which means it's lousy. Glass-ceramic is hardly attacked. Granite is actually pretty good, because it's a mixture of feldspar and silica, but it's got pores. What's wrong with marble? Why is marble attacked by acid? Anybody know the chemical composition of marble? Calcium carbonate. What happens to calcium carbonate in an acid? It decomposes — to carbon dioxide and calcium hydroxide. It sort of seals the surface, but it dulls it. So don't spill lemon juice or vinegar on your marble countertops. They might be beautiful now — they won't be beautiful once you get a little acid on them. They'll lose their polish. Are you going to fix food on this? Well, no — you shouldn't. When they bought it, I'll bet they said, oh, don't get this or that on your marble countertops. So nowadays, rather than marble and granite, they're selling glass-ceramic countertops — much better material selection for food production. Yes?

Student: Don't they seal them?

§7.p7

They do seal them — they put a plastic coating on it, and they're beautiful. One of my favorite sets of elevators in the country is at the Williams Tower, just west of Houston. It's the tallest building on the Beltway at the nine o'clock position, a seventy-story building, and each elevator has a different type of marble from Europe. It's got twelve elevators with twelve different marbles in different colors. Yes, Johnny, you're right, they do seal them. But if you scratch through the sealant, you run into problems.

§7.p8

Student: [follow-up]

§7.p9

I still have Corian countertops, which is a polymer DuPont was selling in the mid-'80s, and it's about time to redo the kitchen. I cooked or had a hot frying pan — one of the griddles — and put it on there without a reflective surface underneath, and heated it up. By thermal expansion it was in compression, but when it cooled back down we got cracks. It turns out DuPont came out with an improved Corian about three years later. We were an early adopter. You learn all kinds of things.

§8. Aluminum: from precious metal to commodity [49:17]

§8.p1

Any questions about any of that? I took a little bit longer as I usually do. I was going to talk about aluminum, and maybe I can just quickly do some of the history of aluminum. Aluminum was once more valuable than gold. In 1850, a baby rattle from the royal family in France was made out of aluminum. It's light — babies aren't that strong. What's on top of the Washington Monument, built in the 1880s? A piece of aluminum. It's a lightning rod, intended to attract lightning, and it's aluminum.

§8.p2

Aluminum in 1852 was $545 a pound. If you divide by sixteen, it was more expensive than gold, which was about $25 an ounce. The price came down. By 1854, Napoleon thought this would be great armor for his soldiers, so he funded the development of aluminum in France. At the time they were using either sodium or potassium to reduce aluminum chloride — still a very intensive process. It wasn't until the 1880s in the United States, the Hall process dropped the price — 1886 I think it was. Hall cut it in half. Remember what happens if you cut the price of a structural material in half? You go up four times in the quantity used. They kept dropping the price. By 1897 it was thirty-six cents a pound.

§8.p3

Aluminum had tremendous growth. In 1889 they sold 7,000 pounds. By 1909 they were selling fifteen thousand tons. The real growth of aluminum came in World War II. This is the world's total for aluminum production — Germany was making more than we were in 1939. By the end of the war we'd outstripped them. The Germans hadn't been able to increase much, but we went from 148 to 695. All of a sudden Alcoa, which owned most of the business in the United States, was making 2.6 million tons of aluminum. Here's Andrew Mellon's aluminum Pierce-Arrow automobile. They were making horse carriages out of aluminum in New Kensington, Pennsylvania in 1909.

§8.p4

[Tom advances slides.] This is what Alcoa said the Pittsburgh Reduction Company looked like — this idyllic picture. And here's the actual picture. It's not quite as idyllic. There's a lot of pollution in the smelting and refining of aluminum.

§8.p5

There's one plot in here about Alcoa's command of the market. Alcoa had a monopoly. They had 100% of the market for bauxite in the world. They were a true monopoly in the aluminum business. George Kenney, who was Joel Clark's first doctoral student, did his doctoral thesis on aluminum and magnesium and showed pretty convincingly that Alcoa and Dow had fixed prices after World War II. Alcoa said, we won't go into the magnesium business if you stay out of the aluminum business. So Dow took over magnesium and had a monopoly there. You could match their prices over time from 1945 up until 1975 when George did his thesis.

§8.p6

When we hear these terrible things about other countries doing terrible things, just remember — we do the same thing, we just don't advertise it the same way. Any questions? You can have Monday off. Today is Tuesday. We've got class Wednesday and Thursday. I'll be here on Thursday — we'll finish up the rest of the periodic table for structural materials. Dr. Belmar will be here next Tuesday for the last of our two sets of lectures. If you haven't signed up, please do. If anybody has questions about the presentations, come see me.

Cases referenced

Layer 2 — cleanup edit
p1 00:00

Obvious okay, where are we, anybody have any questions? I'm going to pass this one in, in fact I can go ahead and pass on this room. If your name is on here it's because when I sent around the sign-up sheets and stuff you basically said that you were daily available those days. Um, we have 40 people in the class, I'm going to pass this around a little bit later, which is a sign-up if you haven't signed up. Your name should be down here. If your name is not anywhere on the sheet, then please let me know, because we don't know you're part of the course, okay.

p2 00:40

Um, if I don't have to go out of town we'll finish before Halloween. If I have to go out of town we'll finish before — what's Veterans Day, or whatever they call it, November 10th, right? 11th, whatever, yeah, 11, right? Or no, 11, 18, right? I think the Armistice was at 11 o'clock or something. 11 or anything one, whatever.

p3 01:15

So does anybody have any questions? And I didn't prepare some special question, I was thinking more about the schedule. So the schedules will come around. You should be signed up for one of the days that you said. Um, and we'll start them next Wednesday, presentations. Anybody have any questions on the presentation? It's supposed to be brief, no more than 10 overheads, needs to be a focused subject. By focused I don't want, you know, the automotive industry or the steel industry or something. Someone had suggested they want to do Venetian glass — that sounds great to me, sounds to me like you can tell everybody what Venetian glass is and why it's different and what's interesting about it, in something like that. The topic can be anything that's of interest to you.

p4 02:10

I guess I could tell you the story of when I interviewed for a Hertz fellowship and I met with — I didn't tell you the story today. I, the guy, I made the first round of interviews. And Hertz is the Hertz rental car fortune, and he's sort of a right-winger, or he was. And so Edward Teller was on his board of directors. And so the guy who interviewed me — this was many years ago, but if I talked to someone at Lawrence Livermore National Lab and I say the guy who interviewed me was Lowell Wood, everybody, "So you interviewed with Lowell Wood." Lowell Wood was Edward Teller's right-hand man, okay. Anybody know who Edward Teller was? If I don't, know he was the father of the hydrogen bomb, okay. And he's super right wing, he was Hungarian, and anyway, and he was an advisor to Eisenhower and Kennedy and all these presidents and stuff.

p5 03:09

And so I made the first round, and second round was when they actually made the final decision. And so I was in the dean's conference room one evening interviewing with this guy, and frankly he was sort of a jerk. And everybody I knew, I've talked to since, says "oh you interviewed with him," and I say "yeah he's sort of a jerk," they say "oh yeah he was," because that's how he ran Lawrence Livermore National [Lab]. He was the number two guy there at the time. And he first asked me, uh, something about — who is Count Rumford? Anybody know who Count Rumford was? Neither did I, okay. Count Rumford was a philanderer from Medford, Massachusetts who disproved the phlogiston theory of matter in the 1790s by — he was reaming out gun barrels and he showed he could get an infinite amount of heat from friction, and therefore heat was not a constituent of the material, it was something that was generated by the work. And that was some early days of thermodynamics. Anyway, Count Rumford was not a count. He went over to France, and so he could be a philanderer with some of the royal people, he could call himself Count Rumford. He wasn't a count, but anyway. One of the deans here at MIT, dean of engineering's got really interested and wrote a book about Count Rumford. Anyway, I didn't have a clue who Count Rumford was.

p6 04:31

So he asked another question, and the question was basically, uh, who was Metternich, okay. He didn't ask it exactly like that, but who would unify the Prussian states in the 1870s or whatever it was. I said Metternich, and at that time Henry Kissinger was — this was the early 70s, he was an advisor to Nixon and things like that, Chief of Staff, whatever he was at the White House. And I said Henry Kissinger did his doctoral thesis on, uh, on Metternich. And uh, he was really impressed that I knew that, what Henry Kissinger did his doctoral thesis — doctor of thesis, big deal, I read it in some magazine. Um, and then he said well, I've been asking you questions, so why don't you — oh no, that we got on to those questions because he said I've been asking you questions, why don't you pick the topic. And I said, I was sort of fed up with this jerk, and I said well how about cooking, because I like to cook. He says well I was thinking something more technical. I said okay, what about history. So we got on to these questions about Count Rumford and Metternich. The only thing that impressed him was that I knew Henry Kissinger's doctoral thesis topic. I didn't get the fellowship, but anyway, I got an NSF fellowship instead. Anyway, uh, anybody have any questions?

p7 05:57

Okay, so what this is, and I handed around a copy for you and I'm going to hand this one around if you're not signed up, please sign up. These are the people who haven't signed up for the, um, presentations. These are the people who've signed up. So we're all scheduled through October 23rd, we've got, um, three empty dates on both of these days, we got four empty slots on these days. Hopefully you can fit into some of this and we'll finish up early, as far as that goes. Uh, beyond that, anybody have any questions about the presentation and what you need to do? Just do something that's fun, right, and interesting.

p8 06:44

Okay, we were talking about glass, and I mentioned that glass manufacturing had improved markedly, or productivity had improved markedly over the ages. I also mentioned glass is a brittle material, but it is a structural material. I mean, it has one of the very interesting properties, it's transparent, and because it's transparent we want to use it in structures. Problem is, I told you that it actually corrodes. And if you look at annealed glass, which comes out of the float glass process — float glass is produced virtually stress-free — and it breaks, it shatters, and it ends up with these long sharp things that have killed people when they walk through, they don't realize they're walking through a glass door. And so now there are codes that you have to either use tempered glass or laminated glass. This is laminated glass, this is tempered glass, I'll talk about what that is. Or more often than not they use plastic in screen doors and stuff. So far as that goes, because you like to have something optical— optically clear, we use glass in a number of different forms.

p9 07:57

You have to anneal glass because glass, having low thermal conductivity and being a brittle material and having small flaws that can create problems and cause it to crack and shatter with hazardous, potentially lethal shards and stuff, we have to do something to make it safer. And so what do they do on windshields, or side — side window? Yes, what?

Student: [inaudible — laminate it on the windshield, temper it on the side]

p10 08:27

They laminate it, and on the side windows they temper it, okay. They laminate it, they put a piece of plastic in between, they make a composite, okay. And so if you get hit, the windshield, if you've ever seen an accident where someone, get someone impacted their windshield with something, you'll see it, you know, it breaks like this, but the plastic acts sort of as a catcher's mitt and holds the stuff and it doesn't go shattering all over everywhere and cutting people and whatnot.

p11 09:00

So they laminate glass, they temper it. Tempering is a process of, um, heating the glass up to a range where it's in a viscous plastic state, and then cooling it rapidly. As you cool it rapidly — and they're just blowing air on it to cool it rapidly — but as you cool it rapidly, the top surface goes into tension because it's shrinking as you cool the top surface. And with poor thermal conductivity the center is still warm or hot and viscous, but because it's viscous it actually contracts while the outside is also contracting. The outside is going below what we call the strain point. The strain point in glass is the temperature at which glass will relax within about an hour. If you cool it rapidly in tens of seconds, you basically can get the outside to harden up, become much less, much more viscous, and get the core to shrink. And when you cool all the way down, the core has shrunk and everything gets back to uniform temperature and the outside surface is in compression.

p12 10:11

One of the rules of residual stresses due to thermal processes is that whatever stress you have at high temperatures will be reversed at low temperatures. So at high temperatures you actually have tension on the surface, but at low temperatures you'll have compression on the surface, and you have to overcome those compressive stresses. If you look at some of the plots of the tempering process, this is the temperature plot through the thickness of the glass. You start cooling it down, quenching time in seconds, so this is over tens of seconds. The center of the glass cools down more slowly than the surface — this is the surface, this is the center — and you'll set up these temperature gradients, okay. When you get down all the way to room temperature down here, you're going to end up with a residual stress pattern that looks something like this, this is stress in megapascals. And you can end up with compressive residual stresses. So as I said, when you first start cooling it down you get tension on the surface, and the thing gets complex and complex, and finally when you get down to room temperature you'll end up with 75 megapascals, which is not a whole lot, okay. It's about 10 ksi. But 10 ksi compressive stress on the surface — as long as you don't break through that, you can bend the glass and put stresses of up to 10 ksi on there, whereas the untempered glass would have a strength of about one ksi due to the notches that you get from the float glass process.

p13 11:54

Okay, now another thing we can do with glass, since it is an important material, is we can do ion exchange. So ion exchange is, you take a glass — in this case they took a sodium aluminosilicate glass — and they did an ion exchange with potassium. So they put it in a salt bath that has potassium, and just because of entropy effects the sodium wants to exchange with the potassium. Potassium is a larger atom. You're doing this at relatively low temperatures where you're below any viscous diffusion or whatever, and you're doing this for hours, okay. And after four hours you can end up increasing the strength of the glass from 140 megapascals, which is what, 20 ksi [20,000 PSI], up to 400 megapascals, which is around — what's that, 60. Modulus of rupture's 60 ksi, but the tensile strength is going to be around 10 ksi or something, no about five or six ksi. This is chemically tempered glass, where you're basically getting compressive residual stresses by exchanging — a chemical exchange of large ions for small ions.

p14 13:15

The John Hancock building over here, when I was a student they were building it, and after they first built it the winds came along and they were creating a suction force and the windows were popping out of the building and falling to the ground.

Student: [inaudible — plywood palace?]

Yeah, probably actually Plywood Palaces. Oh yeah, probably the Palace. I have a — someone lived in the same house I was in, two years younger, and uh he climbed up while they just — the day after they put the top I-beam on it, he snuck in, climbed up to the top and signed the top I-beam. A couple years later — he was sort of a risk taker — a couple years later he died skydiving in Colorado when his parachute didn't open. But in any case, it's chemically tempered glass, because they needed a stronger glass because it was flexing. And they now actually have the building under a slight negative pressure, they have big vents. And they also have — some of it was the swaying of the building. They took a whole floor and they have a big weight in there, and they actually — the swaying frequency of that building is several seconds, and it's a damper.

Student: Tuned mass damper?

p15 14:30

Right, it's a seismic balance, not for earthquakes, but it's a — to keep the thing from bowing too much, okay. They're reducing the vibration of the building, which most buildings they just sway. Anyway, I, you know, about the same time I went to Chicago, went to the top of the Sears building, and they have an observation deck, and you go in the restroom, you see the water sloshing in the toilet, okay, because that's the building that's sloshing, okay. Well the John Hancock building, they didn't want it to — they wanted to damp it seismically. And so they basically have a whole floor and they have a weight that is rotating in opposition to the wind motion, okay, to try to damp it, okay. So they spent a lot of money on that building, hundreds of millions of dollars, to fix it because they used glass as a structural material and ran into problems. Yes?

Student: [inaudible question about ion exchange depth]

p16 15:20

Uh, no, it doesn't come down the whole profile, it probably is only the first two or three thousandths of an inch. So I mean, you know, if you're — this is typically a plate glass, a quarter of an inch thick, you know, no thinner than an eighth of an inch. Float glass might be a sixteenth, an eighth of an inch, or 3/16. Plate glass is where you pour it on a steel plate and grind it and polish it when you get to a quarter inch to half an inch or thicker glass, okay. This ion exchange is just — is relatively thin. You could scratch it with a glass cutter, you won't be beneath that chemically tempered compressive layer, not uh — but if you really got a good gouge in it, took a diamond and gouged, you know, you get below that and this'll shatter on you as you get these and get into the tensile stress residual potential stresses on the inside. So they have to make it, you know, 50 microns deep, and that's why it takes hours to do, okay. I mean, you put it in there, you'll get a very thin layer, but then that slab would be scratched and then you've now created a situation that you've stored energy in it and you release the spring and kapow, okay. So it's got to be a thick enough layer. But on a hard material like glass, it's hard to scratch it three thousandths deep, okay. You can, but if you do you're in trouble.

p17 16:48

I wish I had it, but Professor Uhlmann, who used to teach glass here when I was a student, had a piece of chemically tempered glass that was probably about 18 inches long and about — bowed about three inches high, and he could put it on the table and just flatten it with his hand, okay. Because he wasn't exceeding the compressive stresses in bending. This only works in bending, doesn't help in tension. But big flat sheets, how they fail, they fail in bending. So it works, okay. So I guess the point is people have done a lot of things to make glass a useful material in spite of its brittleness. So all those things I said about how wonderful steel is because it has toughness, well that's true, but people are clever enough to figure out how to make glass into something that's useful even though it's brittle, okay.

p18 17:40

Now, other stories. This is from protective armor systems. This is three layers of glass with one layer of polycarbonate. Polycarbonate is a very tough plastic in his own right. It's got about 10 ksi strength if you pull it slowly. But they used to use it as a bullet stopper, okay, because it's really tough, okay. And so they now have copolymers. I just bought some Vitamixes for my children last night, and they use, uh, Eastman Chemical Tritan or whatever, and I looked it up — it's a polyester copolymer. They used to make them out of polycarbonate, which is very tough and transparent. Now they basically make armor for bullets, and this was an inch and a quarter or something with four-layer, three-layer, four-layers adhesively bonded together. You can't have any bubbles in the adhesive, this has to go through an autoclave in a very roller process for the adhesive bonding. But this will stop, I don't know, I think that will stop a 50 millimeter round, okay. And it does it by cracking the glass, absorbing the energy, hitting the next layer of glass, cracking and shattering and absorbing all that energy. Eventually it gets to the polycarbonate, and the polycarbonate, hopefully you've slowed it down enough.

p19 19:05

That will not stop a rocket-propelled grenade, okay, an RPG. However, they make things that are just under six inches thick that will stop an RPG, okay. And the president's limousine has got this five and three-quarter inch thick material made by these folks, which, you know, it looks like a nice big car, but if you actually get in it, it's pretty scrunched inside. It is a big car, but the doors are about 10 inches thick, okay. It looks like a regular old Cadillac or Lincoln or whatever, you know, he rides in, but it's been modified. And you can buy one yourself. A lot of, a lot of sheikhs and other people in the Middle East buy these types of things, because they have some enemies who would just as soon hit him with an RPG. If you want to stop an RPG, you can. Humvees will typically might have something like that. The big, what they call the — the things in Iraq —

Student: MRAPs.

[20:11] MRAPs, not — well, yeah, called mine sweepers. But the MRAPs were these 60-ton personnel carriers that replaced the Humvees, because of the uh, the whip, the uh, the visha— yeah, the v-shaped on the bottom. And the v-shape on the bottom — it turns out six layers of glass as the uh, as the uh, armor, okay.

p20 20:42

What happened, um, and I can't tell you everything about this because some of it's classified, but I used to sit on the committee that reviewed the materials and mechanics group at Aberdeen Proving Ground. This used to be the materials group out here in Watertown, our Watertown Arsenal Mall now. Well, since the 1860s that was the U.S. Army's materials lab. They used to make cannonballs and things like that in the 1860s over here in Watertown, in the mall area, and some of those buildings were some of the almost-original buildings. But anyway, they moved from down to Aberdeen Proving Ground, which is where the Army does all their ballistic studies and stuff, built them a beautiful new building.

p21 21:25

And it turns out what happened is, the Secretary of the Army — we were losing a lot of soldiers in Iraq, and he came and said look, you're our — you're the people who were supposed to be developing armor for us, we want you to solve this problem. And within 18 months they solved the problem. I mean, soldiers were being blown up in their Humvees and stuff, but within 18 months we quit losing soldiers being blown up in their Humvees. Now the most important thing — because there's one guy on our committee who was actually a captain, he had been a captain, had done two tours in the Middle East — and he said the most important thing was this, the eyes of the soldier. And they go down this road every day, and if they saw anything change on the road, or, you know, within 50 yards of the road, they would stop and they would start looking for some buried whatever it was. And these people aren't very sophisticated, they didn't have remote control things. They basically would be hiding 25 yards off the road ready to trigger the device when someone come by. The best thing was actually the eyes of the soldier, he said. But in fact they developed things, and they didn't know what armor was going to be best, so they tried steel, titanium, aluminum, glass. And they had some reasons to believe the glass might be good. And they just blew them up down there in Aberdeen, all within a month or two, and they found out glass was the best.

p22 22:57

Now, I can't tell you why, because that's classified, but glass worked better than anything else at repelling the rocket. You know, these are shaped charges that send off a stream of molten copper that will just cut through steel and destroy aluminum. It has sonic velocities of this massive dense copper that will just cut through steel. I think I mentioned, I mean, I saw pieces of steel — and you can read this in the literature — that a shaped charge that will shoot out a 36 inch piece of copper will penetrate 36 inches of steel. I've seen the steel that was penetrated, okay, with one of these things. So you can't put 36 inches of steel underneath the v-shaped MRAP. You put six sheets of about half inch, three-quarter inch glass. I can tell you that because any soldier who's out there can look and see that he's being protected by glass, okay.

p23 23:54

So hardness is an important property in armor protection, okay. And glass is harder than steel. It's not stronger, because it's got, you know, flaws will make it break. But if you cause it to break, you're absorbing energy. Maybe only one time, but you only need to do it one time. If you get hit by an RPG, probably not going to use that MRAP again anyway, okay. Um, well rather than tell you about some of those things on glass, let me tell you another story about glass. Yes?

Student: Same kind of material used for IED protection and the underbelly of the Cougars?

p24 24:36

Yeah. And when I — well, I said shaped charges, improvised explosive devices are nothing more than shaped charges, okay. So what happened — I'll give you a little bit of the history. When they first went into Iraq, look, you know, George — President George Bush's time — they would use a four-inch black iron pipe, steel, just a steel pipe, four inch in diameter. And they would put a bottom on it like a machine and put on a — or they could weld the bottom on it. They put their explosive in here, and then you had to have — and I didn't bring it with me, maybe if I remember — you have to have a piece of copper that's sort of dish shaped, like a saucer. And what happens, you put your explosive in this, and when you set off the charge, this actually folds outward. It just, you know, remember little clickers in your head as a kid that you could click and they'd buckle and make a little noise? Basically the copper bows outward, and as it bows outward, the stress causes enough frictional heating that the copper melts, and you end up getting what's called a shaped charge.

p25 25:49

The U.S. Navy discovered this in the 1880s at the Brooklyn Navy Yard by mistake, while they were just doing some explosives work, and they found they could impress, um, the — or they could cut through — just say it'll cut through steel. Anyway, you do this and you get a jet as everything implodes together. I wish I had one of Doc Edgerton's pictures of a splash of milk drop, where you have a drop of water come down in a little dish and it goes out in a wave and it comes back as a wave, and when the wave comes back you get this big spike of milk, okay. Well basically you don't have a wave, but you have this thing flexing, and as it does this all the copper melts from the energy of the explosion and the mechanical shape — it's called a shaped charge — and you end up forming a jet of molten copper. And that will just eat through steel of equal thickness to the length of that jet, approximately.

p26 26:49

So if the RPGs, rocket-propelled grenades, look something like this — they have fins on the back, you know, so they'll fly — but the reason they have the shape is because they actually have a v-shaped piece of copper and the explosives down here, and it implodes this and you make this big jet, and it'll go right through a Humvee, okay. Four inch diameter, I think this was 200 kilojoules of energy, okay. Well, they got a little better and they went to eight inches, and eight inches goes as the square, so it had four times the energy — let's see, four times that, it must have been 400 kilojoules, because they went to 1.6 megajoules, okay. Or no, it goes into the cube. So it was 200 megajoules. They went up eight times, because the volume goes as the cube. Anyway, so they went to 1.6 megajoules. That went below a Humvee, [blew it] into smithereens. And so people were dying in Humvees, so the Secretary of the Army came, said you got to do something, you got to do something.

p27 27:51

And within 18 months they designed and constructed and developed armor for the MRAP vehicles. And the MRAP, they have the seats in the MRAP are sort of interesting, I got to sit in an MRAP. They're big shock absorbers, because if you get a 1.6 megajoule improvised explosive device under you, even though it's shaped like a V for the armor to deflect the blast that way, it will still lift that 60-ton vehicle — this is 60 — it may only be 30 tons, I think it's 60,000 pounds as I think about it — will lift it four or five feet in the air, and you're taking off like a rocket too. So you have to be strapped in your seat belts, and you have to, you know, has these big springs and stuff, so that you don't essentially get a serious spine injury or hit your head on the ceiling and end up dying from a concussion or something. So they have to — there's, you don't want to be hit, okay, while you're in one of these things, but it won't blow the thing to smithereens.

p28 28:48

And of course now that we're, we've moved out of Iraq, what are they doing with the MRAPs? We enjoyed the papers, they're giving them to the local National Guard. And so, where was it, oh it was in Missouri, you know, they come in there after, you know, the riots after the policeman got — the policeman killed the teenager — and they come in there with their MRAP. And so hey, the rioters in Missouri have their, uh, eight inch diameter, uh, improvised explosive devices, the police will be safe. Isn't it great. Anyway.

p29 29:29

To machine this thing — this has to be very precisely machined because you rely on symmetry — you can't just use any old machine shop, and there is no machine shop in Iraq that can make those. I can't tell you what country was giving these to the insurgents in Iraq, okay, because that's classified, but we know where it came from, okay, and who's doing the machining, okay. But all you had to do is take a little disc of copper, then all you need is pipe. They got plenty of pipe in Iraq, that's what they use for the oil business, right. And they just went from four inch to eight inch and they could wipe out Humvees, okay. More than you ever needed to know about explosives.

p30 30:12

But let me tell you, the technology for, uh, weapons is sort of amazing. I remember in 1985, they were first developing some of these really good RPGs, and one of my students who was in the Army at the time over here at Watertown Arsenal doing his doctoral thesis told me a story about, they lined up three tanks on a battlefield — probably down at Aberdeen — and they shot an RPG and it went through six layers of armor, through, you know, both sides of all three tanks. And apparently the general tossed his cookies right there on the battlefield, okay, he just got sick.

p31 31:01

Within a year they had developed new types of armor that could not be punctured. So in like 1984 there was no armor that could not be penetrated, by 1986 there was no propellant that could penetrate the modern armor. But the modern armor was a composite, it might be layered with metal, ceramic, because it's actually a metallurgical reaction that allows the copper to go through that steel — it's an embrittlement reaction of copper and steel. You put ceramic in between, you don't embrittle ceramic with copper, so you can stop it.

p32 31:44

The other thing you can do is these penetrators — I talked about the depleted uranium. They might be a sabot, 36 inch long, half or three-quarter inch diameter depleted uranium rod that gets shot out of a shoulder-mounted weapon or out of a tank weapon that can go through other armor. And it, when it hits, it's going to get stressed to close to 400,000 pounds per square inch. If you actually have on the surface of your armor an explosive that, when it gets hit, it ignites and sends a shock wave through that rod, you'll send a stress wave through that rod which reflects off the other end and the whole rod will shatter. And so they have what they call explosive armor — you have armor, but then on the top surface you have an explosive that will send a shock wave through.

p33 32:38

So then, all you — that works great for the first shot, right. So what do they do, and what did I see in 1985 or whenever I was there? They were doing supercomputer modeling, and they had sabots that had a 12 inch piece that would set off the shock wave, and they had another 24 inch piece right behind it that would go through the hole, because they'd already made the explosive, okay. They're modeling this on supercomputers and finding ways to develop armor that couldn't be penetrated and penetrators that couldn't be defeated by armor. It's pretty interesting, okay. It's sort of gory, but it's sort of interesting to see the technology that goes into this stuff, okay.

p34 33:25

Uh, it's, you don't usually read about this stuff, because what I told you, none of that is classified, you can find that in books and stuff. But there is plenty of stuff that is classified that I can't tell you about, okay.

p35 33:42

So uh, oh, I want to tell you about your computer screens, okay. They're glass. They're actually a composite. I showed you LED screens and how they might be six or seven layers. You've got a layer of plastic on the very outside — you actually, nowadays we actually have glass on the outside because you have indium tin oxide, this transparent semiconductor that allows you to use a touch screen. And it's very interesting to have a transparent material that conducts electricity, because ordinarily if it's transparent that means it doesn't absorb photons in the visible range, which is several electron volts, okay. But if it conducts electrons, it means it's got to have some band gaps in there — it doesn't, again, have very big band gaps. So how can you be transparent in one case, which means you have to have a band gap in the visible range, and then be able to conduct electrons at the same time? Well, indium tin oxide is about the only material that can do this. And I, I've never looked into the band gap structure of it, but it can, and that's why we can use automatic teller machines and do touch screens on your iPads and things like that.

p36 34:55

But the glass — what about the glass? Well, I showed you before, the glass is like 0.3 millimeters thick, 12 thousandths of an inch thick, and you can get it in sheets that are 1.8 meters by 1.6 meters wide. So you can do big-screen TVs and stuff like that, and you can laminate it with all this other stuff and yeah, that gives it some strength. But in fact, I told you that, you know, glass can become brittle within hours by it's being attacked by humidity. Well it turns out, in the float glass process, the top air surface, where it just is using gravity and air to give you a flat surface, gives you an extremely pure flat surface, and if they use the right composition glass it won't be attacked by the moisture. But the one on the tin bath — although the tin bath they keep it from oxidizing and everything, you shouldn't have big defects, but if you go in there with an atomic force microscope and measure the flatness, the tin side is nowhere near as flat and as perfect as the air side of the float glass.

p37 36:02

So what do they do when they go through these very thin things? They want both sides to be float glass. And again, I'm sorry, I can't tell you — I've seen the Corning plant that does this, but I had to sign a confidentiality, um — they basically — I won't tell you how they do it, but they take two sheets of float glass and they weld them together. I'll just tell you that, okay. So the outside surface on both sides is float glass, and then they — it ends up being only twelve thousandths of an inch thick, but the bad surfaces, the tin surfaces, are buried as they weld the glass together. But I can't tell you the details of that. What's an interesting technology, it's about a quarter-million-dollar plant, okay. Yeah?

Student: [inaudible question]

p38 37:00

Yeah, it's basically — if you look at the structure of glass, you've got a bunch of silica atoms with tetrahedral bonds in lots of different, you know, orientations. They're not perfect tetrahedra because glass is amorphous, it's not crystalline, right. But you got all these silicons with oxygens in between, this implies a silicon-oxygen-silicon bond, and that basically is one of the strongest bonds. It's even potentially stronger energetically, thermodynamically, than even a carbon-carbon bond in diamond. But it's not — pure quartz is not as strong, because of fracture properties, as diamond. But you also have in here, to break this network up, you have some sodium, okay. You put in some Na2O and some alumina and stuff, and so you have some sodium. Well, some of those sodium atoms will hit the surface, and when sodium sees moisture, it might form sodium hydroxide, might form a little pit right there, okay. Well it won't keep forming the pit forever, and depending on the composition of the glass and this network structure, the silica is fairly immune to corrosion by moisture, but the sodium and the potassium are not. And so you basically form hydroxides.

p39 38:27

And you might say, well gee, it's that's only a few, you know, angstroms deep. Yeah, well go look at the fracture toughness of glass and look at the Ashby plot and see the critical flaw size — and you're 10 to the minus 4 millimeters, that's critical flaw size. You know, all you have to have is a few sodiums together and you get a pit over here that's a little deeper, okay. Not very deep, I mean you have to, you can't see it in a regular microscope, okay. If you go in polished glass, like plate glass, you'll never get the strength that you get from float glass in terms of bending strength, because the whole polishing process leaves little scratches all over the surface, microscopic. You can't see them, they're smaller than the wavelength of light, okay. But the wavelength of light is on hundreds of angstroms or nanometers, or whatever it is, hundreds of nanometers. And you can't see the scratches because it's polished finer than that. But if you go in there with a fine enough microscope, you'll see you have little notches in there, and moisture can do that. It doesn't take long. Yes?

Student: So if you use ion exchange you don't really change the sensitivity to humidity?

p40 39:36

No, you don't. Uh, well, you can, but now you've ended up with a compressive layer that's thousands of microns deep, not angstroms, okay. Well, not thousands, but it might be 500 or a thousand microns deep, okay, in some cases. So what do I care about little small flaws? They're still in a compressive state, okay.

p41 40:00

But one of these — I think I brought it — I mean, you don't ever hear about these things, but I think it's, um...

[Tom looks through his materials.]

[40:28] Well, this is basically just explaining some things I've already said. Annealed glass, not a safety glazing material, has very low internal stress, is brittle and can be easily broken. You get large sharp dangerous shards, okay. If using a vehicle they're hazardous, for this reason — they use unlaminated glass cannot be used in motor vehicles. Tempered glass has very high internal stresses, okay. And over distances of microns or tens of microns, even 100 microns, that increase impact resistance. Upon a breakage small blunt particles result. It's not this page, but one page, uh, I was looking at, and it actually talked about the moisture resist— oh, I think it's — let's see if I can find it.

[Tom continues looking.]

p42 41:34

The strength of — I told you that fiberglass is potentially very strong when it's first made. Uh, 462. There's ion exchange. So, okay, here. Glass is a brittle material, thank you, okay. When it fails instantaneously and completely, the ultimate strength of glass is not so much a function of its chemistry — although this potassium and the sodium, if I don't have anything else where there's no residual stresses like float glass, then I can get critical flaw sizes. If I can introduce compressive stresses from other things, or I can protect it by lamination — but he says pristine glass fibers, that is those without flaws, have exhibited tensile strength of 14 gigapascals, 2000 ksi. That's when they're brand new, okay, and they haven't been attacked. However, ordinary everyday glass is never in pristine condition. The surfaces of flat glass in particular are cumulatively damaged on a microscopic scale during the initial float glass manufacturing process as well as subsequent operations: handling, cutting, grinding, tempering. You only need flaws on the order of tens of nanometers to significantly weaken that from its 2000 PSI [ksi] strength level.

p43 42:56

Hey, that's four times the best steel wire that we can come up with, okay. If we get iron single crystal whiskers where you have a screw dislocation down the middle, you'll get steel with 2000 ksi strength. The inherent strength of the bonds is fantastic, but we never achieve it in metals because dislocations move before we ever get to those strength levels. And in brittle materials like glass, they shatter by fracture mechanics before we ever get there, unless we take nice new fibers and we encase them in protective epoxy so they don't get attacked by things, okay. So you can make composites out of glass, and we do have glass transparent structural materials.

p44 43:47

So here's a lesson on — eventually I'm going to get to how to pick your kitchen countertops. But transparent structural materials: polycarbonate — that stuff that's in between those glass layers and the transparent armor — acrylic, which is stretched acrylic, which is basically polymethyl methacrylate, Plexiglas, or chemically tempered glass. And you have tensile strengths that are very low for the plastics, very high for the glass. Modulus of elasticity, the glass is very stiff. Hey, that plastic window, you can flex, you can lean against it and you're allowed to pop the window out. Modulus of elasticity is very high. Design stress for the plastics — they give you design stresses three and four ksi, that's nothing compared to a metal. But you do have some design stress for glass — they won't even tell you, because it's a brittle material, you better not put it — it's just like Portland cement, you better not put in tension, okay. It's fine in compression, but don't let it ever see tension, okay. Turns out Portland cement has about one ksi strength in tension, but the codes give it zero strength in tension. You have to put steel in there as a reinforcement.

p45 45:04

Now, glass-ceramic compared to marble and granite as building materials. So how many of you have a home where your parents have marble or granite countertops? All right. Now, you want to know what's wrong with that? Well, what's wrong with that is — glass-ceramic, marble and granite, you can get a bending strength that's three times as great in the glass-ceramic. The water absorption, a glass-ceramic doesn't absorb water, marble and granite do. In fact, you can change the color of granite all the way through by doing some ion exchange, and you get different colors of the granite, and you can make it go half an inch through. And you can take white granite and turn it into red granite by a chemical process, if you know how to do it. And red granite sells for a lot more than white granite, okay. You can take cheap white granite and turn it into red granite. It's beautiful, this stuff, marble and granite. But this water absorption — do you really want to be fixing food on something that's absorbing water, okay? But that's not the real problem.

p46 46:14

Acid resistance and alkaline resistance. Marble, acid resistance, one percent acid, sulfuric acid, it's got a 10.3 rating, which means it's lousy. Glass-ceramic is hardly attacked. What's this other one — granite is actually pretty good, because granite's a mixture of feldspar and silica and other things, but it's got pores in it. Alkaline resistance, okay. What's wrong with marble? Why is marble attacked by acid? Anybody know what the chemical composition of marble is? Calcium carbonate. What happens to calcium carbonate in an acid? It decomposes to carbon dioxide. So carbon dioxide and calcium hydroxide. So it sort of seals the surface, but it dulls it. If you put — if you get acid — so don't spill lemon juice or vinegar on your marble countertops. They might be beautiful now, they won't be beautiful once you get a little acid on them. They're going to lose their polish. And you're going to fix food on this? Well no, you shouldn't fix it. And I'll bet you when they bought it, if you go there, they say oh, well don't get this and that and the other thing on your marble countertops. So nowadays, rather than marble and granite countertops, they're actually selling glass-ceramic countertops, much better material selection for food production. Yes?

Student: [inaudible — don't they seal them?]

p47 47:32

They do seal them, okay, they put a plastic coating on it, and they're beautiful. I mean, one of my favorite set of elevators in the country is the Williams Tower in, uh, just west of Houston. It's the tallest building on the Beltway around Houston at the nine o'clock position as you go around the Beltway, and it's a 70-story building, and all the elevators — each elevator has a different type of marble from Europe. I mean, there's just, you walk into an elevator and you're just going to see different marbles, okay. It's got 12 different elevators and 12 different marbles of different colors. And of course the marbles have — they're beautiful. Anyway. Oh, yes, they do seal them, Johnny, you're right. But if you scratch through the sealant and everything else, you run into problems.

Student: [inaudible]

p48 48:31

Yeah, you know, I still have Corian countertops, which is a polymer that DuPont was selling in the mid-80s, and it's about time to redo the kitchen. But, um, uh, we've — I cooked or had a hot frying pan or whatever, you know, one of the griddles — and I put it on there without a reflective surface underneath it, heated it up. And by thermal expansion it was in compression, but when it cooled back down we got cracks, okay. So it turns out DuPont came out with, um, an improved Corian about three years later. We were an early adopter of Corian. Uh, so you learn all kinds of things, okay.

p49 49:17

Any questions about any of that? So I took a little bit longer as I usually do on topics. I was going to talk about aluminum, and maybe I can just quickly do some of the history of aluminum. Aluminum was once more valuable than gold. If you look in 1850, a baby rattle from the royal family in France, it was made out of aluminum. It's light. Hey, babies aren't that strong. If you look, anybody know what's on the top of the Washington Monument, built in the 1880s? Piece of aluminum. It's a lightning rod right on top of the Washington Monument, [intended] to attract lightning, and it's aluminum, okay.

p50 50:00

Aluminum in 1850 — let's say, I should have the prices here. Aluminum in 1852 was $545 a pound. If you divide by 16, it was more expensive than gold, which is about $25 an ounce, okay. The price came down. By 1854, Napoleon was — thought this would be a great armor for his soldiers and stuff, so he was funding the development of aluminum in France. And at the time they were using either sodium or potassium to reduce aluminum chloride. It was still a very intensive process. It wasn't until the 1880s in the United States the Hall process dropped the price — actually in 1886 I think it was — but anyway, the price was coming down, but Hall cut it in half. Remember what happens if you cut the price of a structural material in half? You will go up four times in the quantity used. And they kept on dropping the price, between — up by 1897 it was 36 cents a pound, or dollars a pound, 36 cents — yeah, 36 cents a pound.

p51 51:09

So aluminum had tremendous growth. If you look at the product sales, uh, 1889, they sold 7,000 pounds. By 1909 they were selling 15 tons, or fifteen thousand — fifteen thousand tons, okay, of aluminum. And if you keep going, the real growth of aluminum came in World War II. And you said, this is world's total for aluminum production. Germany was making more than we were in 1939. By the end of the war we kind of outstripped them. The Germans hadn't been able to increase it much, but we went from 148 to 695. And all of a sudden Alcoa, which owned most of the business in the United States, was making 2.6 million tons of aluminum, whereas the United States was making less than 10 times that. Here's Andrew Mellon's aluminum Pierce-Arrow automobile. They were making horse carriages out of aluminum in New Kensington, Pennsylvania in 1909.

p52 52:19

There was something else I was going to show you in here.

[Tom looks through slides.]

Oh, well this isn't the one I was thinking of. There is a good one in here. Farming, oh — well this is a good one, this is what Alcoa said this is what Pittsburgh Reduction Company looks like, this idyllic picture. And here's the actual picture, okay, it's not quite as idyllic, okay. There's a lot of pollution in the smelting and refining of aluminum.

p53 52:58

But there's one plot in here, which — I could find it — talked about Alcoa's command of the market. I'm not seeing it right now, but basically Alcoa had a monopoly. They had 100% of the market for bauxite in the world, okay. They were a true monopoly in the aluminum business. Um, and I think I mentioned that George Kenney, who was Joel Clark's first doctoral student, did his doctoral thesis on aluminum and magnesium and showed pretty convincingly that Alcoa and Dow had to have fixed prices after World War II. And Alcoa said, we won't go into the magnesium business if you stay out of the aluminum business now. And so Dow took over the magnesium business and had a monopoly there. And the two of them had — you could match their prices over time from 1945 up until 1975 when George did his thesis.

p54 54:03

Um, so, when we hear these terrible things about other countries doing terrible things, just remember, we do the same thing, we just [don't] advertise it quite the same way, okay. Any questions? If not, uh, you can have Monday off, or anything — what's today, Tuesday, yeah. Okay, we got class Wednesday, Thursday. I'll be here on Thursday, we'll finish up all the rest of the periodic table on Thursday, I guess, um, for structural materials. And then um, Dr. Belmar will be here next Tuesday for the last of our two sets of lectures. And then Wednesday — I need to sign up, if you haven't signed up please do, we're going to send it around, make sure everybody gets signed up. If anybody has any questions about the presentations, come see me.