March Materials Madness candidates

Inspired by March Mammal Madness and the Periodic Playoff, I have now mused to my fellow materials science colleagues:

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But this means we need materials to put in a bracket. I have some ideas below. If we want to really this be materials and not just chemicals, we probably need to specify structure/processing in addition to composition. So I say Czochralski silicon instead of just “silicon” because that process makes the silicon used in modern electronics. However, I’m not sure if we need to split up related categories of materials more. On the other hand, I’m fine with not 100% specifying composition if changing the elements may be part of processing/design, which comes up a lot with transition metal dichalcogenices and perovskites. But do we need to specify those more into sub-groups that have more consistent crystal structures? (See this recent paper on what exactly IS a perovskite?)

Maybe we don’t need 64 for a first attempt, but 32 might nice. I would love to hear more ideas from people on WordPress and Twitter!

  1. Gold nanoparticles
  2. Transition metal dichalcogenides
  3. Metallic glass
  4. Nacre
  5. Silver nanoparticles
  6. Nitinol
  7. Mesoporous metals
  8. Clays
  9. Collagen
  10. Silk
  11. Graphene
  12. Carbon nanotubes
  13. Diamond
  14. Perovskites – does this need to be split out more?
  15. Czochralski silicon
  16. PDMS
  17. hexagonal boron nitride
  18. Antimicrobial copper-alloy touch surfaces
  19. Cadmium telluride
  20. Stainless steel
  21. Neodymium magnets (Nd2Fe14B)
  22. Cellulose
  23. Chitin

Materials Advent 2018 Part 17 – Snow

Hexagonal plate with dendritic extensions. (precipitating snow).
Snow in an electron microscope.

The US Department of Agriculture has a seriously fascinating page on microscopy of snow flakes because it helps advance understanding of weather and crystal formation.

Snowflakes (usually) have hexagonal symmetry because this reflects the crystal structure of water molecules in the solid. This old article from Scientific American goes a bit more into the details on the formation of snowflakes, but it’s also something we still don’t entirely understand

Materials Advent 2018 Part 16 – Glitter

The New York times has already run the most whimsical materials science piece of the day and I won’t attempt to top the delightful Caity Weaver. So discover What is Glitter, or aluminum metalized polyethylene terephthalate.

PET polymer chain
Model of polyethylene terephthalate. Oxygen atoms are red, hydrogen atoms are white/gray, and carbon atoms are black.

Materials Advent 2018 Part 12-15 – Silver and Gold, large and small

Uses of silver in the U.S.
uses of gold in the USA

I’ll slightly tweak my rules again, because you know what silver and gold look like, and I actually think it’s interesting to tell people that we have lots of practical uses for them. Gold and silver are transition metals, that special middle part of the periodic table which represents the addition of a new set of electron orbitals (the d-orbitals). Electrons in the d-orbitals are special because they tend to overlap in energy with those in the s- or p-orbitals, helping increase the number of electrons that are free to move. This is actually why gold and silver are shiny – they have electrons that are easily excited and interact with visible light and reflect it back. Gold gets its unique yellow color because its electrons move so fast they actually need to be described by relativity and it shows that their energies decrease (essentially because of their increased relativistic mass at high speed).

The energy levels of silver hydride (AgH) and gold hydrige (AuH) before (n.r.) and after accounting for relativity. From this Reddit conversation on relativity in chemistry.

You’re probably less familiar with the nanoscale forms of gold and silver. Or you might be with silver because we now use the nanoparticles in lot of things for their antimicrobial properties. Our lab actually makes a lot of metal nanoparticles, and so I can show you a high-resolution image of these particles.

Silver nanoparticles on amorphous carbon. The lines in the particles are actually the organized rows of atoms. From this paper by my research lab.

Gold nanoparticles (and many other metals) are neat because they can completely change the color of solutions they are in, often to red in the case of gold. This is different from the yellow we see for large gold pieces because at a very small size, the electrons in the particles have different energy levels than at the macro scale, and so they absorb light from different colors. Old stained glass actually gets its colors from tiny amounts of metallic nanoparticles being incorporated into the glass while it was being formed. We’re still not entirely sure how the nanoparticles were incorporated in stained glass. Theories range from it being caused by poor cleaning of gold residue from the surfaces glass was worked on or contamination in the source materials.

The Lycurgus Cup is a particularly special kind of stained glass that changes color depending on how it is lit.

Materials Advent 2018 Parts 9, 10, and 11 – Weird Glasses

A teardropped shaped piece of glass seems to have an iridescent sheen
A photo of a Prince Rupert’s drop taken with a special polarizer that helps reveals stresses in the material

Following up on yesterday, I thought it would be fun to look at some weirder glasses.

Prince Rupert’s drops are teardrop (or tadpole) shaped pieces of glass made by dropping molten glass into cold water. They are famous for their bizarre strength. You can pound on the head all you want, and it will almost never break, but nick the tail a little bit and it spectacularly explodes.

Poof

This turns out to come from the way the drop forms. That initial bit that hits the water cools so fast it actually gets compressed by the cooling, making it stronger, but the tail is basically a path to the weak core. The trippy oil-puddle-esque image above is taken with a special kind of set-up that looks at light that ends up being polarized by stresses within the glass. Prince Rupert’s drops turn out to be technologically important, because efforts to understand them since the 1600s have inspired research into ways to make other kinds of glass stronger, leading to the Gorilla Glass and other toughened glass that now lines our smartphones and many other displays.

Metallic glasses are just what they sound like. Just like how I mentioned yesterday that metals are usually crystals, it turns out we can also try making them into glasses by cooling them so quickly their atoms can’t form an ordered structure. This requires either incredibly fast cooling (on the scale of at least 1000 degrees a second for some compositions) or an interesting work around using a lot of different metals together. It turns out that mixing a bunch of atoms of different sizes makes it harder for them to pack into a neat pattern.

The mix of atoms in metallic glasses helps them stay disordered.
A microscopy image showing the real atoms in a glassy alloy of unspecified composition. From Physical Metallurgy (Fifth Edition)

You might wonder why we want to make glass out of metals. It turns out to provide a special property – bounciness. And we literally demonstrate that with “atomic trampolines”. It’s really easy to deform a crystalline metal because that orderly crystal structure makes it easy to slide rows of atoms past each other when you hit them hard enough, just like it’s easy to push a row of desks lined up in a classroom. The glass can’t deform – there’s no preferred direction to push the atoms, so instead the energy just goes back to whatever it hits. This has a cost though – if you hit it too hard, just like regular glass, a metallic glass just shatters instead of accepting a dent. There was initially a lot of hope for them as new materials for the shells of devices like smartphones since they don’t transmit that energy to the components inside, but that’s proved harder to make than hoped. However, you can buy a golf club that takes advantage of the bounciness to essentially transmit all the energy from your swing into the ball. (Going farther back, they evidently also form the basis of most of those theft prevention tags that ring alarms.)

Finally, I’m breaking my rule a bit with this last one by not having an image, but did you know that toffee is also a glass? (Sorry, no one has put toffee under a high-resolution microscope or run it under an X-ray source for weird images for me yet) Or at least good toffee is. That crisp crunch you get from well-made toffee is because of glass shattering. When toffee feels gritty, it is because it has actually started to crystallize and typically has hundreds of little mini-crystals that want to deform. This is why some recipes suggest adding corn syrup. The bigger sugar molecules in corn syrup mixed up with the sucrose in regular table sugar mix up in a way like the metallic glasses above and make it harder for them to set into their crystal structure. Similarly, an early kind of stunt glass for special effects was literally made by boiling sugar into a clear candy.

Materials Advent 2018 Part 8 – Glass

Silica goes from crystalline to amorphous (glassy) from right to left

I’m going to (hopefully) permanently end the popular misconception that glass is a liquid with this post. Glass is not a really slow liquid – it is in fact a solid, based on its flow properties (yay rheology!). But glass is a solid without structure, or in fancy terms, an amorphous solid. Many solids you see are crystalline, not just the pretty stones pop cultures tends to reserve the name “crystal” for. A crystalline material is one where their atoms or molecules are arranged in a repeating 3D pattern. The metals in your car, the silicon in your computer, and the calcium phosphate mineral in your bones are also all crystals because we can see their atoms follow some crystal structure. While the atoms/molecules can differ, mathematicians have found out that there are only about 200 distinct ways to make a repeating pattern in 3D with no gaps or overlaps (and only 17 for 2D). This might seem low, but the point is that while tiny details may change, there’s only so many ways to combine the symmetries you can find, like reflections or rotations, and still fill up all of space (or your wall).

The image above is a high-resolution transmission electron micrograph literally showing you the atoms in silica (silicon oxide) – the material that makes up regular glass. On the left, it’s a crystal and the dots on the bottom show you in red and green where the different atoms are in a hexagon arrangement. Around 3/4 of the way to the right you see that the atoms are no longer always in hexagons and the shapes start to change. This side is amorphous.

Materials Advent 2018 part 7 – Liquid Crystals

An image shows bright regions of color on a black background. The left shows features reminiscent of oil spills. The right shows multiple butterfly-like features of four same-colored spots around a central point.
A polarized light image shows the patterns caused by two different arrangements of liquid crystals within the same sample. From Wikipedia: Liquid crystal

Liquid crystals are everywhere now (if you’re looking at this on a computer, your display is probably LCD, and a decent chance any TV you looked at lately is an LCD too). They’re another one of those weird in-between states like we see in rheology. Liquid crystals are liquids based on their mechanical properties, but their molecules show some large-scale ordering that resembles solid crystals. This is because the molecules in liquid crystals tend to be relatively large, like a polymer chain, so you make distinct structures by lining them up, but it can also still be hard to pack them closely to make a true solid. The first liquid crystal was actually found studying cholesterol!

Rods pointing in the same direction but randomly spaced out.
A “nematic” liquid crystal – the molecules are lined up in the same direction, but there is not clear pattern in how they are spaced. 

Most LCDs are based on liquid crystals in the nematic phase seen above. (Although evidently not LCD TVs) Because the molecules are asymmetric, they can be oriented by electric fields because their electrons will be pulled by the electric force. The power in an LCD is basically to turn on and off the voltage to twist the crystals. This twisting is done to change how light passes through. A bunch of nematic liquid crystals lined up next to each other essentially act as a filter called a polarizer and line up the waves of light passing through. At the top and bottom layer of your display are two permanently oriented filters that are perpendicular to each other, an arrangement which would not let any light pass through without the crystals being lined up in a way to help align the light somewhere in between. (This is also why you can sort of see the pixels of LCDs at off-angles and why the picture can look so off away from the center of LCD TVs – the light is really only lined up for someone looking straight through the display.)

Materials Advent 2018 3 (and 4 and 5): Pearl and its components

A black pearl rests on an iridescent shell in a black background
A black pearl on the shell of a black-lipped pearl oyster. From Wikipedia: https://en.wikipedia.org/wiki/Pearl

Pearls are quite beautiful and also (kind of) rare, which makes us appreciate them even more. But it turns out they are made of very common components – a variant of chalk (calcium carbonate) bound in strings of the polymer that makes up insect, shrimp, and crab shells (called chitin, as well as a few other polymers). The calcium carbonate variant (or “polymorph“) is called aragonite, which technically has a different crystal structure from the form we actually use as chalk, which is called calcite. To make pearls even more interesting, aragonite isn’t actually the stable form of calcium carbonate at typical temperatures on the surface of Earth, but something about the way clams and other molluscs grow shells assembles that structure instead of calcite (and researchers still aren’t entirely sure why). 

Image result for crystal structure of aragonite

Despite essentially being a combination of chalk and insect shells, pearls and the related materials in mollusc shells are incredibly strong. We often attribute this to the strength of curves at our macro level, but it also turns out the way these parts are combined at the micro level is really important. The main solid part is essentially laid out slabs made of smaller bricks of aragonite, not unlike a brick house. And they are separated by small spaces due to rough bits on each brick, which is also where the entangling bits of polymers go. It’s really hard for cracks to get far in this arrangement – to travel through a slab it has to keep going through the alternating order of bricks and through the more flexible polymers separating them, and to go through multiple slabs a crack has to get through even more polymer and also change preferred directions along the crystals because the bricks change arrangement across slabs. As a result, pearls and clam shells are about 10 times stronger than individual hunks of aragonite or the polymers. This makes pearls an incredibly interesting composite that engineers want to mimic. In fact,a professor I work with at UVA has published multiple papers about the strength of mother-of-pearl (often called nacre in technical contexts) and tried to mimic this structure with graphene

original
An electron microscope image of flakes of aragonite in a mother-of-pearl sample

Industrially, humans get a lot of chitin from industrial processing of shellfish and use it as fertilizer as a food additive to help improve texture. 

Image result for chitin

So What is Materials Science (and Engineering)?

So this is my 100th post, and I felt like it should be kind of special. So I want to cover a question I get a lot, and one that’s important to me; what exactly is materials science? My early answer was that “it’s like if physics and chemistry had a really practical baby.” One of my favorite versions is a quote from this article on John Goodenough, one of the key figures in making rechargeable lithium ion batteries: “In hosting such researchers, Goodenough was part of the peculiar world of materials scientists, who at their best combine the intuition of physics with the meticulousness of chemistry and pragmatism of engineering”. Which is a much more elegant (and somewhat ego-boositng) way of wording my description. In one of my first classes in graduate school, my professor described materials science as “the study of defects and how to control them to obtain desirable properties”.

A more complete definition is some version of the one that shows up in most introductory lessons: materials science studies the relationship between the structure of a material, its properties, its performance, and the way it was treated. This is often represented as the “materials science tetrahedron”, shown below. Which turns out to be something people really love to use. (You also sometimes see characterization float in the middle, because it applies to all these aspects.)

A tetrahedron with blue points at the vertices. The top is labelled structe, the bottom three are properties, processing, and performance.

The materials science tetrahedron (with characterization floating in the middle).

Those terms may sound meaningless to you, so let’s break them down. In materials science, structure goes beyond that of chemistry: it’s not just what makeup of an atom or molecule that affects a material, but how the atoms/molecules are arranged together in a material has a huge effect on how it behaves. You’re probably familiar with one common example: carbon and its various allotropes. The hardness of diamond is partially attributed to its special crystal structure. Graphite is soft because it is easy to slide the different layers across each other. Another factor is the crystallinity of a material. Not all materials you see are monolithic pieces. Many are made of smaller crystals we call “grains”. The size and arrangement of these grains can be very important. For instance, the silicon in electronics is made in such a way to guarantee it will always be one single crystal because boundaries between grains would ruin its electronic properties. Turbine blades in jet engines and for wind turbines are single crystals, while steels used in structures are polycrystalline.

On the top is a diamond and a piece of graphite. On the bottom are their crystal structures.

Diamond and its crystal structure is on the left; graphite on the right.

Processing is what we do to a material before it ends up being used. This is more than just isolating the compounds you’ll use to make it. In fact, for some materials, processing actually involves adding impurities. Pure silicon wouldn’t be very effective in computers. Instead, silicon is “doped” with phosphorus or boron atoms and the different doping makes it possible to build various electronic components on the same piece. Processing can also determine the structure – temperature and composition can be manipulated to help control the size of grains in a material.

A ring is split into 10 different sections. Going counterclockwise from the top, each segment shows smaller crystals.

The same steel, with different size grains.

Properties and performance are closely related, and the distinction can be subtle (and honestly, it isn’t something we distinguish that much). One idea is that properties describe the essential behavior of a material, while performance reflects how that translates into its use, or the “properties under constraints“. This splits “materials science and engineering” into materials science for focusing on properties and materials engineering for focusing on performance. But that distinction can get blurred pretty quickly, especially if you look at different subfields. Someone who studies mechanical properties might say that corrosion is a performance issue since it limits how long a material could be used at its desired strength. Talk to my colleagues next door in the Center for Electrochemical Science and Engineering and they would almost all certainly consider corrosion to be a property of materials. Regardless, both of these depend on structure and processing. Blades in wind turbines and jet engines are single crystals because this reduces fatigue over time. Structural steels are polycrystals because this makes them stronger.

Now that I’ve thought about it more, I realize the different parts of the tetrahedron explain the different ways we define materials science and engineering. My “materials science as applied physics and chemistry” view reflects the scale of structures we talk about, from atoms that are typically chemistry’s domain to the crystal arrangement to the larger crystal as a whole, where I can talk about mechanics of atoms and grains. The description of Goodenough separates materials science from physics and chemistry through the performance-driven lens of pragmatism. My professor’s focus on defects comes from the processing part of the tetrahedron.

The tetrahedron also helps define the relationship of materials science and engineering to other fields. First, it helps limit what we call a “material”. Our notions of structure and processing are very different from the chemical engineers, and work best on solids. It also helps define limits to the field. Our structures aren’t primarily governed by quantum effects and we generally want defects, so we’re not redundant to solid-state physics. And when we talk about mechanics, we care a lot about the microstructure of the material, and rarely venture into the large continuum of mechanical and civil engineers.

At the same time, the tetrahedron also explains how interdisciplinary materials science is and can be. That makes sense because the tetrahedron developed to help unify materials science. A hundred years ago, “materials science” wouldn’t have meant anything to anyone. People studying metallurgy and ceramics were in their own mostly separate disciplines. The term semiconductor was only coined in a PhD dissertation in 1910, and polymers were still believed to be aggregates of molecules attracted to each other instead of the long chains we know them to be today. The development of crystallography and thermodynamics helped us tie all these together by helping us define structures, where they come from, and how we change them. (Polymers are still a bit weird in many materials science departments, but that’s a post for another day)

Each vertex is also a key branching off point to work with other disciplines. Our idea of structure isn’t redundant to chemistry and physics, but they build off each other. Atomic orbitals help explain why atoms end up in certain crystal structures. Defects end up being important in catalysts. Or we can look at structures that already exist in nature as an inspiration for own designs. One of my professors explained how he once did a project studying turtle shells from an atomic to macroscopic level, justifying it as a way to design stronger materials. Material properties put us in touch with anyone who wants to use our materials to go into their end products, from people designing jet engines to surgeons who want prosthetic implants, and have us talk to physicists and chemists to see how different properties emerge from structures.

This is what attracted me to materials science for graduate school. We can frame our thinking on each vertex , but it’s also expected that we shift. We can think about structures on a multitude of scales. Now I joke that being a bad physics major translates into being great at most of the physics I need to use now. The paradigm helps us approach all materials, not just the ones we personally study. Thinking with different applications in mind forces me to learn new things all the time. (When biomedical engineers sometimes try to claim they’re the “first” interdisciplinary field of engineering to come on the scene, I laugh thinking that they forget materials science has been around for decades. Heck, now I have 20 articles I want to read about the structure of pearl to help with my new research project.) It’s an incredibly exciting field to be in.