Sunday, May 21, 2023

What is a glass?

I want to write about a recently published paper, but to do so on an accessible level, I should really lay some ground work first.

At the primary school level, typically people are taught that there are three states of matter: solid, liquid, and gas.  (Plasma may be introduced as a fourth state sometimes.)  These three states are readily distinguished because they have vastly different mechanical properties.  We now know that there are many more states of matter than just those few, because we have developed ways to look at materials that can see differences that are much more subtle than bulk mechanical response.  As I discussed a little bit here, something is a "solid" if it resists being compressed and sheared; the constituent atoms/molecules are right up against each other, and through their interactions (chemical bonds, "hard-core repulsion"), the material develops internal stresses when it's deformed that oppose the deformation.   

Broadly speaking, there are two kinds of solids, crystals and glasses.  In crystals, which physicists love to study because the math is very pretty, the constituent atoms or molecules are spontaneously arranged in a regular, repeating pattern in space.  This spatial periodicity tends to minimize the interaction energy between the building blocks, so a crystalline structure is typically the lowest energy configuration of the collective bunch of building blocks.  The spatial periodicity is readily detectable because that repeating motif leads to constructive interference for scattering of, e.g., x-rays in particular directions - diffraction spots.  (Most crystalline solids are really polycrystalline, an aggregation of a bunch of distinctly oriented crystal grains with boundaries.)

The problem is, just because a crystalline arrangement is the most energetically favored situation, that doesn't mean that the building blocks can easily get into that arrangement if one starts from a liquid and cools down.   In a glass, there are many, many configurations of building blocks that are local minima in the potential energy of the system, and the energy required to change from one such configuration to another is large compared to what is available thermally.  A paper on this is here.  In ordinary silica glass, the local chemistry between silicon and oxygen is the same as in crystalline quartz, but the silicon and oxygen atoms have gotten hung up somehow, kinetically unable to get to the crystalline configuration.  The glass is mechanically rigid (on typical timescales of interest - glass does not meaningfully flow).  Try to do x-ray diffraction from a glass, and instead of seeing the discrete spots that you would with a crystal, instead you will get a mushy ring indicating an average interparticle distance, like in a liquid (when the building blocks are also right up against each other).  
Figure (credit: Chiara Cammarota, from here): A schematic rugged
energy 
landscape with a multitude of energy minima,
maxima, and saddles. Arrows denote some of the possible
relaxation pathways. 

A hallmark of glasses is that they have a very broad distribution of relaxation times for structural motions, stretching out to extremely long timescales.  This is a signature of the "energy landscape" for the different configurations, where there are many local minima with a huge distribution of "barrier heights".  This is illustrated in the figure at right (sourced from the Simons Collaboration on Cracking the Glass Problem).  Glasses have been a fascinating physics problem for decades.  They highlight challenges in how to think about thermodynamic equilibrium, while having universality in many of their properties.  Window glass, molecular glasses, many polymers that we encounter - all of these disparate systems are glasses.

13 comments:

Pizza Perusing Physicist said...

In my opinion, no theory of glass will be complete unless it also explains Anthony Davis of the Lakers.

Anonymous said...

What does a complete theory of glassiness look like? For superconductivity it would be something like a machine which gives you Tc for a material and the contributions from basic microscopic interactions (phonons, spin...). What's the analog for glasses?

Stefan Bringuier said...

You mention two primary types of solids, namely, crystals and glasses. I would have done the same, but I'm curious about your thoughts on how quasicrystals might integrate into this schema?

I particularly find quasicrystals intriguing in that they exhibit periodic and aperiodic ordering. It's like they have the medium-range atomic symmetries of crystals, i.e., rotational with very limited-translation symmetry, but break true translation symmetry like glasses do.

Any thoughts on the interplay of order and disorder seen in quasicrystals could be explained in terms of "...distribution of relaxation times for structural motions, stretching out to extremely long timescales"? Maybe quasicrystal formation theory is well-developed already; not sure.

Anonymous said...

I think quasi crystal formation is understood from local interactions,.not from a glass transition dynamical picture.

There is no periodic order in 3D this. No translational periodicity. There is such order in higher dimensions from which a 3d qc can be projected down.

Douglas Natelson said...

PPP, as an Astros fan, I would've said Lance McCullers these days.

Anon@11:17, good question. Perhaps some way to start from the building blocks and be able to predict the scaling of viscosity vs temperature and the frequency-dependent dynamics. Maybe mode coupling theory would be a good starting point.

Stefan, thanks for your comment. As Anon@7:47 says, I think from this perspective quasicrystals are basically crystals. Aperiodicity (when projected down into 3D) is not disorder in the sense of having large open volume and kinetic hindrance/jamming as in glasses.

Stefan Bringuier said...

@Douglas & @Anon 7:47PM

I see, so I need to think of it as the aperiodicity arising from the specific way that a higher-dimensional periodic structure can be projected to form an aperiodic structure in lower dimensions.

Andy Foulke said...

Thanks for the post!

So what does annealing do? I'm assuming the added thermal energy allows the "barrier heights" to be conquered somewhat - but not too much - so the resulting structure can adjust and have less stress

Andrew Dane said...

Hi Doug- you linked to a number of papers, but I wasn't sure which one you wanted to highlight- did you link to it?

Douglas Natelson said...

Andy, yes, thermal energy via annealing allows the system to rearrange itself by overcoming some of those barriers. The tricky bit is that these systems are strongly interacting, so that as the building blocks reconfigure and move around, the energy landscape itself evolves. Messy.

Aedane, I haven't gotten there yet. I'm going to write something next about spin glasses, and then highlight the paper. Wanted to do structural glasses first.

Adnoor said...

I understand. Basically, it means that the lack of regular patterns comes from how a higher-dimensional repeating structure is transformed into a non-repeating structure in lower dimensions.

Jeena Blogs said...
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Jeena Blogs said...
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