How does a gel become mechanically stable?

Gels are strange materials. They are mostly made of a liquid, however they are solid. This solidity comes from the structure of the gel: a dilute solid network.

Transmission electron micrograph of a casein gel.

See the network in the above picture? Here the strands of the network are made of aggregated proteins. The holes, or pores, are permeated by water.

A gel network can be made of various building blocks. For example if you take very long, linear molecules that you crosslink from time to time, you get a polymer network. If this network is swelled by a solvent, then it is a gel. That is the case of panna cotta, where long collagen molecules from the gelatin associate into a network to imprison the creamy milk.

In the case of a yogurt, you start from globular proteins called caseins (think of little balls) dispersed in water. If you make them attract each other, the proteins will spontaneously aggregate into a network.

From a mechanical point of view, these two cases look quite different. Long molecules are floppy, adopt many configurations. If you pull on such a long molecule, you are decreasing the number of configurations it can adopt. This is costly in terms of (free) energy, so it is hard to pull, as if the chain was a little spring. Now is you assemble such springs into a network, it is quite obvious that you will get a solid that is easy to deform.

Using the path in black, it is possible to go from one end of the sample to the other. This sample is percolated. The black path is a percolation path.

Now, if you assemble sticky balls into a network, and if you pull on it, will it deform elastically or immediately break down into pieces? What are the conditions to make a particle gel stable? The answer to these question is not obvious and there have been many different answers in the literature.

1. In polymer gels, having a percolating network is enough to have mechanical stability. Percolation means that it is possible to find a path along the network that goes from one end of the sample to the other. But many observation concluded that this was not enough to have mechanical stability in the case of particle gels.
2. A glass is mechanically stable because its particles are not able to rearrange, trapped by the cage formed by their neighbours. This concept was imported into gels by saying that particles were trapped by the attractive bonds they formed with their neighbours. This theory allows arrest, but does not explain the network structure of the gel. For a long time it was thought that a combination of percolation and glassy arrest could explain gel stability.
3. About a decade ago the paradigm shifted. There was this class of phase separation called "spinodal decomposition" that spontaneously formed a bicontinous pattern: a phase rich in particles intertwined with a phase poor in particles. Usually the pattern coarsen with time until complete separation of the phases. But it was found that if the particle-rich phase is dense enough to undergo a glass transition, then it becomes arrested and the structure stop evolving. So we get a network structure and thus a gel. This is called the arrested spinodal theory. However at very low volume fractions it does not describes well some observations. More importantly, it does not predicts the mechanical behaviour of the gel.
4. But there are other ideas in the literature that come more from a mechanical point of view. Back in the 19th century, Maxwell stated that mechanical stability was ensured if the number of mechanical constraints is equal to the number of degrees of freedom. From example, if you live in 3D space (I do), you have 6 degrees of freedom : you can move east, west, north, south, up and down and any combination of theses. If you are blocked so that you can't move north, can't move south, can't move east, can't move west, can't move up and can't move down, then you cannot move anywhere. So you are stable. This concept of "isostaticity" is very useful at the macroscopic scale, when you want to build a bridge or when you want to understand sand piles. But is this concept relevant when each particle is jiggling around due to thermal motion? In 2012, a paper found that when you look at a gel before and after breaking it, you find a decrease of the particles that have 6 or more bonds. These are actually the particles that should be stable, since each bond is a constrains, so higher than 6 you shouldn't be able to move.
5. In 2016, percolation stroke back. A paper found that not all paths along the network were important. If you considered only paths that never turned back, that were "directed", then you are interested in "directed percolation", not "isotropic percolation". The authors found that all their samples where directed percolation took place were mechanically stable, and that no other sample was. So, is directed percolation the cause of mechanical stability? For the moment, just remember that their samples were very dilute (less than 10% of particles).

The path in black is a percolation path that never turn back. This is a directed percolation path.

Here we arrive on the scene with our method to follow experimentally each individual particle during the process of gelation. All previous experiments were done by observing the state of the already formed gel. So the only influence that had been studied was the fraction of solid particles and the strength of the interactions. Here we add another axis: time.

We asked this question: can we observe when a gel become mechanically stable, and how is the microstructure changing at that moment?

First, we had to find a way of checking whether the suspension was mechanically stable or not. Usually you do that by putting the suspension in a rheometer, you oscillate at very low amplitude to measure the mechanical response. This response has two parts: elastic and viscous. If the viscous part is larger than the elastic part, the suspension is still liquid. If the elastic part is larger than the viscous part, the suspension is solid, so the gel has become mechanically stable. But in our case we need large (3 micron) particles to be able to observe everything in minute details. Large particles makes extremely soft gels. So soft that the rheometer does not have enough sensitivity.

Therefore, we ditch the idea of a rheometer altogether and only look at the response of the system to thermal agitation. The sample is just under the microscope and we record the trajectories of all the particles due to thermal agitation. If particles are able to diffuse away freely, it means that the suspension is liquid. If the particles are stuck and vibrate around a mean position, it means that the suspension is solid. Actually, a clever method call microrheology manages to transform the displacement of the particles into a measure of the mechanical response, elastic or viscous. In this way, we know exactly when our suspension becomes a mechanically stable gel.

In parallel, we can follow the progress of percolation. The usual isotropic percolation occurs always way before mechanical stability. Explanation (1) is out of the game.

We can also follow directed percolation. It occurs later than isotropic percolation, and actually for dilute gels (below 10-12% particle fraction), the time of directed percolation matches very well the time of mechanical stability. But, it does not work at all a higher volume fraction. Mechanical stability occurs sometimes 5-15 times later than the directed percolation. So, obviously explanation (5) is not general.

Now, we can look at isostatic particles, these particles that have 6 or more neighbours. Are these particles percolating? Yes, they are, and always at the exact time where mechanical stability sets in (see error bars in the paper, because science has error bars). So explanation (4) seems to be the correct one.

But then, why does explanation (4) give the right time at low particle fraction?

Look at the cartoons below. This is in 2 dimensions, so isostaticity means having 4 neighbours, not 6 like in 3D. Isostatic particles are shown in purple.

Path to gelation in the dilute case

In the dilute case (less than 10-12%)

• When particles begin to aggregate, they form very loose clusters, very open and far from each other.
• These clusters compact. Particles make more bonds within the same cluster, but clusters are too far away from each other to meet now. Because of this compaction, the heart of each cluster is now isostatic.
• Clusters finally begin to meet and form larger and larger clusters, until you get a percolating path. In this situation, you have groups of isostatic particles that are bridged by floppy non-isostatic bridges.
• In order to make more bonds, floppy bridges have to straighten. So at the time isostaticity percolates through the system, the network is mostly made of straight paths. So directed percolation is easy and occur at the same time.

Path to gelation in the dense case

In the dense case (more than 10-12%)

• When particles begin to aggregate, they are so close together that there is no space between clusters. Very quickly a percolating network is formed.
• That is only after the formation of this initial network that rearrangements occur. More bonds are created locally and this is enough to obtain a directed percolating path.
• Compaction continues to proceed until isostaticity percolates. That only then that the gel is mechanically stable.

That explains why directed percolation looks like a good explanation if you look only at dilute samples.

To conclude, we can view a gel as a network that is sculpted and arrested by mechanical forces. Our mechanical explanation does not really contradict the arrested spinodal theory that is more thermodynamics. But we hope that explaining gels by mechanics will help understand the mechanics of gels. For example, we still do not understand why some particle gels break into well-defined and irreversible fractures (think yogurt) whereas some others just flow plastically and reversibly (think toothpaste or fresh cement).

If you want to dig more in depth, our paper is scheduled to be published the 31th of May 2019 in Science Advances, and a preprint is already available on ArXiv:
H. Tsurusawa, M. Leocmach, J. Russo, H. Tanaka, Direct link between mechanical stability in gels and percolation of isostatic particles. Sci. Adv. 5, eaav6090 (2019). arXiv:1804.04370

Want to study how flocs, swarms or crowds flow? I'm looking for prospective PhD student

Have you ever seen the patterns made by birds, sheeps or insects when they come together? There is no boss in the mass of living bodies, however they self-organize.



The same kind of patterns can be seen at the microscopic scale in colonies of bacteria or in living tissues.



And recently, I've been working on non-living microscopic particles that self-propel, displaying the same kind of patterns.

Long exposure picture of self-propelled particles

A lot of beautiful physics has been done in the last decade about this class of system. Now it's known as "Active Matter".

Patterns are mesmerizing, physics is intellectually pleasing, but what is the purpose? What do you make out of this "Active Matter"? Can you build a bridge? Power your home? Cure cancer ?

Well, maybe.

It becomes clearer by the day that cancer metastasis is a swarm of cancer cells migrating through the body, very close to the above patterns. In which conditions the solid tumour becomes a liquid-like swarm? How to influence this transition? These are actual questions physicists and biophysicists are asking right now.

Maybe you can't power a house with active matter, but maybe you can make it do the worm of pumping the water of your shower. It has been found that a suspension of swimming micro-organisms flow more readily (has a lower viscosity) than the suspension of dead micro-organisms. Furthermore, in some situations, the viscosity is even lower than the liquid alone, without micro-organisms! They swim, converting their food into movement, and this moment helps the water flow up the pipe.

And can we build something? Maybe not a bridge, but a muscle that would be able to contract from the action of trillions of micro-motors. Or some kind of new material that would react to a push to the left by deforming to the right?

To understand this last point, I am looking for a PhD student interested in physics, mechanics, materials and afraid neither to code nor to perform experiments. This is an experimental investigation. See the announcement (2 pages, FR then EN) on my lab's website.

Crystalline gels ArXiV

Our paper on how crystalline gels form is out on the ArXiV http://arxiv.org/abs/1802.00772

Very timely weather today in Lyon: first day of snow of the year (second of the winter). Lots of Bergeron processes happening up there.

Crystalline gels

What happened this summer, part 2/n

We have a paper out in Nature Materials on how crystallisation can help make a gel.
Tsurusawa, H., Russo, J., Leocmach, M., & Tanaka, H. (2017). Formation of porous crystals via viscoelastic phase separation. Nature Materials, 16(10), 1022–1028.

This is the second result of my collaboration with the lab of Hajime Tanaka, where I did my PhD. You haven't heard about the first result? We are still writing it down. In academia chronological order is not always granted.

It all started with a crazy idea from the boss and an even crazier “I'll try that” from a fresh PhD student around April 2008. It took Hideyo almost three years, including a depression, to hammer this idea into a working experimental setup and one more year to perform the experiments before graduating. Then he joined a private company and left me with a mountain of data to analyse. I had followed the story from the beginning as we started our PhD at the same time. I had completed my PhD on colloidal glass a year before he finished his about colloidal gels. Different subjects but many common methods. Hideyo was a skilled experimentalist, I was more keen on developing analysis methods.

We were both working with large colloidal particles (plastic balls of 3 microns in diameter) dispersed in an oily solvent. This system is perfect for observing in 3D at the particle level whatever physical phenomenon. The particles are charged and repel each other at long range. In water, you usually have plenty of dissolved ions. These ions tend to screen electrostatic repulsion, which means that same charges do not repel each other if they are further than 10 nm, at most 100 nm in extremely pure and neutral water. However in our oily solvent there are very few dissolved ions and electrostatic charges still can feel each other 10 microns apart.

Engineering interactions between colloidal particles. Refractive index matching and hairs ensures hard repulsion at contact. Charges provide long range repulsion but can be screened by ions. Non adsorbing polymers induces short range depletion attraction.

For me it was a bane since I wanted colloidal glasses, that is concentrated suspensions with particles close to contact. So I added some strange salts able to dissolve into the oil, providing ions that would shorten the range of repulsion. At that time, it was known that if you added polymers to the mix, they induced a short ranged attraction between particles and even at low particle content you could obtain a network of particles.

A colloidal gel observed by confocal microscopy

Such a solid network intertwined with a liquid solvent is called a gel. Yogurt is a gel, as most of our foods, organs, and many cosmetics. How gels form is still quite mysterious. We know that particles that attract each other would prefer to be grouped all together, leaving a large swath of empty solvent aside. A bit like when salad dressing unmix with oil on one side and vinegar on the other. Except that a yoghurt does not expel all the whey otherwise nobody wants to eat it. Some phenomenon stops the separation and allows the stability of the network. Except that your skin cream that was nice and stable yesterday just collapsed in a separated mess this morning. Nobody knows why and when a gel will suddenly lose its stability.

To understand that, we have to know why the phase separation arrests in the first place. We have to know how a gel forms. And for this we want to observe gel formation with our large colloids to be able to follow what is going on in every detail. But nobody knew how to do that.

Sketch of the semi-permeable cell

That when Hajime Tanaka had his crazy idea. Let's mix particles and polymers together but without salt. We have a short range attraction that is hidden by the long range repulsion. The suspension is stable with particles that stay far away from each other. We put this suspension in a chamber suitable for microscopy where the bottom is a membrane filter. Pore size is chosen so that neither colloidal particles nor polymers can go through, but salt can. Now we put everything under the microscope, add a salty solution on the other side of the membrane, and see the suspension forming a gel.

What is especially great with this idea is that with large particles and thin enough sample chamber ions diffuse so fast across the chamber that switching off the repulsion is practically instantaneous from the point of view of the slowly diffusing particles.

It seems simple but it took a couple of years or engineering to get the method right. Thanks Hideyo for toiling on that. Thanks also to John who analyzed a subset of the data and found that there was something strange going on; something that was at odd with existing models. Thanks also for calling me back to participate in that exciting story, even if I originally had to analyse a different subset of the data.

The most common model for gel formation relies on glass transition. If you cool a liquid without crystallising it it will slow down so much that it hardly flows anymore. One could wait the age of the universe before observing any flow. So practically what was a liquid is now a solid, disordered like a liquid. This is the definition of a glass. You can also obtain a glass by compression rather than cooling. The phase separation between a particle poor phase and a particle rich phase is analog to a gas-liquid phase separation. The colloidal gas contains almost only solvent and the colloidal liquid is very concentrated in particles. What the model says is that the liquid is son concentrated, so dense, that it become a glass. To sum up, a special type of phase separation (a “spinodal decomposition”) creates a liquid network, but this liquid becomes a glass and so the network arrests and becomes solid.

Reconstruction of gel structure. Gas particles in orange, liquid in grey, crystal in purple. Left: strong attration, thin network. Right: weaker attraction, stress-driven rearrangement is possible and thus crystallisation.

In our experiments we observed a very different scenario. The network formed, but strands were so thin (one or two particles thick) that we had a hard time calling it a liquid or a glass phase. In some conditions (weaker attraction) some strands snapped and the network could coarsen a bit more, maybe 4-5 particles thick. Here occurred the unexpected: crystallisation.

Because there was enough space available in the liquid network, the particles in the network were able to rearrange locally to form crystal nuclei. Instead of a disordered glass we obtained a network full of ordered crystals.

Growth of the crystals beyond the original liquid network

At some point, a crystal reached the edge of the liquid network. And it did not stop there. Particles in the gas adsorbed on the crystal, allowing it to grow further than the envelope of the original network. But there are so few particles in the gas, they should be quickly spent? Not if other parts of the system sublimate or vaporize. What we found is that particles in the liquid network vaporized and then adsorb on crystals far away, making them grow.

Ice crystal grow at the expense of surrounding supercooled water droplets.

Interestingly, this sequence of events is very probably what is responsible for rain. Atmospheric clouds are made of water droplets. It is cold up there and the water is supercooled, liquid despite a temperature below freezing. Thermodynamics tells us that water vapor in contact with supercooled liquid water has to be at higher pressure than water vapor in contact with ice at the same temperature. Actually when one droplet eventually freezes we obtain an ice crystal in contact with vapor which pressure is too high because set by the surrounding supercooled water droplets. So the gas condenses on the crystal, and the crystal grows at the expense of surrounding droplets that need to evaporate to maintain the vapor pressure. The crystal sucks the water out of the droplets without touching them. At some point the crystal becomes large enough to fall out of the cloud. Tens of meters below the temperature is hot enough to melt the crystal into a rain drop. This is called the Bergeron process. Next time you open your umbrella, think about this complicated sequence of events involving three phases - crystal, liquid and vapor.

Of course, if the temperature is below freezing down to the floor we get snow. The delicate geometric shapes of snowflakes are made possible by their formation process. Vapor adsorption on crystals allows a much slower and more harmonious growth than direct liquid condensation. Crystalline planes are more ordered, cleanly arranged. That is what we observed in our crystal-gels.

So, to sum up, we have observed an other way to arrest a phase separation into a gel that involves crystallisation rather than glass transition. This process creates a crystalline network with a large area of neat, vapor-deposited crystalline planes. It screams “catalysis” to my ear, or any kind of application that needs a large area of crystalline materials. And we demonstrated that such porous materials could be made in one pot, with the system tumbling down all the different steps by itself: phase separation, stress-driven rearrangements, crystal nucleation, vapor deposition. I hope people designing “real materials” (not made with fancy colloids) will be able to make such crystal-gels with nice applications down the line.

ANR grant! Recruiting PhD student.

Unstacking what went on this summer 1/n

I had the pleasure to learn that my research proposal to the French national research agency (ANR) will be funded. I'll have 4 years to look into the microscopic mechanisms of gel fracture.

It means I'll be recruiting a PhD student from October 2018. If you are interested, let me know.

Selected in TOC ROFL!

Our graphical abstract for the "polymer in procession" paper has been selected by TOC ROFl, a Tumblr that collects "funny table-of-contents images from scientific journal articles."

http://tocrofl.tumblr.com/post/160821117531/caterpillar

Polymers in procession

Almost three years ago I became involved in an interdisciplinary project between physicists and chemists. The chemists were specialists in organic chemistry, that is to say, make complicated molecules mostly based on carbon. The physicists were specialists of the mechanics of soft materials, that is to say, how matter in between fluid and solid deform, break or flow.

Making these two groups of people work together was very difficult. Interdisciplinary science is hard. Scientists spend years or decades to understand enough a narrow field of knowledge to be able to make it progress. So when you put together scientists of different fields, they do not have the same vocabulary, the same methods, the same questions or the same expectations. When among physicists we were saying "We impose a constant shear stress" as a matter of fact, chemists were seeing us as

Physicist as seen by chemists

but we only meant "we apply a sideways constant force on the sample". And of course when chemists were telling us "This counter-ion is more chaotropic" we thought they were doing something like this:

Chemist as seen by physicists

To understand what the chemists meant I had to remember my chemistry classes like 15 years ago. Fortunately I quite liked chemistry in undergrads. I even defined myself as a chemical physicist, a much needed missing transmission belt. I was able to play the role of translator between the two groups. What the chemists meant was that the ion was disturbing a lot the water around itself.

At the end, we were able to work together. We made mechanical experiments on samples that were about a millimetre thick and we understood the results at the level of atoms. Conversely, we used this chemical understanding to design the mechanical properties of our samples. Let me explain to you what we did, in terms that both my physicist and chemist colleagues are able to understand.

All started with a new synthesis method used by the chemists. Polymers are long molecules where the same unit is repeated many times, a bit like a caterpillar. To make polymers the chemists started from a head and added about 70 body segments one by one. Then they added the chemical groups they wanted to each unit, like if they added legs to every body segment.

Here they managed to have a head with two negative charges and each body segments with one positive charge. In water the polymer schematically looks like that:

A polymer were most of the counterions are far away.

The minus charges floating around are counter ions. They are here to ensure that matter has a neutral charge in average. Some counter ions are floating far from the polymer, other are very close to the body segment they neutralise. We say that they are "condensed" on the polymer. The more condensed counter ions, the less the polymer looks charged from far away.

If you put that short linear polymer in pure water, it forms a very soft gel. Interestingly, you can inject it with a syringe. The gel is solid at rest, flows through the needle, and is solid again on the other side. Quite nice if you want to use a gel as a scaffold for cell growth in vivo. Nowadays, the gel is a soft solid that breaks irreversibly. You need a surgical procedure to put it in the body. With our type of gel a needle is enough.

Unfortunately for the applications, we found that our gel was very easily disturbed. If instead of pure water we used salty water the gel collapsed. If we started from a neutral head instead of the head bearing two minuses, no gel could form. Our mechanical measurements found no difference between the polymer solution and water alone. So we thought that the gel was formed due to charge interactions: minus head sticking to plus body. If no minus on the head, no gel. If salts, themselves charged, get in the way of the electrostatic attraction, no gel.

Also, something was quite strange: the gel was too soft. Like a thousand times too soft for such short polymers. A polymer gel is a 3D network whose edges are polymer chains and whose nodes are where chains meet, also called cross-links. The more meeting points you have, the harder the gel is. In other words, if you have short chains between cross-links, few body segments, the gel is hard. We measured the elasticity of the gel, and it was so soft that we predicted something like 60 000 body segments between meeting points! That is enough to make 880 of our short polymers!

Pine processionary caterpillars (source)

As the caterpillars on the picture above, our short polymers go on a single file.

So, we physicists were like "wow! that's strange" while the chemists were not caring much. Actually, the chemists were playing with their synthesis method to change the legs of the caterpillar.

Two ways to change the legs of the caterpillars: shape of leg correspond to the nature of the cation, either Immidazolium (aromatic cycle) or Pyrrolidinum (all single bonds). The colour corresponds to the counterion: F^-, Cl^-, Br^- or I^-.

For some compositions, the polymer was basically insoluble. No way to make a gel with it. To understand that, we have to remember that polymers are usually not very happy in water. What allows them to dissolve is their charges. If a polymer carries a lot of same charges (here pluses) these charges will repel each other, the polymer will stretch and will accept a lot of contact with water. If a polymer carries little charges, it will just collapse on itself to minimize the contact with water. You may remember from above that the more counter ions are condensed, the less charges the polymer carry, the less soluble it is.

A polymer with complete counterion condensation. Probably insoluble.

And indeed, we observed insolubility for the three compositions where the interaction between the repeated cation and its counterion was the strongest.

On the opposite, when the repeated cation and its counterion interacted weakly, we observed very strong gels, indicating shorter processions. Actually for two compositions we observed gels exactly 880 times stronger than the original one, meaning that the processions were just a single chain long.

So far so good, but all of this was learned by probing gently the softness of the gels, at deformations so low that they were not flowing but behaving as solids. To understand what is going on at larger strains, we have to have a look at the internal structure of a procession.

The procession at different scales.

As we said before, the monomers hates being in contact with water, so their preferred shape for the procession is a sphere. However plus charges prefer to be as far away as possible, so their preferred shape for the procession is a rod. It append that water-hating monomers are stronger on the small scales and that estranged charges are stronger on the large scales. So there is a scale D were the two influences balance. If the procession is just long enough to coil into a sphere of diameter D, then charges do not complain too much. But if the procession is longer, the charges refuse to make a larger sphere, and instead the procession grows into a cylinder of diameter D.

This cylinder does no grow in a straight line indefinitely. On scales large enough, counterions screen the charges from each other and the procession winds its way away.

Two charges in the mood for fight screened from each other by counterions.

So when we pushed harder on the gel to make them flow we found two threshold deformations. The first threshold corresponds to when the large scale winding path of the processions becomes extended. On small scales the procession is still collapsed to avoid contact with water. To stretch it further more monomers has to come in contact with water, it cost much more energy and this is visible on the mechanical measurements. The second threshold corresponds to the breaking of head to body bonds and it's when the gel flows.

Each circle is a blob of momomers collapsed to avoid contact with water.

For all compositions, the first threshold deformation is very small, telling us that the processions are almost linear at rest. It implies that the amount of charge condensation is directly related to the softness of the gel. So we are able to estimate charge condensation that varies from 10 free counterions per polymers (lots of charges) to one free counterion every 9 polymers in the procession (very few charges).

By contrast the second threshold vary widely between compositions between 10% and 800%.  Some gels flow immediately, others need to be stretched height time their initial size before flowing. This indicates that the head to body bonds are incredibly strong. Usually in water ionic bonds are about 100 times weaker that chemical (covalent) bonds. For our lowest charge polymer we measure head to body bonds that are within 20% of the carbon-carbon bond!

Our explanation is that with few charges the procession collapse around the head-to-body bond to avoid water. So the environment just around the bond is not water, it's hydrophobic polymer. Such environment is like an oil, where charges are few but interact very strongly. Indeed in oils other people have measured ionic bonds that strong. Actually this strategy is used by life itself: proteins can have just one charge in the middle of a large hydrophobic patch. When two such proteins with opposite charges meet the two hydrophobic patched stick together, expelling water from the direct environment of the charged and the ionic bond become very strong. This forms a lock and key mechanism that helps for example our immune system to recognise and block pathogens.


Time to wrap up, thanks for reading down to here. At the end, we have done very standard mechanical measurements at the millimetre scale to extract informations at the chemical level. Our model tells us what to change to tune the mechanical properties of our gel by a factor thousand. Thanks to a referee, we also did a back of the envelope calculation to see what these gels would give in a physiological environment, and we have a good candidate to inject in a living body. If anybody is interested on the biology side...

Reference:

Srour H, et al. Ion pairing controls rheological properties of “processionary” polyelectrolyte hydrogels. Soft Matter. 2016. ArXiv 1611.07721.