Reversible switching Schematic illustrating the hard/soft transition of the hydrogel/NAAC composite. (Courtesy: CC BY 4.0/Int. J. Extrem. Manuf. 10.1088/2631-7990/adbd97)
Complex hydrogel structures created using 3D printing are increasingly employed in fields including flexible electronics, soft robotics and regenerative medicine. Currently, however, such hydrogels are often soft and fragile, limiting their practical utility. Researchers at Zhejiang University in China have now fabricated 3D-printed hydrogels that can be easily, and repeatably, switched between soft and hard states, enabling novel applications such as smart medical bandages or information encryption.
“Our primary motivation was to overcome the inherent limitations of 3D-printed hydrogels, particularly their soft, weak and fragile mechanical properties, to broaden their application potential,” says co-senior author Yong He.
The research team created the hard/soft switchable composite by infusing supersaturated salt solution (sodium acetate, NAAC) into 3D-printed polyacrylamide (PAAM)-based hydrogel structures. The hardness switching is enabled by the liquid/solid transition of the salt solution within the hydrogel.
Initially, the salt molecules are arranged randomly within the hydrogel and the PAAM/NAAC composite is soft and flexible. The energy barrier separating the soft and hard states prevents spontaneous crystallization, but can be overcome by artificially seeding a crystal nucleus (via exposure to a salt crystal or contact with a sharp object). This seed promotes a phase transition to a hard state, with numerous rigid, rod-like nanoscale crystals forming within the hydrogel matrix.
Superior mechanical parameters
The researchers created a series of PAAM/NAAC structures, using projection-based 3D printing to print hydrogel shapes and then soaking them in NAAC solution. Upon seeding, the structures rapidly transformed from transparent to opaque as the crystallization spread through the sample at speeds of up to 4.5 mm/s.
The crystallization dramatically changed the material’s mechanical performance. For example, a soft cylinder of PAAM/1.5NAAC (containing 150 wt% salt) could be easily compressed by hand, returning to its original shape after release. After crystallization, four 9x9x12 mm cylinders could support an adult’s weight without deforming.
For this composite, just 1 min of crystallization dramatically increased the compression Young’s modulus compared with the soft state. And after 24 h, the Young’s modulus grew from 110 kPa to 871.88 MPa. Importantly, the hydrogel could be easily returned to its soft state by heating and then cooling, a process that could be repeated many times.
The team also performed Shore hardness testing on various composites, observing that hardness values increased with increasing NAAC concentration. In PAAM/1.7NAAC composites (170 wt% salt), the Shore D value reached 86.5, comparable to that of hard plastic materials.
The hydrogel’s crosslinking density also impacted its mechanical performance. For PAAM/1.5NAAC composites, increasing the mass percentage of polymer crosslinker from 0.02 to 0.16 wt% increased the compression Young’s modulus to 1.2 GPa and the compression strength to 81.7 MPa. The team note that these parameters far exceed those of any existing 3D-printed hydrogels.
Smart plaster cast
He and colleagues demonstrated how the hard/soft switching and robust mechanical properties of PAAM/NAAC can create medical fixation devices, such as a smart plaster cast. The idea here is that the soft hydrogel can be moulded around the injured bone, and then rapidly frozen in shape by crystallization to support the injury and promote healing.
The researchers tested the smart plaster cast on an injured forearm. After applying a layer of soft cotton padding, they carefully wrapped around layers of the smart plaster bandage (packed within a polyethylene film to prevent accidental seeding). The flexible hydrogel could be conformed to the curved surface of limbs and then induced to crystallize.
Medical fixation device Application of the PAAM/NAAC composite to create a smart plaster cast. (Courtesy: CC BY 4.0/Int. J. Extrem. Manuf. 10.1088/2631-7990/adbd97)
After just 10 min of crystallization, the smart plaster cast reached a yield strength of 8.7 MPa, rapidly providing support for the injured arm. In comparison, a traditional plaster cast (as currently used to treat bone fractures) took about 24 h to fully harden, reaching a maximum yield strength of 3.9 MPa
To determine the safety of the exothermic crystallization process, the team monitored temperature changes in the plaster cast nearest to the skin. The temperature peaked at 41.5 °C after 25 min of crystallization, below the ISO-recommended maximum safe temperature of 50 °C.
The researchers suggest that the ease of use, portability and fast response of the smart plaster cast could provide a simple and effective solution for emergency and first aid situations. Another benefit is that, in contrast to traditional plaster casts that obstruct X-rays and hinder imaging, X-rays easily penetrate through the smart plaster cast to enable high-quality imaging during the healing process.
While the composites exhibit high strength and Young’s modulus, they are not as tough as ideally desired. “For example, the elongation at break was less than 10% in tensile testing for the PAAM/1.5NAAC and PAAM/1.7NAAC samples, highlighting the challenge of balancing toughness with strength and modulus,” He tells Physics World. “Therefore, our current research focuses on enhancing the toughness of these composite materials without compromising their modulus, with the goal of developing strong, tough and mechanically switchable materials.”
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In 2014 the American mathematical physicist S James Gates Jr shared his “theorist’s bucket list” of physics discoveries he would like to see happen before, as he puts it, he “shuffles off this mortal coil”. A decade later, Physics World’s Margaret Harris caught up once more with Gates, who is now at the University of Maryland, US, to see what discoveries he can check off his list; what he would still like to see discovered, proven or explored; and what more he might add to the list, as of 2025.
The first thing on your list 10 years ago was the discovery of the Higgs boson, which had happened. The next thing on your list was gravitational waves.
The initial successful detection of gravity waves [in 2015] was a spectacular day for a lot of us. I had been following the development of that detector [the Laser Interferometer Gravitational-wave Observatory, or LIGO] almost from its birth. The first time I heard about detecting gravity waves was around 1985. I was a new associate professor at Maryland, and a gentleman by the name of [Richard] Rick Isaacson, who was a programme officer at the National Science Foundation (NSF), called me one day into his office to show me a proposal from a Caltech-MIT collaboration to fund a detector. I read it and I said this will never work. Fortunately, Isaacson is a superhero and made this happen because for decades he was the person in the NSF with the faith that this could happen; so when it did, it was just an amazing day.
Why is the discovery of these gravitational waves so exciting for physicists?
Albert Einstein’s final big prediction was that there would be observable gravitational waves in the universe. It’s very funny – if you go back into the literature, he first says yes this is possible, but at some point he changes his mind again. It’s very interesting to think about how human it is to bounce back and forth, and then to have Mother Nature say look, you got it right the first time. So such a sharp confirmation of the theory of general relativity was unlike anything I could imagine happening in my lifetime, quite frankly, even though it was on my bucket list.
The other thing is that our species knows about the heavens mostly because there have been “entities” that are similar to Mercury, the Greek god who carried messages from Mount Olympus. In our version of the story, Mercury is replaced by photons. It’s light that has been telling us for hundreds of thousands of years, maybe a million years, that there’s something out there and this drove the development of science for several hundred years. With the detection of gravitational waves, there’s a new kid on the block to deliver the message, and that’s the graviton. Just like light, it has both particle and wave aspects, so now we have detected gravitational waves, the next big thing is to be able to detect gravitons.
We are not completely clear on exactly how to see gravitons, but once we have that knowledge, we will be able to do something that we’ve never been able to do as a species in this universe. After the initial moments of the Big Bang, there was a period of darkness, when matter was far too hot to form neutral atoms, and light could not travel through the dense plasma. It took 380,000 years for electrons to be trapped in orbits around nuclei, forming the first atoms.
Eventually, the universe had expanded so much that the average temperature and density of particles had dropped enough for light to travel. Now what’s really interesting is if you look at the universe via photons, you can only look so far back up to that point when light was first able to travel through the universe, often referred to as the “first dawn”. We detected this light in the 1960s, and it’s called the cosmic microwave background. If you want to peer further back in time beyond this period, you can’t use light but you can use gravitational waves. We will be able as a species eventually to look maybe all the way back to the Big Bang, and that’s remarkable.
What’s the path to seeing gravitons experimentally?
At the time that gravitational waves were detected by LIGO there were three different detectors, two in the US and one on the border of France and Italy called Virgo. There is a new LIGO site coming online in India now, and so what’s going to happen, provided there continues to be a global consensus on continuing to do this science, is that more sites like this are going to come online, which will give us higher-fidelity pictures. It’s going to be a difference akin to going from black and white TV to colour.
Wish fulfilled Aerial view of the Virgo detector in Italy. This facility became the third to detect gravitational waves, in 2017, after the two LIGO detectors in the US. As more gravitational-wave facilities come online around the world, we increase our chance of detecting gravitons. (CCO 1.0 The Virgo collaboration)
In the universe now, the pathway to detecting gravitons involves two steps. First, you probably want to measure the polarization of gravitons, and Fabry–Pérot interferometers, such as LIGO, have that capacity. If it’s a polarized graviton wave, the bending of space-time has a certain signature, whether it’s left or right-handed. If we are lucky enough we will actually see that polarization, I would guess within the next 10 years.
The second step is quantization, which is going to be a challenge. Back in the 1960s a physicist at the University of Maryland named Joseph Weber developed what are now called Weber bars. They’re big metal bars and the idea was you cool them down and then if a graviton impinges on these bars, it would induce lattice vibrations in the metal, and you would detect those. I suspect there’s going to be a big push in going back and upgrading that technology. One of the most exciting things about that is they might be quantum Weber bars. That’s the road that I could see to actually nailing down the existence of the graviton.
Number three on your bucket list from a decade ago was supersymmetry. How have its prospects developed in the past 10 years?
At the end of the Second World War, in an address to the Japanese people after the atomic bombing of Hiroshima and Nagasaki, the Japanese emperor [known as Showa in Japan, Hirohito in the West] used the phrase “The situation has developed not necessarily to our advantage”, and I believe we can apply that to supersymmetry. In 2006 I published a paper where I said explicitly I did not expect the Large Hadron Collider (LHC) to detect supersymmetry. It was a back-of-the-envelope calculation, where I was looking at the issue of anomalous magnetic moments. Because the magnetic moments can be sensitive to particles you can’t actually detect, by looking at the anomalous magnetic moment and then comparing the measured value to what is predicted by all the particles that you know, you can put lower bounds on the particles that you don’t know, and that’s what I did to come up with this number.
It looked to me like the lightest “superpartner” was probably going to be in the range of 30 Tev. The LHC’s initial operations were at 7 TeV and it’s currently at 14 TeV, so I’m feeling comfortable about this issue. If it’s not found by the time we reach 100 Tev, well, I’m likely going to kick the bucket by the time we get that technology. But I am confident that SUSY is out there in nature for reasons of quantum stability.
Also, observations of particle physics – particularly high-precision observations, magnetic moments, branching ratios, decay rates – are not the only way to think about finding supersymmetry. In particular, one could imagine that within string theory, there might be cosmological implications (arXiv:1907.05829), which are mostly limited to the question of dark matter and dark energy. When it comes to the dark-matter contribution in the universe, if you look at the mathematics of supersymmetry, you can easily find that there are particles that we haven’t observed yet and these might be the lightest supersymmetric particle.
And the final thing in your bucket list, which you’ve touched on, was superstring theory. When we last spoke, you said that you did not expect to see it. How has that changed, if at all?
Unless I’m blessed with a life as long as Methuselah, I don’t expect to see that. I think that for superstring theory to win observational acceptance, it will likely come about not from a single experiment, but from a confluence of observations of the cosmology and astrophysics type, and maybe then the lightest super symmetric particle will be found. By the way, I don’t expect extra dimensions ever to be found. But if I did have several hundred years to live, those are the kinds of likely expectations I would have.
And have you added anything new to your bucket list over the past 10 years?
Yes, but I don’t quite know how to verbalize it. It has to do with a confluence of things around quantum mechanics and information. In my own research, one of the striking things about the graphs that we developed to understand the representation theory of supersymmetry –we call them “adinkras” – is that error-correcting codes are part of these constructs. In fact, for me this is the proudest piece of research I’ve ever enabled – to discover a kind of physics law, or at least the possibility of a physics law, that includes error-correcting codes. I know of no previous example in history where a law of physics includes error-correcting codes, but we can clearly see it in the mathematics around these graphs (arXiv:1108.4124).
That had a profound impact on the way I think about information theory. In the 1980s, John Wheeler came up with this very interesting way to think about quantum mechanics (“Information, physics, quantum: the search for links” Proc. 3rd Int. Symp. Foundations of Quantum Mechanics, Tokyo, 1989, pp354–368). A shorthand phrase to describe it is “it from bit” – meaning that the information that we see in the universe is somehow connected to bits. As a young person, I thought that was the craziest thing I had ever heard. But in my own research I saw that it’s possible for the laws of physics to contain bits in the form of error-correcting codes, so I had to then rethink my rejection of what I thought was a wild idea.
In fact, now that I’m old, I’ve concluded that if you do theoretical physics long enough, you too can become crazy – because that’s what sort of happened to me! In the mathematics of supersymmetry, there is no way to avoid the presence of error-correcting codes and therefore bits. And because of that my new item for the bucket list is an actual observational demonstration that the laws of quantum mechanics entail the use of information in bits.
In terms of when we might see that, it will be long after I’ve gone. Unless I somehow get another 150 years of life. Intellectually, that’s how long I would estimate it will take as of now, because the hints are so stark, they suggest something is definitely going on.
We’ve talked a little bit about how science has changed in the past 10 years. Of course, science is not unconnected with the rest of the world. There have been some changes in other things that impinge on science, particularly those recently developing in the US. What’s your take on that?
Unfortunately, it’s been very predictable. Two years ago I wrote an essay called “Expelled from the mountain top?” (Science 380 993). I took that title from a statement by Martin Luther King Jr where he says “I’ve been to the mountaintop”, and the part about being “expelled” refers to closing down opportunities for people of colour. In my essay I talked about the fact that it looked to me like the US was moving in a direction where it would be less likely that people like me – a man of colour, an African American, a scientist – would continue to have access to the kind of educational training that it takes to do this [science].
I’m still of the opinion that the 2023 decision the Supreme Court made [about affirmative action] doesn’t make sense. What it is saying is that diversity has no role in driving innovation. But there’s lots of evidence that that’s not right. How do you think cities came into existence? They are places where innovation occurs because you have diverse people coming to cities.
You add to that the presence of a new medium – the Internet – and the fact that with this new medium, anyone can reach millions of people. Why is this a little bit frightening? Well, fake news. Misinformation.
Still hopeful Jim Gates discusses his career and his lifelong interest in supersymmetry with an audience at the Royal College of Art in London earlier this year. (Courtesy: Margaret Harris)
I ran into a philosopher about a year ago, and he made a statement that I found very profound. He said think of the printing press. It allowed books to disseminate through Western European society in a way that had never happened before, and therefore it drove literacy. How long did it take for literacy levels to increase? 50 to 100 years. Then he said, now let’s think about the Internet. What’s different about it? The difference is that anyone can say anything and reach millions of people. And so the challenge is how long it will take for our species to learn to write the Internet without misinformation or fake news. And if he’s right, that’s 100, 150 years. That’s part of the challenge that the US is facing. It’s not just a challenge for my country, but somehow it seems to be particularly critical in my country.
So what does this have to do with science? In 2005 I was invited to deliver a plenary address to the American Association for the Advancement of Science annual meeting. In that address, I made statements about science being turned off because it was clear to me, even back then in my country, that there were elements in our society that would be perfectly happy to deny evidence brought forth by scientists, and that these elements were becoming stronger.
You put this all together and it’s going to be an extraordinarily important, challenging time for the continuation of science because, certainly at the level of fundamental science, this is something that the public generally has to say “Yes, we want to invest in this”. If you have agencies and agents in society denying vaccines, for example, or denying the scientific evidence around evolution or climate change, if this is going to be something that the public buys into, then science itself potentially can be turned off, and that’s the thing I was warning about in 2005.
What are some practical things that members of the scientific community can do to help prevent that from happening?
First of all, come down from the ivory tower. I’ve been a part of some activities, and they normally are under the rubric of restoring the public’s trust in science, and I think that’s the wrong framing. It’s the public faith in science that’s under attack. So from my perspective, that’s what I’d much rather have people really thinking about.
What would you say the difference is between having trust in science and having faith in science?
In my mind, if I trust something, I will listen. If I have faith in something, I will listen and I will act. To me, this is a sharp distinction.
Personally, even though I expect that it’s going to be really hard going forward, I am hopeful. And I would urge young people never to lose that hope. If you lose hope, there is no hope. It’s just that simple. And so I am hopeful. Even though people may take my comments as “oh, he’s just depressed” – no, I’m not. Because I’m a scientist, I believe that one must, in a clear-eyed, hard-headed manner, look at the evidence that’s in front of us and not sentimentally try to dodge what you see, and that’s who I am. So I am hopeful in spite of all the things that I’ve just said to you.
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If a water droplet flowing over a surface gets stuck, and then unsticks itself, it generates an electric charge. The discoverers of this so-called depinning phenomenon are researchers at RMIT University and the University of Melbourne, both in Australia, and they say that boosting it could make energy-harvesting devices more efficient.
The newly-observed charging mechanism is conceptually similar to slide electrification, which occurs when a liquid leaves a surface – that is, when the surface goes from wet to dry. However, the idea that the opposite process can also generate a charge is new, says Peter Sherrell, who co-led the study. “We have found that going from dry to wet matters as well and may even be (in some cases) more important,” says Sherrell, an interdisciplinary research fellow at RMIT. “Our results show how something as simple as water moving on a surface still shows basic phenomena that have not been understood yet.”
Co-team leader Joe Berry, a fluid dynamics expert at Melbourne, notes that the charging mechanism only occurs when the water droplet gets temporarily stuck on the surface. “This suggests that we could design surfaces with specific structure and/or chemistry to control this charging,” he says. “We could reduce this charge for applications where it is a problem – for example in fuel handling – or, conversely, enhance it for applications where it is a benefit. These include increasing the speed of chemical reactions on catalyst surfaces to make next-generation batteries more efficient.”
More than 500 experiments
To observe depinning, the researchers built an experimental apparatus that enabled them to control the sticking and slipping motion of a water droplet on a Teflon surface while measuring the corresponding change in electrical charge. They also controlled the size of the droplet, making it big enough to wet the surface all at once, or smaller to de-wet it. This allowed them to distinguish between multiple mechanisms at play as they sequentially wetted and dried the same region of the surface.
Their study, which is published in Physical Review Letters, is based on more than 500 wetting and de-wetting experiments performed by PhD student Shuaijia Chen, Sherrell says. These experiments showed that the largest change in charge – from 0 to 4.1 nanocoulombs (nC) – occurred the first time the water contacted the surface. The amount of charge then oscillated between about 3.2 and 4.1 nC as the system alternated between wet and dry phases. “Importantly, this charge does not disappear,” Sherrell says. “It is likely generated at the interface and probably retained in the droplet as it moves over the surface.”
The motivation for the experiment came when Berry asked Sherrell a deceptively simple question: was it possible to harvest electricity from raindrops? To find out, they decided to supervise a semester-long research project for a master’s student in the chemical engineering degree programme at Melbourne. “The project grew from there, first with two more research project students [before] Chen then took over to build the final experimental platform and take the measurements,” Berry recalls.
The main challenge, he adds, was that they did not initially understand the phenomenon they were measuring. “Another obstacle was to design the exact protocol required to repeatedly produce the charging effect we observed,” he says.
Potential applications
Understanding how and why electric charge is generated as liquids flow during over surfaces is important, Berry says, especially with new, flammable types of renewable fuels such as hydrogen and ammonia seen as part of the transition to net zero. “At present, with existing fuels, charge build-up is reduced by restricting flow using additives or other measures, which may not be effective in newer fuels,” he explains. “This knowledge may help us to engineer coatings that could mitigate charge in new fuels.”
The RMIT/Melbourne researchers now plan to investigate the stick-slip phenomenon with other types of liquids and surfaces and are keen to partner with industries to target applications that can make a real-world impact. “At this stage, we have simply reported that this phenomenon occurs,” Sherrell says. “We now want to show that we can control when and where these charging events happen – either to maximize them or eliminate them. We are still a long way off from using our discovery for chemical and energy applications – but it’s a big step in the right direction.”
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An international team led by chemists at the University of British Columbia (UBC), Canada, has reported strong experimental evidence for a superfluid phase in molecular hydrogen at 0.4 K. This phase, theoretically predicted in 1972, had only been observed in helium and ultracold atomic gases until now, and never in molecules. The work could give scientists a better understanding of quantum phase transitions and collective phenomena. More speculatively, it could advance the field of hydrogen storage and transportation.
Superfluidity is a quantum mechanical effect that occurs at temperatures near absolute zero. As the temperatures of certain fluids approach this value, they undergo a transition to a zero-viscosity state and begin to flow without resistance – behaviour that is fundamentally different to that of ordinary liquids.
Previously, superfluidity had been observed in helium (3He and 4He) and in clusters of ultracold atoms known as Bose-Einstein condensates. In principle, molecular hydrogen (H2), which is the simplest and lightest of all molecules, should also become superfluid at ultracold temperatures. Like 4He, H2 is a boson, so it is theoretically capable of condensing into a superfluid phase. The problem is that it is only predicted to enter this superfluid state at a temperature between 1 and 2 K, which is lower than its freezing point of 13.8 K.
A new twist on a spinning experiment
To keep their molecular hydrogen liquid below its freezing point, team leader Takamasa Momose and colleagues at UBC confined small clusters of hydrogen molecules inside helium nanodroplets at 0.4 K. They then embedded a methane molecule in the hydrogen cluster and observed its rotation with laser spectroscopy.
Momose describes this set-up as a miniature version of an experiment performed by the Georgian physicist Elephter Andronikashvili in 1946, which showed that disks inside superfluid helium could rotate without resistance. They chose methane as their “disk”, Momose explains, because it rotates quickly and interacts only very weakly with H2, meaning it does not disturb the behaviour of the medium in which it spins.
Onset of superfluidity
In clusters containing less than six hydrogen molecules, they observed some evidence of friction affecting the methane’s rotation. As the clusters grew to 10 molecules, this friction began to disappear and the spinning methane molecule rotated faster, without resistance. This implies that most of the hydrogen molecules around it are behaving as a single quantum entity, which is a signature of superfluidity. “For clusters larger than N = 10, the hydrogen acted like a perfect superfluid, confirming that it flows with zero resistance,” Momose tells Physics World.
The researchers, who have been working on this project for nearly 20 years, say they took it on because detecting superfluidity in H2 is “one of the most intriguing unanswered questions in physics – debated for 50 years”. As well as working out how to keep hydrogen in a liquid state at extremely low temperatures, they also had to find a way to detect the onset of superfluidity with high enough precision. “By using methane as a probe, we were finally able to measure how hydrogen affects its motion,” Momose says.
A deeper understanding
The team say the discovery opens new avenues for exploring quantum fluids beyond helium. This could lead scientists to a deeper understanding of quantum phase transitions and collective quantum phenomena, Momose adds.
The researchers now plan to study larger hydrogen clusters (ranging from N = 20 to over a million) to understand how superfluidity evolves with size and whether the clusters eventually freeze or remain fluid. “This will help us explore the boundary between quantum and classical matter,” Momose explains.
They also want to test how superfluid hydrogen responds to external stimuli such as electric and magnetic fields. Such experiments could reveal even more fascinating quantum behaviours and deepen our understanding of molecular superfluidity, Momose says. They could also have practical applications, he adds.
“From a practical standpoint, hydrogen is a crucial element in clean energy technologies, and understanding its quantum properties could inspire new approaches for hydrogen storage and transportation,” he says. “The results from these [experiments] may also provide critical insights into achieving superfluidity in bulk liquid hydrogen – an essential step toward harnessing frictionless flow for more efficient energy transport systems.”
Connexion
