Tag Archives: chemical synthesis

3D printed all liquid electronics

Even after watching the video, I still don’t quite believe it. A March 28, 2018 news item on ScienceDaily announces the work,

Scientists from the Department of Energy’s Lawrence Berkeley National Laboratory (Berkeley Lab [or LBNL]) have developed a way to print 3-D structures composed entirely of liquids. Using a modified 3-D printer, they injected threads of water into silicone oil — sculpting tubes made of one liquid within another liquid.

They envision their all-liquid material could be used to construct liquid electronics that power flexible, stretchable devices. The scientists also foresee chemically tuning the tubes and flowing molecules through them, leading to new ways to separate molecules or precisely deliver nanoscale building blocks to under-construction compounds.

A March 28, 2018 Berkeley Lab March 26, 2018 news release (also on EurekAlert), which originated the news item, describe the work in more detail,

The researchers have printed threads of water between 10 microns and 1 millimeter in diameter, and in a variety of spiraling and branching shapes up to several meters in length. What’s more, the material can conform to its surroundings and repeatedly change shape.

“It’s a new class of material that can reconfigure itself, and it has the potential to be customized into liquid reaction vessels for many uses, from chemical synthesis to ion transport to catalysis,” said Tom Russell, a visiting faculty scientist in Berkeley Lab’s Materials Sciences Division. He developed the material with Joe Forth, a postdoctoral researcher in the Materials Sciences Division, as well as other scientists from Berkeley Lab and several other institutions. They report their research March 24 [2018] in the journal Advanced Materials.

The material owes its origins to two advances: learning how to create liquid tubes inside another liquid, and then automating the process.

For the first step, the scientists developed a way to sheathe tubes of water in a special nanoparticle-derived surfactant that locks the water in place. The surfactant, essentially soap, prevents the tubes from breaking up into droplets. Their surfactant is so good at its job, the scientists call it a nanoparticle supersoap.

The supersoap was achieved by dispersing gold nanoparticles into water and polymer ligands into oil. The gold nanoparticles and polymer ligands want to attach to each other, but they also want to remain in their respective water and oil mediums. The ligands were developed with help from Brett Helms at the Molecular Foundry, a DOE Office of Science User Facility located at Berkeley Lab.

In practice, soon after the water is injected into the oil, dozens of ligands in the oil attach to individual nanoparticles in the water, forming a nanoparticle supersoap. These supersoaps jam together and vitrify, like glass, which stabilizes the interface between oil and water and locks the liquid structures in position.

This stability means we can stretch water into a tube, and it remains a tube. Or we can shape water into an ellipsoid, and it remains an ellipsoid,” said Russell. “We’ve used these nanoparticle supersoaps to print tubes of water that last for several months.”

Next came automation. Forth modified an off-the-shelf 3-D printer by removing the components designed to print plastic and replacing them with a syringe pump and needle that extrudes liquid. He then programmed the printer to insert the needle into the oil substrate and inject water in a predetermined pattern.

“We can squeeze liquid from a needle, and place threads of water anywhere we want in three dimensions,” said Forth. “We can also ping the material with an external force, which momentarily breaks the supersoap’s stability and changes the shape of the water threads. The structures are endlessly reconfigurable.”

This image illustrates how the water is printed,

These schematics show the printing of water in oil using a nanoparticle supersoap. Gold nanoparticles in the water combine with polymer ligands in the oil to form an elastic film (nanoparticle supersoap) at the interface, locking the structure in place. (Credit: Berkeley Lab)

Here’s a link to and a citation for the paper,

Reconfigurable Printed Liquids by Joe Forth, Xubo Liu, Jaffar Hasnain, Anju Toor, Karol Miszta, Shaowei Shi, Phillip L. Geissler, Todd Emrick, Brett A. Helms, Thomas P. Russell. Advanced Materials https://doi.org/10.1002/adma.201707603 First published: 24 March 2018

This paper is behind a paywall.

Concrete proof that materials at the nanoscale behave differently than materials at any other scale

I hadn’t realized this still needed to be proved but it’s always good to have your misconceptions adjusted. Here’s more about the work from the University of Cambridge in a Sept. 30, 2016 news item on phys.org,

Scientists have long suspected that the way materials behave on the nanoscale – that is when particles have dimensions of about 1–100 nanometres – is different from how they behave on any other scale. A new paper in the journal Chemical Science provides concrete proof that this is the case.

The laws of thermodynamics govern the behaviour of materials in the macro world, while quantum mechanics describes behaviour of particles at the other extreme, in the world of single atoms and electrons.

A Sept. 29, 2016 University of Cambridge press release, which originated the news item, hones in on the peculiarities of the nanoscale,

In the middle, on the order of around 10–100,000 molecules, something different is going on. Because it’s such a tiny scale, the particles have a really big surface-area-to-volume ratio. This means the energetics of what goes on at the surface become very important, much as they do on the atomic scale, where quantum mechanics is often applied.

Classical thermodynamics breaks down. But because there are so many particles, and there are many interactions between them, the quantum model doesn’t quite work either.

And because there are so many particles doing different things at the same time, it’s difficult to simulate all their interactions using a computer. It’s also hard to gather much experimental information, because we haven’t yet developed the capacity to measure behaviour on such a tiny scale.

This conundrum becomes particularly acute when we’re trying to understand crystallisation, the process by which particles, randomly distributed in a solution, can form highly ordered crystal structures, given the right conditions.

Chemists don’t really understand how this works. How do around 1018 molecules, moving around in solution at random, come together to form a micro- to millimetre size ordered crystal? Most remarkable perhaps is the fact that in most cases every crystal is ordered in the same way every time the crystal is formed.

However, it turns out that different conditions can sometimes yield different crystal structures. These are known as polymorphs, and they’re important in many branches of science including medicine – a drug can behave differently in the body depending on which polymorph it’s crystallised in.

What we do know so far about the process, at least according to one widely accepted model, is that particles in solution can come together to form a nucleus, and once a critical mass is reached we see crystal growth. The structure of the nucleus determines the structure of the final crystal, that is, which polymorph we get.

What we have not known until now is what determines the structure of the nucleus in the first place, and that happens on the nanoscale.

In this paper, the authors have used mechanochemistry – that is milling and grinding – to obtain nanosized particles, small enough that surface effects become significant. In other words, the chemistry of the nanoworld – which structures are the most stable at this scale, and what conditions affect their stability, has been studied for the first time with carefully controlled experiments.

And by changing the milling conditions, for example by adding a small amount of solvent, the authors have been able to control which polymorph is the most stable. Professor Jeremy Sanders of the University of Cambridge’s Department of Chemistry, who led the work, said “It is exciting that these simple experiments, when carried out with great care, can unexpectedly open a new door to understanding the fundamental question of how surface effects can control the stability of nanocrystals.”

Joel Bernstein, Global Distinguished Professor of Chemistry at NYU Abu Dhabi, and an expert in crystal growth and structure, explains: “The authors have elegantly shown how to experimentally measure and simulate situations where you have two possible nuclei, say A and B, and determine that A is more stable. And they can also show what conditions are necessary in order for these stabilities to invert, and for B to become more stable than A.”

“This is really news, because you can’t make those predictions using classical thermodynamics, and nor is this the quantum effect. But by doing these experiments, the authors have started to gain an understanding of how things do behave on this size regime, and how we can predict and thus control it. The elegant part of the experiment is that they have been able to nucleate A and B selectively and reversibly.”

One of the key words of chemical synthesis is ‘control’. Chemists are always trying to control the properties of materials, whether that’s to make a better dye or plastic, or a drug that’s more effective in the body. So if we can learn to control how molecules in a solution come together to form solids, we can gain a great deal. This work is a significant first step in gaining that control.

Nicely written!

Here’s a link to and a citation for the paper,

Solvation and surface effects on polymorph stabilities at the nanoscale by A. M. Belenguer, G. I. Lampronti, A. J. Cruz-Cabeza, C. A. Hunter, and J. K. M. Sanders. Chem. Sci., 2016, Advance Article DOI: 10.1039/C6SC03457H First published online 02 Sep 2016

This paper is open access.

Given that the news release mentions crystals, this lovely image illustrates the press release,

 Snow Crystal Landscape Credit: Peter Gorges

Snow Crystal Landscape Credit: Peter Gorges