Liquid to a solid: Boron-modified silazanes for synthesis of SiBNC ceramics

"We have created a liquid that remains a liquid at room temperature and has a longer shelf life than other SiBNC polymers," Singh said. "But when you heat our polymer, it undergoes a liquid to solid transition. This transparent liquid polymer can transform into a very black, glasslike ceramic."

Ceramics are valuable because they withstand extreme temperatures and are used for a variety of materials, including spark plugs, jet engines, high-temperature furnaces or even space exploration materials.

Using five ingredients – silicon, boron, carbon, nitrogen and hydrogen – [the researchers have] created a liquid polymer that can transform into a ceramic with valuable thermal, optical and electronic properties. The waterlike polymer, which becomes a ceramic when heated, also can be mass-produced.

• The ceramic derived from this polymer can survive extreme temperatures as high as approximately 1,700 degrees Celsius. Yet the ceramic has a mass density three to six times lower than that of other ultrahigh-temperature ceramics, such as zirconium boride and hafnium carbide.

• The polymer can make ceramic fibers. If the polymer is heated to approximately 50 to 100 degrees Celsius, it becomes a gel similar to syrup or honey. During this gel state, the polymer can be pulled into strings or fibers to create ceramic textiles or ceramic mesh.

• The liquid polymer has processing flexibility. It can be poured into molds and heated to accurately make complex ceramic shapes.

• Because the polymer is a liquid, it is sprayable or can be used as a paint to make ceramic coatings. The ceramic can protect materials underneath or can create more efficient machinery that works in high-temperature environments, such as steam turbines or jet engine blades. The polymer also may be used for 3-D printing of ceramic parts using a benchtop SLA printer.

• When combined with carbon nanotubes, the polymer has even more applications. It can create a black material that can absorb all light -- even ultraviolet and infrared light -- without being damaged. The combined nanomaterial can withstand extreme heat of 15,000 watts per square centimeter, which is about 10 times more heat than a rocket nozzle.

• The polymer could be used to produce ceramic with tunable electrical conductivity ranging from insulator or semiconductor.

• The presence of silicon and graphenelike carbon in the ceramic can improve electrodes for lithium-ion batteries.

The silicon in the ceramic bonds to nitrogen and carbon but not boron; boron bonds to nitrogen but not carbon; and carbon bonds to another carbon to form graphenelike strings.

ScienceDaily, March 30, 2017 - Engineer Patents Waterlike Polymer to Create High-Temperature Ceramics.

I somehow missed this. Anyway, sorry for the complicated name but that is what his paper is titled. The source cited title did not have any pizazz hence the curious and funny science title (click bait, really! ETA: A more to the point title).

Welcome to the new world!!

This is what material science has been waiting for. One giant hammer blow unleashed upon this world. This is truly disruptive technology. Everything that carries water or oil at any temperature will get a coating. Steam engines? Not thinking “future” enough! Try, “supercritical CO2 turbines” where instead of steam the evil gas, carbon dioxide, is kept under pressure and heat (~750 °C) and is used to turn the turbine. This material will stand up to that!

National Energy Technology Laboratory - Supercritical CO2 Turbomachinery.

How about the “ceramic fibers”? Bullet proof vests, football helmets, gee, there are more uses than I can think of right now.

Lighter car frames any one? Save on fuel, save the planet because less emissions.

Speaking of engines… a ceramic engine! The ability to combust at higher temperature means a more complete fuel burn.

Kitchen knives and cutting wheels, bridges, battery anodes (both Li-ion and flow batteries), electronics, disk brakes, guitar amplifiers, space exploration (Mars habitat anyone?), pipelines, submarines, aircrafts, and that is just the first hour!!

Truly disruptive technology! This will touch all facets of modern life in one form or another. This may get graphene out of the lab and into real world applications at the very least, carbon nanotubes will be everywhere.

From ancient times where archeologists still turn up shards of yesterday's life to today we have come full circle.

Has TEOT lost it and gone over the edge? I bet there are people out here on ATS that know of other uses for ceramics. Opinions? Thoughts? Complaints?

PS - I don't know what the heck a "silazane " is but it sounds cool and you can dance to it!

I see some electrical property talk.

Could this be used to 3d print motherboards?

a reply to: grey580

The news story does not say much on the "electrical properties" but they do say the polymer can be used in off the shelf, good old, SLA machines already out there.

The article is almost a reprint of the Kansas State article (not much more information, a cool info graphic on the ceramic arrangement, though),

Kansas State article (k-state.edu): here

Technical ceramics tend to be excellent electric insulators (high dielectric strength). They are especially useful in high-temperature applications where other materials’ mechanical & thermal properties tend to degrade. Some ceramics have low electrical loss & high dielectric permittivity; these are typically used in electronic applications like capacitors and resonators. Additionally, the ability to combine an insulator with a structural component has lead to many product innovations.

precision-ceramics.com - Electrical properties

For those also interested in the vaguely worded, "electrical properties" this is what they are referring to (utilizing other properties of ceramics in addition to electrical uses).

a reply to: TEOTWAWKIAIFF

It can withstand heat but ceramics are brittle correct? If so it wouldn't make for good car frames or bridges.

Cool stuff nonetheless

a reply to: MfId77

When compressed ceramics are actually stronger than titanium.

The addition of carbon nanotubes increase the strength. Which is what the graphene quip was about--here is an application where graphene will be kept inside while people enjoy functionality of the ceramic. It will be like magic!

I also think they will combine usage with other materials. If you can make ceramic fiber, you can add those to carbon fiber for certain situations. It is the combined strength and light weight where most applications will benefit.

Material science has come of age! I wonder how creative the use will get?

a reply to: MfId77

Super strong. But yes they can be brittle.

However when combined with other materials. Then possibly.

a reply to: TEOTWAWKIAIFF

Hey Teot,
I am somewhat of a materials nerd, boy they sure seem to think it can do anything.
It will be interesting to see how it pans out. One thing I did not see was a setting temp., how hot do they have to get it to set.

Teot, have you followed any of the discussion in the aircraft forum, on the "green lady"?. If not, and for anybody else unaware, the green lady is a presumed "black project" aircraft that may burn a borane based fuel. Boranes were experimented with as a high energy fuels. They can be so energy dense that a basket ball sized amount of fuel was used to start the engines of the sr71.
The boranes had a bad sids though, a by product of their combustion was the production of boron carbides and carbonitrides, ceramics that would precipitate out of the exhaust. They abraded and fouled engine parts, so work publicly stopped, or did it?
Could this material be a by product of this earlier research?
Anyway it is a fascinating material.

I want to 3-d print a custom ceramic cod-piece.

originally posted by: skunkape23
I want to 3-d print a custom ceramic cod-piece.

So, you admit that you have something to hide?

originally posted by: MfId77
a reply to: TEOTWAWKIAIFF

It can withstand heat but ceramics are brittle correct? If so it wouldn't make for good car frames or bridges.

Cool stuff nonetheless

The plates in my body armor are ceramic. It doesn't HAVE to be brittle.

originally posted by: punkinworks10
Could this material be a by product of this earlier research?

HMMM. ;D

originally posted by: TEOTWAWKIAIFF
PS - I don't know what the heck a "silazane " is but it sounds cool and you can dance to it!

Silicones are silicon-carbon compounds, silizanes are silicon-nitrogen compounds. There is some overlap.

originally posted by: grey580
I see some electrical property talk.

Could this be used to 3d print motherboards?

Probably not. However, you can make pcbs pretty cheap and they work really well.

a reply to: punkinworks10

Yup. Following the Green Lady talk. Not recently but do catch up every now and then. Before I joined I did spend a bunch of time in the aircraft project forum.

Setting temp is not actually stated. I misread this originally. They are claiming the ceramic will work up to 1,000 C not that it is set there. I have re-read this three times and it does not specify what the setting temp is!

9. The structure of claim 6, wherein said layer is resistant to: oxidation in flowing air at a temperature of up to about 1000.degree. C.; or laser irradiation up to about 15 kWcm.sup.-2 at a wavelength of about 10.6 .mu.m, for about 10 seconds without burning, delamination, or deformation of said layer.

U.S. Patent filed for this process


a reply to: Bedlam

Cool, thanks for the clarification!




I like this quote from the OP...

Now we can think of using ceramics where you could never even imagine.

An example (recent too) of how ceramics can be used in Li-ion batteries.

Electric batteries are electrochemical devices that convert chemical energy stored in electricity. They consist of one or several electrochemical cells, and each cell is made up of one positive (cathode) electrode and one negative (anode) electrode, separated by an electrolyte which allows the ions to move between the electrodes. Currently, lithium-ion batteries are the main electrochemical storage systems in electronic devices and the area of transportation. "What we have patented are new ceramic electrodes that are much safer and can work in a wider temperature interval," explained Professor Alejandro Várez

It is a method of making ceramic sheets by way of a thermoplastic extrusion mold.

Phys.org, March 30, 2017 - Lighter, more efficient, safer lithium-ion batteries.

This was just done in Spain. The US patent actually goes back to 2012 when the silizane-carbon ceramic was first created. So they have been working on perfecting the process and mixture for over 5 years! The Spanish researchers created a ceramic powder that can used in an injection mold to get the shape they desire (they did both a flat sheet and a cylinder).

The liquid polymer only needs to be partially heated before being used in an injection mold. That means this is near production ready. Non-exploding lithium ion batteries would be a welcome relief! Not certain about the flip side--recycling. But the non-explosion makes up for that.

That is just one example where ceramics can make an immediate improvement in out daily lives!

a reply to: TEOTWAWKIAIFF

Well ceramics can last for a long time.

While not bio degradable. Ceramics and be pulverized.

Pretty interesting when you think about the uses.

In the sol-gel process, a solution of an organometallic compound is hydrolyzed to produce a "sol," a colloidal suspension of a solid in a liquid. Typically the solution is a metal alkoxide such as tetramethoxysilane in an alcohol solvent. The sol forms when the individual formula units polymerize (link together to form chains and networks). The sol can then be spread into a thin film, precipitated into tiny uniform spheres called microspheres, or further processed to form a gel inside a mold that will yield a final ceramic object in the desired shape. The many crosslinks between the formula units result in a ceramic that is less brittle than typical ceramics.

chemistryexplained.com - Ceramics.

The sol-gel process is how current advanced ceramics are made. The idea is the same though. The colloidal particles are mixed together in a suspension. In the boron-modified silizane of OP, the actual chemical elements are mixed together in the proper proportions. As they stated, they are mixed in a liquid polymer. The sol-gel process is more complicated as they introduce alkoxide which as the "oxide" indicates contains oxygen. The tetramethyl orthosilicate is organic and also needs to be processed out of the sol-gel. That makes the production costs increase. They essentially "burn it off" at a low temperature. And Jerry, there is shrinkage! Source cited says "10 - 40%". But the better you can interconnect the chemicals the stronger it becomes while also resulting in a less brittle finished product.

Comparatively, the boron-modified silizane seems simpler with less additional steps. They did not say if the liquid polymer is "burnt off" or actually becomes part of the finished ceramic product. And I have yet to find their sintering temperature (sorry grey580). Regular clay needs to be heated up to 1,300 °C for comparison sake.

Maybe, in future, if TEOT is still around, and needs a hip replacement, I can opt for boron-modified silizane or what ever combination is used for medical purposes!

A ceramic engine made from this stuff might have the weight
and strength ratio to be the top performer of all engines as
it can hold up to 1000 C in an engine running at 12000 RPM.

The Space Shuttle tiles get to 2300 C, but maybe a mix of
silazene and something else will make it hold up to 2300 C.

Since it is so simple, 5 elements, and has carbon, it naturally
bonds to nano-tubes. Carbon black is not graphene but similar
and could be used to form solids with it.

a reply to: TEOTWAWKIAIFF

One of the biggest shortcomings with 3d printing is materials. With advances like this, that can really change.

I suspect that we will see a large boom in new materials and widespread adoption/implementation of 3d printing technology in the near future. Of course, there are more applications than just 3d printing, but I'm hedging my bets on the concept of a reimagined manufacturing sector based on decentralized printers, rather than factories.

If anyone is even remotely interested in any of this (and it is cool stuff), now is probably a good time to get involved.

a reply to: Serdgiam

Hey nice to see you!!

I'm on mobile but there are two things I would link in if I could: 1 - The MIT story of 3D printing graphene into shapes that are strong with minimal material; 2 - The GE 3D printed supercritical CO2 turbine. Both are ready to go and benefit from this technology.

I'll link both in when I can.

You're right on getting in while nobody knows!!

@ThatHappened, yup, there is graphene and CNTs sitting there ready to be used. Which is why I am psyched on this news!