Showing posts with label silicon. Show all posts
Showing posts with label silicon. Show all posts

Tuesday, July 29, 2014

Silicon-capped hydrocarbons: Mysterious molecules in space

This graph shows absorption wavelength as a function of the number of carbon atoms in the silicon-terminated carbon chains SiC_(2n+1)H, for the extremely strong pi-pi electronic transitions. 

When the chain contains 13 or more carbon atoms, not significantly longer than carbon chains already known to exist in space, these strong transitions overlap with the spectral region occupied by the elusive diffuse interstellar bands. 

Credit: D. Kokkin, ASU

Over the vast, empty reaches of interstellar space, countless small molecules tumble quietly though the cold vacuum.

Forged in the fusion furnaces of ancient stars and ejected into space when those stars exploded, these lonely molecules account for a significant amount of all the carbon, hydrogen, silicon and other atoms in the universe.

In fact, some 20 percent of all the carbon in the universe is thought to exist as some form of interstellar molecule.

Many astronomers hypothesize that these interstellar molecules are also responsible for an observed phenomenon on Earth known as the "diffuse interstellar bands," spectrographic proof that something out there in the universe is absorbing certain distinct colours of light from stars before it reaches the Earth.

But since we don't know the exact chemical composition and atomic arrangements of these mysterious molecules, it remains unproven whether they are, in fact, responsible for the diffuse interstellar bands.

Now in a paper appearing this week in The Journal of Chemical Physics, from AIP Publishing, a group of scientists led by researchers at the Harvard-Smithsonian Center for Astrophysics (CfA) in Cambridge, Mass. has offered a tantalising new possibility: these mysterious molecules may be silicon-capped hydrocarbons like SiC3H, SiC4H and SiC5H, and they present data and theoretical arguments to back that hypothesis.

At the same time, the group cautions that history has shown that while many possibilities have been proposed as the source of diffuse interstellar bands, none has been proven definitively.

"There have been a number of explanations over the years, and they cover the gamut," said Michael McCarthy a senior physicist at the Harvard-Smithsonian Center for Astrophysics (CfA) who led the study.

Molecules in Space and How We Know They're There
Astronomers have long known that interstellar molecules containing carbon atoms exist and that by their nature they will absorb light shining on them from stars and other luminous bodies.

Because of this, a number of scientists have previously proposed that some type of interstellar molecules are the source of diffuse interstellar bands, the hundreds of dark absorption lines seen in color spectrograms taken from Earth.

In showing nothing, these dark bands reveal everything. The missing colours correspond to photons of given wavelengths that were absorbed as they travelled through the vast reaches of space before reaching us.

More than that, if these photons were filtered by falling on space-based molecules, the wavelengths reveal the exact energies it took to excite the electronic structures of those absorbing molecules in a defined way.

Armed with that information, scientists here on Earth should be able to use spectroscopy to identify those interstellar molecules, by demonstrating which molecules in the laboratory have the same absorptive "fingerprints."

But despite decades of effort, the identity of the molecules that account for the diffuse interstellar bands remains a mystery.

Nobody has been able to reproduce the exact same absorption spectra in laboratories here on Earth.

"Not a single one has been definitively assigned to a specific molecule," said Neil Reilly, a former postdoctoral fellow at Harvard-Smithsonian Center for Astrophysics (CfA) and a co-author of the new paper.

Now Reilly, McCarthy and their colleagues are pointing to an unusual set of molecules, silicon-terminated carbon chain radicals, as a possible source of these mysterious bands.

As they report in their new paper, the team first created silicon-containing carbon chains SiC3H, SiC4H and SiC5H in the laboratory using a jet-cooled silane-acetylene discharge.

They then analysed their spectra and carried out theoretical calculations to predict that longer chains in this family might account for some portion of the diffuse interstellar bands.

However, McCarthy cautioned that the work has not yet revealed the smoking gun source of the diffuse interstellar bands.

To prove that these larger silicon capped hydrocarbon molecules are such a source, more work needs to be done in the laboratory to define the exact types of transitions these molecules undergo, and these would have to be directly related to astronomical observations.

But the study provides a tantalising possibility for finding the elusive source of some of the mystery absorption bands, and it reveals more of the rich molecular diversity of space.

"The interstellar medium is a fascinating environment," McCarthy said. "Many of the things that are quite abundant there are really unknown on Earth."

More information: The Journal of Chemical Physics, July 29, 2014. DOI: 10.1063/1.4883521

Wednesday, March 14, 2012

Making silica aerogel at home - YouTube



He followed instructions in the silica TMOS recipe from http://www.aerogel.org and successfully produced some small pieces of aerogel in my home shop.

The two main difficulties are: 1. Getting TMOS or TEOS (the key chemical ingredient), and 2. Building a supercritical drying chamber. The components for the chamber can be bought from http://www.mcmaster.com or another source of industrial pipe fittings.

You'll also need a supply of liquid carbon dioxide. I used a 20-lbs cylinder, which I bought from a local welding store. Most of the cost is in the cylinder itself, since a refill costs only $20 to $30. You may find a welding supply shop that will rent the cylinder.

Getting the TMOS is difficult since chemical suppliers are generally unwilling to sell to individuals.

The process to make aerogel is:

  1. Mix TMOS, methanol, and ammonium hydroxide. Pour this mixture into molds, and wait for a gel to form.
  2. Submerge the gel in methanol, and wait a day for the remaining water in the gel to diffuse into the methanol.
  3. Discard the methanol, and replace with fresh methanol. Wait a day, and repeat. Repeat this process a few times over three days.
  4. Transfer the gel into the supercritical drying chamber, and fill the chamber with methanol.
  5. Add liquid CO2, then open the chamber's bottom valve to remove the methanol. Make sure the gels are always covered with liquid CO2.
  6. Wait a day for methanol to diffuse into the liquid CO2.
  7. Open the bottom valve and remove more methanol.
  8. Repeat the methanol draining procedure while making sure the gels stay submerged in liquid CO2. Repeat the CO2 draining/exchange a couple times over 2-3 days.
  9. Raise the chamber temperature to cause the CO2 to become supercritical. Slowly vent the chamber while applying heat to ensure the CO2 moves from the supercritical phase to the gas phase. 
  10. Continue venting the chamber slowly, then remove the finished aerogels.