chief
National Hazard
Posts: 630
Registered: 19-7-2007
Member Is Offline
Mood: No Mood
|
|
Silicon electrode for electrolysis
Since in the diamond-thread nobody answered:
Has anyone tried to use Si as an electrode in a chlorate cell ? Could it stand the chemistry ? Finally it is contained in solar-cells, old
power-transistors, etc. ...
It has, at least, the very same structure as diamond, also the same sort of bonding ... ; only that carbon (diamond) has a much smaller atom and a
much stronger bond ...
|
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
Hello Chief,
First it would have to be doped Si, as pure Si is non-conducting.
I tried a piece of pure Si once only to discover is is non-conducting.
Dann2
|
|
|
not_important
International Hazard
Posts: 3873
Registered: 21-7-2006
Member Is Offline
Mood: No Mood
|
|
Something like this :
Silicon a New Electrode for Electrochemical Reduction of Nitrates: Comparison with Boron-doped Diamond
Attachment: ise081249.pdf (33kB)
This file has been downloaded 1117 times
|
|
|
chief
National Hazard
Posts: 630
Registered: 19-7-2007
Member Is Offline
Mood: No Mood
|
|
Of course it has to be doped ; usually it's easier to get doped material, since any electronics-Si is either p- or n- doped, at least at the surfaces
... ; maybe someone could try this ? Some slaughtered power-mosfet or power-transistor or solar-cell ?
If it works for nitrate-reduction, as in the paper mentioned by not_important, then maybe it will for chlorate ??? Though there the chemistry would be
more agressive ...
Maybe even that a higher current-density would be achieved (limited by the electrolyte), since the surface of a power-mosfet is small (but it can
conduct 100 A), and the cooling is effectively in place by the electrolyte ...
[Edited on 10-2-2009 by chief]
[Edited on 10-2-2009 by chief]
|
|
|
tentacles
Hazard to Others
Posts: 191
Registered: 11-11-2007
Member Is Offline
Mood: No Mood
|
|
Chief: Why not just buy a doped wafer on ebay? They're pretty cheap.
http://cgi.ebay.ca/8-inch-Blanket-Black-Diamond-Wafer-on-sil...
http://cgi.ebay.ca/12-inch-Silicon-Germanium-Wafer_W0QQitemZ...
|
|
|
chief
National Hazard
Posts: 630
Registered: 19-7-2007
Member Is Offline
Mood: No Mood
|
|
I just want to find out before I try ; probably someone has it around and will try it anyhow, then report ... ... . One fine day I might abuse one of
my old 2N3055-Power-Transistors for that, or one of my burned diodes ...
|
|
|
Ragnarok
Harmless
Posts: 22
Registered: 22-5-2008
Member Is Offline
Mood: No Mood
|
|
The paper is about reduction of nitrates. You are talking about oxidizing chlorine. Quite a different beast.
The silicon crystal lattice is mmuch weaker than the carbon varieties. It is also much more reactive (you can find essentially pure carbon in nature,
but pure silicon has to be made). It also forms polymers (silicates), from Si(OH)4 units. A carbon analogue for that does not exist.
In my opinion, silicon would not survive a combination of water, oxigen and chorine. But you are free to try, nonetheless.
|
|
|
chemoleo
Biochemicus Energeticus
Posts: 3005
Registered: 23-7-2003
Location: England Germany
Member Is Offline
Mood: crystalline
|
|
Well, Si is certainly resistant to HCl, and it reacts with Cl2 gas only above 400 deg C. I would certainly give it a try!
Titanium is also oxidised in nature, yet it is used as an electrode.
Never Stop to Begin, and Never Begin to Stop...
Tolerance is good. But not with the intolerant! (Wilhelm Busch)
|
|
|
Ragnarok
Harmless
Posts: 22
Registered: 22-5-2008
Member Is Offline
Mood: No Mood
|
|
Titanium is covered with a layer of oxide, thus forming a quasi-inert barrier. Much like the passivation of aluminum in acids. On the other hand,
aluminum reacts energically with water in basic media. Anyway, Ti is slowly consumed. The best materials used as anodes are metal oxides, which can
not be further oxidised.
Silicon doesn't react with HCl because oxidising conditions are not present. The choride ion is not an oxidizer. Electric current, on the other hand,
is the best oxidizer known to man. The fact that oxigen and chlorine are also generated at the anode and are good oxidisers too further complicates
the issue.
The oxidation of Si would form Si-OH bonds in macro-mollecular compounds, which can then rearrange to the practically inert and highly insulated SiO2
with the help of heat. In water, however, a silicagel of some sort would form, or maybe Si-Cl compounds.
The main difference from the reduction of the nitro group is that in the reduction scenario, the Si can not be further reduced, whereas in the
oxidation scenario oxidation products can be formed and passivation is unlikely.
Hell, I'd like it to work, because it would be quite useful. I have a large assortment of big old transistors, too. But I think it's an unfounded
hope.
|
|
|
jpsmith123
National Hazard
Posts: 764
Registered: 24-6-2005
Member Is Offline
Mood: No Mood
|
|
Silicon is mentioned in a few patents such as this one as having been "suggested" for use as an anode in a perchlorate cell.
And in the archives of some ancient discussions on the newsgroup rec.pyrotechnics, someone claimed to have had promising results with
silicon, although it wasn't clear whether the cell in question was for chlorate or perchlorate.
At one time I tried to find a suitable piece of silicon for an experiment, but I couldn't find any and subsequently gave up on it.
|
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
Hello,
The Silicon is being used for Nitrates reduction (as pointer out by others), ie. it is a Cathode in the cell.
When it is stated that Ti is use as an Electrode (Anode anyways) the writer is always referring to the substrate. Often MMO (Ti substrate) is
referred to as a 'Titanium' Anode. This is very misleading. The MMO is making all the difference.
Bare Ti can be used as a Cathode of course.
I have some Si wafers with and without circuits on them. The pure Si is non conducting.
I put a meter on the stuff with circuits and got resistances of approx. 15 ohms between some die sites (chips before they are cut out). Resistances on
the same die site are as low as 1 ohm. It depends on where on the die site you put the probes. Some adjacent die sites do not seem to have any
connection to each other at all.
A single die site a approx. 11mm by 2mm BTW!.
Will try in a cell and see what happens.
I have very very little hope of anything useful happening.
The conducting layer on a Silicon wafer is very very thin. A pure Si wafer is taken and exposed to heat and a gas (containing P say). The P diffuses
into the wafer to create N-Type semiconductor. Other methods are also used.
The layer of conducting stuff is very very thin, Microns?. This (if it works) will wear away quickly and you are left with pure Si (non conducting).
Also the Micron thick coating (if the die sites don't have it cut up in the first place) is going to be useless for carrying large Chlorate or
Perchlorate cell currents.
The fact the (say) a 2N3055 can carry 30(?) amps is not an indication of the amperage that could be run through its guts as an anode, not to talk
about corrosion of connectios.
You would need a thick piece of Silicon that has NOT been produced from the electronics business, ie. with some impurities in it to make it conductive
throughout its (reasonably substantial) mass.
Dann2
|
|
|
chief
National Hazard
Posts: 630
Registered: 19-7-2007
Member Is Offline
Mood: No Mood
|
|
Another thought: If the Si could be consumed electrolytically, then this could be a cheap way to make the expensive "aerosil", which is
nanocrystalline SiO2, for reactions (wanted for the large surface-area).
So eiher way it might be worth trying it out (and just hereby making it unpatentable ...)
|
|
|
Ragnarok
Harmless
Posts: 22
Registered: 22-5-2008
Member Is Offline
Mood: No Mood
|
|
You might end up with some chlorine in your product, instead of -OH, but it can be tried. Something useful for you has a really high combined
probability of occurring 
|
|
|
tentacles
Hazard to Others
Posts: 191
Registered: 11-11-2007
Member Is Offline
Mood: No Mood
|
|
I should see if my foundry grade silicon is conductive.. Next time I run across the damn chunks, guys. I think I know where they are.
|
|
|
chief
National Hazard
Posts: 630
Registered: 19-7-2007
Member Is Offline
Mood: No Mood
|
|
I might throw in here, that gemstone-quality opal is nothing else byt nanospheres of silicon-dioxide, regularly arranged ...
It may be synthesized, and a well known Pierre Gilson made it since decades, but he keeps the process secret ...
[Edited on 12-2-2009 by chief]
|
|
|
dann2
International Hazard
Posts: 1523
Registered: 31-1-2007
Member Is Offline
Mood: No Mood
|
|
Hello Folks,
I checked the piece of wafer below with an Ohm meter. Most of the die were isolated. The resistance accross individual die was one or two Ohm. It
depended where you put the probes. In places there was no connection. There was no hope of simply placing a connection at the top of the wafer and
having currrent going to the rest of the die, because, (as I said they are electrically isolated).
I connected the piece of Si wafer to the + of a power supply and placed into a NaCl solution together with a Cathode.
About 200mA flowed at 12Volts from a single die but it was hard to tell if it was the wet wafer that carried some of the current. Each die measures
10mm by 2 mm approx. It is a hopeless Anode IMHO.
Dann2
|
|
|
not_important
International Hazard
Posts: 3873
Registered: 21-7-2006
Member Is Offline
Mood: No Mood
|
|
| Quote: | Originally posted by chief
I might throw in here, that gemstone-quality opal is nothing else byt nanospheres of silicon, regularly arranged ...
It may be synthesized, and a well known Pierre Gilson made it since decades, but he keeps the process secret ... |
Silica, not silicon.
|
|
|
chief
National Hazard
Posts: 630
Registered: 19-7-2007
Member Is Offline
Mood: No Mood
|
|
I corrected it ; That's what I meant, sorry for the typo and thaks for the hint.
Besides this gemstone-quality opal is quite something to get _very_ rich upon, one of my would-be projects, in case I had the time ... ; but I have
other projects as well, ... ...
@dann: Such a piece of waver is chemically resistent: I once dissolved several pentiums (133 pro, mmx etc.) in aqua-regia (including all the gold):
The waver was untouched ! Maybe it has a surface-layer for isolation (maybe also just for the dielectric constan of the layer) ...
Thats why I would propose an old powerdiode: It just has 2 plain regions: 1 p and 1 n ; with just a piece of silicon one might get all sorts of
rectifying-effect etc.
[Edited on 12-2-2009 by chief]
|
|
|
garage chemist
chemical wizard
Posts: 1803
Registered: 16-8-2004
Location: Germany
Member Is Offline
Mood: No Mood
|
|
As already said, those wafers are nonconducting because they are too pure. If they were made of crude industrial silicon (like, maybe, 99,5% pure)
they would conduct perfectly fine.
The answer to this problem is making your own silicon.
Two methods are viable for the amateur, one is reduction of SiO2 with Al, the other one SiO2 with Mg.
The reaction of the first one is not self-sustaining because it is not exothermic enough. It is neccesary to add an oxidiser and additional aluminium
to provide the heat.
A standard laboratory preparation of silicon, found in several german textbooks, uses a mix of SiO2 and Al with sulfur:
120g sulfur
100g aluminum
90g silica flour
This reaction gives melted globules of silicon and lots of aluminum sulfide as byproduct (produces H2S with HCl, this can be useful and is worth
collecting or absorbing with NaOH).
The silicon can be freed of adhering SiO2 by means of treatment with warm HF.
With Mg instead of Al and no sulfur (!), the reaction is self-sustaining and produces Si as a medium fine grey powder. It can be melted together in a
quartz ampule using an oxy-propane blowtorch
Si is resistant to oxidation in air at up to 1100°C and is not attacked by HF, in contrast to SiO2.
With NaOH solution, it reacts to give hydrogen and sodium silicate solution (here's a "cold" method of producing sodium silicate!).
[Edited on 12-2-2009 by garage chemist]
|
|
|
chief
National Hazard
Posts: 630
Registered: 19-7-2007
Member Is Offline
Mood: No Mood
|
|
SiC (silicon carbide) is a semiconductor too ; it industrially is made by laying out a trace of coal (several meters long), covering it with a lot of
sand (several tons), and then passing directly some 220/380 Volts through the coal, which thereby, insulated by the sand, heats up nicely and reacts
with somewhat sand to SiC .
That SiC might be even closer to diamond ... in some ways ...
By the way: Just braking a power-diode in 2 will yield some well-contacted ("bonded") and doped Si, for the quick test. Insulate the bonding-material
by some glue or paraffine ... and there you go !
[Edited on 12-2-2009 by chief]
|
|
|
ewalcacer
Harmless
Posts: 6
Registered: 23-4-2012
Location: Brazil
Member Is Offline
Mood: No Mood
|
|
I'm thinking about starting a research on this... I can't find a reliable method to analyse the reduced silicon (described as a fine grey powder) and
prove the content of the crystal. I'm also thinking about doping it with two other metals.
BTW, can anyone recommend some publications on reduction methods for silicon carbide and silicon oxide?
Thanks.
|
|
|
![[*]](images/xpblue/default_icon.gif){kind=icon}
