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Rosco Bodine
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| Quote: | Originally posted by Xenoid
The perchlorate cell is crap, and will only last a few more hours! |
Anticipated result , tracks with literature .
| Quote: |
Stop running around like headless chickens, and do some basic systematic studies. |
Hey , I'm very focused here , and have been studying my ass off while trying to flag what probably won't work and why ,
against what reportedly does work and why , along with
conclusions drawn from both which suggest things worth trying . It doesn't get more systematic . Also have been
obtaining components , even have some things on the way now . These schemes we are contemplating are "real"
MMO anodes , and done right , they should work fine .
| Quote: |
Four coats of simple Co oxide has just about got halfway through a chlorate run, it should be able to tweak it a bit to go a full run and beyond.
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There is little or no reason in the literature to believe that will prove true . I'm am not trying to discourage you , but
that spinel interface is just that , not a complete anode .
It's like driving a car away from the body shop after they put the primer coat on , and saying it's painted good enough
before the finish goes on . Maybe a bit impatient ?
| Quote: | | The perchlorate is a bigger problem! |
YGTFR ! 
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Rosco Bodine
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| Quote: | Originally posted by jpsmith123
IIRC, there are other examples in his subsequent patents using preformed oxides...and some of these are not Ruthenium.
In any case, apparently every single example of Beer's involves baking at high temperature. Right now I'm trying to figure out the cheapest and
quickest way to bake these things. |
Yeah the temperature of formation for the spinels is precisely what makes Co give favorable results as they tend to develop at much lower temperatures
, a third what it takes
for many other spinels that aren't based on cobalt .
Keeping the temperature down , lets the spinel seal off the
Ti at a point where it hasn't been hot enough long enough
to develop a serious TiO2 passivation layer . Co spinels
nip that shit in the bud whereas other spinels might not .
The same is true for the solid solution effect of SnO2 , which
seals off the surface before the passivation layer can grow .
Generally speaking high temperature bakes on Ti are bad ,
especially for the initial coating until the Ti gets a protective layer . So this narrows down the choices significantly of
what goes on first .
I want to post that perchlorate anode related link again
http://www.wipo.int/pctdb/en/wo.jsp?WO=1979%2F00842&IA=W...
[Edited on 12-12-2007 by Rosco Bodine]
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dann2
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| Quote: | Hello,
| Quote: | Originally posted by jpsmith123
If you look at patent #3632498, you'll see that Beer mixes TiO2 up with everything but the kitchen sink (e.g., gold, iron, lead, ruthenium, etc).
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I LOVE IT!!!!!!!!!!
Could not agree more. The company he left to go to Diamond Shamrock are still hitting themselves.
| Quote: | Originally posted by jpsmith123
snip
I don't know if it makes sense, all I know is that one of the most successful inventors claims that it works; so I'm just saying, I think it's worth a
try.
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Thats the way I am inclined to think. The people who are writing up the patents know alot more regarding what worked and what did not. They have
tried lots and lots and lots of combinations, processes, procedures etc etc. They have not just tried what has appeared in the examples at the end.
The examples (I am inclined to think) are there most successful results. If they were to document and publish all there failures in the patent(s),
each patent would be a large book.
@Rosco
For example the DTO (for anodes) has always had a high Sb content with HCl in the precursor. Many patents repete a very similar precursor/procedure,
not all patents coming from the same company/people. They did not come up with that same procursor/procudure by chance. They would have tried %'s
above and below or read a previous patent, tried it, and had success. The glass conductive coatings are interesting but not on our pitch (as it were).
Is there anywhere (patents or journal article or elsewhere) where a sol-gel or mixed valency inorganic polymer has been reported as useful as a way to
make an anode, experimental, industrial or otherwise?
Looked at the DTO coating under a microscope today and it still looks pretty much the same as it did when it started some 200 hours ago. It is novel,
much better than anything before. It may also be improved by those's more skilled in the art.... (o dear, think these's patents are getting to me)
Dann2
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dann2
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Hello,
Regarding modifier oxides....
The following (exciting) extracts are from US 4142005. A particilar favourite of mine!
Modifier oxides may be incorporated into the Co.sub.3 O.sub.4 coating to provide a tougher coating. The modifier oxide is selected from among the
following listed groups:
[SNIP SNIP]
Group IV-B (Titanium, Zirconium, Hafnium)
[SNIP]
The modifier oxide is, preferably, an oxide of cerium, bismuth, lead, vanadium, zirconium, tantalum, niobium, molybdenum, chromium, tin, aluminum,
antimony, titanium, or tungsten. Mixtures of modifier oxides may also be used.
Most preferably, the modifier oxide is selected from the group consisting of zirconium, vanadium, and lead, or mixtures of these, with zirconium
<FONT COLOR=RED>(STONE IN MY SHOE)</FONT>being the most preferable of these.
[SNIP]
It has been determined that when coatings are applied by a plurality of layer applications, as in the following examples, each subsequent layer is not
the same thickness as the preceding layer. Therefore, a coating built-up of, say twelve layers is not twice as thick as a coating built-up of six
layers.
[SNIP]
The single-metal spinel of Co3O4 is sufficiently adherent to the substrate for most applications; however, the use of the "modifier oxides" generally
improves the adherence, hardness, and toughness of the coating.
[SNIP]
As used herein, the expression "contained", when referring to the modifier oxide in the spinel structures, means that the modifier oxides are
essentially homogeneously or evenly distributed through the single-metal spinel structure.
________________________________________-
They do not say that the modifier Oxides give the anode a greater resistance to Chemical attack, but just physical thoughness, hardness.(exactly what
that means). Also improves adhesion.
TiO2 (ye old kitchen sink oxide) is included in the modifier list! Zr (Number one, eh), Vanadium and Lead are top of the lot.
Are there any patents etc that specifically state that modifier oxides will make the coating more resistant to Chemical attack in Chlorate, Perchlorte
or even Chlorine production?
Dann2
[Edited on 13-12-2007 by dann2]
[Edited on 13-12-2007 by dann2]
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Rosco Bodine
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it's deja vu all over again
| Quote: | Originally posted by dann2
@Rosco
For example the DTO (for anodes) has always had a high Sb content with HCl in the precursor. Many patents repete a very similar precursor/procedure,
not all patents coming from the same company/people. They did not come up with that same procursor/procudure by chance. They would have tried %'s
above and below or read a previous patent, tried it, and had success. The glass conductive coatings are interesting but not on our pitch (as it were).
Is there anywhere (patents or journal article or elsewhere) where a sol-gel or mixed valency inorganic polymer has been reported as useful as a way to
make an anode, experimental, industrial or otherwise?
Dann2 |
Well that settles that , huh?
How could I possibly dispute the science .
You are absolutely not reading the patents with comprehension , but are picking out what you want to believe in different terms and out of context
from its meaning .
I'm not even going into it more at this point .
And have you checked the price on Zirconyl nitrate ,
or is it that you think just dumpng in some Zirconia ,
maybe cubics well ground to powder is what is needed ,
why not cabosil or just sand ought to work its just a filler right , no real chemistry involved there .
[Edited on 13-12-2007 by Rosco Bodine]
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R.P.Wang
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Hi guys!
I do not know whether it is suitable to poster here about the PbO2 anode, I really want to share some my experience about anode preparation here.
I have made several PbO2 anodes before.
1, Ti/SnO2+Sb+MnOx/PbO2
2, Ti/SnO2+Sb/PbO2
3, Ti/SnO2+MnOx+Y/PbO2(quite well)
4,Ti/SnO2+CeO2/PbO2(have the shortest service life)
5, Ti/SnO2+sb+CF/PbO2 this one is prepared by others in my lab, (CF=Carbon fiber, this one is said to be the best)
some one tell me the Ti/SnO2+Sb/alfa-PbO2/belta-PbO2 is also very reliable.
I have made other anode such as DTO,I have not made Co3O4 anode before,(my job is watertreatment using Ti/PbO2 or Ti/SnO2, and study the mechnism of
solid solution oxides in anode)I do not know why your guys made Ti/Co3O4 , what it use for? for using in Cl2 evolution or Perchlorate
electrosynthesis?
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Rosco Bodine
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It's just a convenient stable conductive interface material for preventing passivation of a Ti substrate .
Working anode coatings like Bi2O3/SnO2 or PbO2 ,
must be used to prevent erosion , and increase oxygen
overvoltage for perchlorate cells .
Potentially other complex spinels may be useful as working anode coatings .
[Edited on 13-12-2007 by Rosco Bodine]
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dann2
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Hello,
| Quote: | Originally posted by Rosco Bodine
| Quote: | Originally posted by dann2
@Rosco
For example the DTO (for anodes) has always had a high Sb content with HCl in the precursor.
SNIP
Is there anywhere (patents or journal article or elsewhere) where a sol-gel or mixed valency inorganic polymer has been reported as useful as a way to
make an anode, experimental, industrial or otherwise?
Dann2 |
Well that settles that , huh?
How could I possibly dispute the science .
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Yes 
| Quote: | Originally posted by Rosco Bodine
You are absolutely not reading the patents with comprehension , but are picking out what you want to believe in different terms and out of context
from its meaning .
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By 'Boo Hooing' the examples in the patents or suggesting that the patents were 'cobbled together in a hurry' you are in fact contradicting people
who have spent a hugh part to their professional life making actual successful anodes. Beer (and the patent people we are quoting here) know more
about anodes that all the people on this discussion put together. Thats my opinion, feel free to disagree.
I am not trying to suggest that I have comprehension of all the parameters, processes, chemistry etc.
Sol-Gel and Mixed valency inorganic polymer for anodes? 
If I see a single example (or a hint of an examply) for a anode I will withdraw the shaking head.
That's a good deal.
| Quote: | Originally posted by Rosco Bodine
And have you checked the price on Zirconyl nitrate ,
or is it that you think just dumpng in some Zirconia ,
maybe cubics well ground to powder is what is needed ,
why not cabosil or just sand ought to work its just a filler right , no real chemistry involved there .
[Edited on 13-12-2007 by Rosco Bodine] |
Zirconium Oxide is available from ceramics store. Not_importent suggested a way to convert to Nitrate.
Dann2
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dann2
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Hello,
Welcome on board R.P.
| Quote: | Originally posted by R.P.Wang
Hi guys!
I do not know whether it is suitable to poster here about the PbO2 anode, I really want to share some my experience about anode preparation here.
I have made several PbO2 anodes before.
1, Ti/SnO2+Sb+MnOx/PbO2
2, Ti/SnO2+Sb/PbO2
3, Ti/SnO2+MnOx+Y/PbO2(quite well)
4,Ti/SnO2+CeO2/PbO2(have the shortest service life)
5, Ti/SnO2+sb+CF/PbO2 this one is prepared by others in my lab, (CF=Carbon fiber, this one is said to be the best)
some one tell me the Ti/SnO2+Sb/alfa-PbO2/belta-PbO2 is also very reliable.
I have made other anode such as DTO,I have not made Co3O4 anode before,(my job is watertreatment using Ti/PbO2 or Ti/SnO2, and study the mechnism of
solid solution oxides in anode)I do not know why your guys made Ti/Co3O4 , what it use for? for using in Cl2 evolution or Perchlorate
electrosynthesis? |
We hope it will make Chlorate and Perchlorate. No one here is interested in Chlorine production.
Do you think Co304 on Ti will stand up to a Chlorate or Perchlorate cell. The chlorate cells we run are always at a high pH, that is, they are not pH
controlled as in industry.
The Lead Dioxide anode has been a long running project in the amateur world of Electrosynthesis. Very few have been able to produce a stable anode
using 'home' construction methods. The hope is that the Ti substrate with a Sn/Sb Oxides undercoat will be successful.
As the original person (Alembic who introduced the LD on Ti with DTO coat to this board) explained:
"Lead Dioxide will oxidize Ti, an interface coat in needed."
I would love to hear of details of the interface coats, LD coating methods etc, etc.
What is the Sb content of your Doped Tin Oxide interface coatings on Ti?
Cheers,
Dann2
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Xenoid
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| Quote: | Originally posted by R.P.Wang
Hi guys!
I do not know whether it is suitable to poster here about the PbO2 anode, I really want to share some my experience about anode preparation here.
I have made several PbO2 anodes before.
1, Ti/SnO2+Sb+MnOx/PbO2
2, Ti/SnO2+Sb/PbO2
3, Ti/SnO2+MnOx+Y/PbO2(quite well)
4,Ti/SnO2+CeO2/PbO2(have the shortest service life)
5, Ti/SnO2+sb+CF/PbO2 this one is prepared by others in my lab, (CF=Carbon fiber, this one is said to be the best)
some one tell me the Ti/SnO2+Sb/alfa-PbO2/belta-PbO2 is also very reliable.
I have made other anode such as DTO,I have not made Co3O4 anode before,(my job is watertreatment using Ti/PbO2 or Ti/SnO2, and study the mechnism of
solid solution oxides in anode)I do not know why your guys made Ti/Co3O4 , what it use for? for using in Cl2 evolution or Perchlorate
electrosynthesis? |
Please enlighten us, we are all ears!
It's all very well, creating exotic anode coatings in a fully equipped laboratory, with access to high purity chemicals and scientific literature. I'm
sure any competent chemist can accomplish this! Unfortunately we are not competent chemists (well I'm not anyway)...
What we are trying to accomplish is anode coating preparation from relatively easily obtained chemicals, using simple techniques and equipment.
If your procedures satisfy these criteria, please let us know, or start a new thread outlining them. But really it needs to be something the average
amateur chemist can do in the kitchen, garage or backyard shed. Anything else isn't really relevant as far as I'm concerned. Most of us don't even
have access to lead ccompounds, strong acids or sophisticated facilities for plating.
Again, if what you are doing is simple, please let us know!
Edit: Actually if they are basically PbO2 electrodes, please post your procedures and techniques in the "More on PbO2 Electrodes" thread. We look
forward to seeing them...
[Edited on 13-12-2007 by Xenoid]
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Rosco Bodine
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Let's just take the "magic Zirconium" here as an example of what I'm trying to point out about how you just don't get it . Why is it you think that
among all the "modifier oxides" listed that Zirconium is *the* one of interest , except that the patent , " the teacher " say it is most preferable ?
You automatically reckon that's the oxide you must want , just because the patent says so .
Most preferable for what application ? And for what sort of cell ..... most preferable for a perchlorate cell of course because that is *your*
interest , not because the patent
says specifically that Zirconium is most preferable for a
*perchlorate* cell anode . In fact if you look at the list
of modifier oxides , there are several like lead , tin , manganese and bismuth that are far more interesting
because they have a known usefulness in *perchlorate*
production .
So why Zirconium ?
The point here is that even after you go through all the
entirely predictable pseudoscience antics which fail to produce a *perchlorate anode* by the course you are taking , it is absolutely irrelevant and
unnecessary .
The *interface* which you have labored to achieve with your chlorides based ATO scheme will not approach the interface achieved by the cobalt spinel ,
or its bimetal spinel with nickel ......won't touch it in terms of conductivity .
*But* just because the spinel makes an excellent interface doesn't mean a damn thing for its worth as a working coating , so use it for what it does
best , and then use the other materials (as their more compatible implementations) to *complement* the good interface that the spinel provides .
You don't need a chlorides based precursor and all the theories why they are needed for producing an interface
with titanium , when a spinel is already doing that job beautifully well . Come back over that spinel with a kinder gentler and less corrosive ATO
precursor or just a plain TO
precursor to simply seal it . The interface is already there ,
so the ATO or plain TO has an easy task to do now that
the "heavy lifting" has been done by the spinel . You don't need ten coats of ATO anymore , a couple would probably do it , unless you use a crappy
water thin chlorides mix having wetting problems instead of using something like the polymer
which has its own wetting properties ....at least for the first
coat . Or you could oxidative cold soak the TO layer on
and follow it with the Doping with antimony also using
non-corrosive method .....and then bake it to develop .
You have more options and more precise and predictable options on how to proceed . And once your DTO is applied , you can follow the baked DTO with
whatever
coatings as you would use via your other scheme ,
plating on of an Alpha PbO2 and then Beta PbO2 , with
or without Bismuth . The thin layer formations required
shouldn't need elaborate plating scenarios . This
"plan B " was anticipated early in the thread . So far as I know there has been only one "baked anode" working coating reported useful for a
perchlorate anode and
it is not US4142005 like you seem to think is applicable ,
but it is US4072586 you should be looking at for perchlorate anode specific information , Zirconium being mentioned nowhere BTW as useful . But 5%
Co(NO3)2 along with
up to 20% Pb(NO3)2 or 20% *Tin Nitrate* (not chloride) ,
along with the remainder of Mn(NO3)2 were described
as useful "modifier oxides" .
But it seems you are leading straight to a purely speculative
"plan C" pursuit involving a modifier oxide that is not specifically stated as useful for *perchlorate* anodes , knowing and perhaps hoping ? it will
probably fail , so you can proceed to dismiss a superior *interface* technology and return straight back to what you have been pushing "Alembics
anode" , yes who first enlightened the forum about the magnificence of Ti substrate PbO2 anodes , as if somehow that magnificence would not be
preserved having the higher tech undercoatings which I have been proposing .
Continue advancing the probably wrong theory
that the first order of business for making Ti substrates
anti-passivating , just must be using the chlorides based 16% Sb system which you seem to insist
is the singular solution , while it is only *one* of many approaches , and probably not the best one .
And that is really what is likely to be proved here
in this thread, which is exactly why you are not a happy camper , for having invested so heavily in what is so likely
a lower tech , more complicated , and inferior method .
The data will tell the tale , but only if the test is relevant .
BTW ......
Among the modifier oxides , mixtures are allowable also .
One of the interesting possible products is zinc stannate .
What may be its chemical resistance or catalytic properties
I'm not sure , but it is a highly conductive ceramic material . It is one of the possible stannates which occured to me while reading that list and it
would have good thick film conductivity as it has been used in experimental battery anodes in monolithic form . Electrically it is probably better
than ebonex as a conductive ceramic . I wonder if it might
have usefulness as an anode all by itself , never seen it mentioned before for electrolytic uses .
[Edited on 13-12-2007 by Rosco Bodine]
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Xenoid
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| Quote: | Originally posted by Rosco Bodine
So far as I know there has been only one "baked anode" working coating reported useful for a perchlorate anode and
it is not US4142005 like you seem to think is applicable ,
but it is US4072586 you should be looking at for perchlorate anode specific information , Zirconium being mentioned nowhere BTW as useful . But 5%
Co(NO3)2 along with
up to 20% Pb(NO3)2 or 20% *Tin Nitrate* (not chloride) ,
along with the remainder of Mn(NO3)2 were described
as useful "modifier oxides" .
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Yes!...Yes!...Yes!...
I'm getting there!... I'm getting there!...
Do you realise how difficult it is to make and purify Mn nitrate (this stuff decomposes when you look at it the wrong way and has to be stabilised
with nitric acid) and other nitrates! Give us a chance!... I do have to mow the lawn and do the shopping!... 
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Rosco Bodine
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Hey yeah that's me too ! I have a downed tree from a storm still laying on my lawn , my dogs need baths ,
and I'm dealing with a couple of inept attorneys who
can't read statutes unless the price of reading fees is
agreeable and negotiated on a word per word basis
I stay ass deep in alligators , but keep shooting , hoping
alligators get short before ammo
IIRC , a carbonate intermediate may be the way to go
there with the Mn . Or perhaps decomposition of some permanganate and then cycling to a nitrate would be
better than ever working from sulfate , I'm not sure .
I'm slower than Christmas for not having everything on hand myself , and otherwise being occupied , but will get around to experiments too when I can
. Anyway , nobody put on the blinders and get tunnel vision about any one
patent or any one "recipe" , as there is more than one way to skin a cat , some maybe not even invented yet till the next cat comes along
Many chemical processes have highly branched "flow charts" for possible routes from various starting materials
to various end results so nothing is necessarily written
in stone as one and only right pathway of doing something .
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dann2
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Hello,
| Quote: | Originally posted by Rosco Bodine
Let's just take the "magic Zirconium" here as an example of what I'm trying to point out about how you just don't get it .
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When I said Zr is what you want (Rant icon here), I was talking rather tounge in cheek. It was in relation to Co Oxide anodes only.
I am of the opinion that Co Oxide will not make Perchlroate. Perchlorate has not been mentioned in ANY Co Oxide patent.
The other patent you are quoting is Mn Oxide. Would agree that (as others have said) that may be the best way forward. I thing the Co. is a dead end
for Perchlorate.
| Quote: | Originally posted by Rosco Bodine
snip
Come back over that spinel with a kinder gentler and less corrosive ATO precursor or just a plain TO
precursor to simply seal it . The interface is already there ,
so the ATO or plain TO has an easy task to do now that
the "heavy lifting" has been done by the spinel . You don't need ten coats of ATO anymore , a couple would probably do it , unless you use a crappy
water thin chlorides mix having wetting problems instead of using something like the polymer
which has its own wetting properties ....at least for the first
coat . Or you could oxidative cold soak the TO layer on
and follow it with the Doping with antimony also using
non-[Edited on 13-12-2007 by Rosco Bodine] |
DTO as per Diamond shamrock patent is capable of any 'heavy lifting' (roll eyes icon here).
The Mixed Valency OP or sol-gel for anodes interface coats is pure speculation on your behalf.
Can you give me a single pointer to it theses techniques being used for anode applications? Therory can only go so far.
Are you suggesting that a Co Spinel will be compatable with a DTO or Lead Dixode coating?
Speculation is well and good if you/we have the time to explore a HUGH space of possible combination etc. Better to go with working examples that have
been shown to work by professionals. They must be possible in the home workshop of course.
Too much theory, no working examples is like the classic saying:
I hear the bee's,
I don't see the honey.
Dann2
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Xenoid
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| Quote: | Originally posted by dann2
I am of the opinion that Co Oxide will not make Perchlroate. Perchlorate has not been mentioned in ANY Co Oxide patent.
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Short-lived as they have been, the Co oxide anode has produced perchlorate (as tested with methylene blue). I have no idea about the amount or
efficiency. Anyway it's irrelevant as we'll be putting something over the top... 
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Twospoons
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Well, I'm nearly ready to join the hunt. Got 95/5 Sn/Sb solder, Co carbonate and NiO yesterday. Wanted some vanadium to play with but they were out
of stock. Looking for Bi shot, so I can try that too. Christmas hols coming up, so that should give me a bit of time.
I'm thinking along the lines of trying to get an Al substrate working (because I have no Ti), using a Ni strike plate, followed by Co spinel (with
some Ni ?) to obtain a stable conductive substrate. Then PbO2 over the top. Or maybe seal with DTO, then PbO2. So many things to try ...
Helicopter: "helico" -> spiral, "pter" -> with wings
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jpsmith123
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Anybody that has some Mn Sulfate and Co Sulfate might want to try anodic co-electrodeposition of the respective oxides, followed by a heat treatment
at 300 to 400 degrees C. (I ordered some Mn Sulfate but I don't have it yet).
This is as per my email correspondence with a grad student who's doing this for another application.
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Rosco Bodine
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@dann2
This is a *science* forum , not a let's all be copycats
of what patent xyz declares is the "ultimate truth" ,
being some witless coven of cauldron stirring drones .
You don't understand the reaction mechanisms
that are applicable or you wouldn't be making
the arguments you are making , which are
pseudoscience . Unproved yet well founded
scientific hypotheses are a hell of a lot more
substantive than "speculation" . For you it
seems that a patent you like is the bible on
some peculiar aspect of a much broader technology .
Where you can find a common denominator in
more than one patent , you *assume* that
somehow proves that represents the "state of the art" ,
even though no data is presented to suggest that .
If you read carefully , the very language
of patents is often ambiguous , and deliberately
so , as to "precise recipes" which may be closely
guarded trade secrets . Being skilled in the art
begins with understanding mechanisms for
certain reactions , getting the point of what
is the general idea , you then see many variations
on a theme and that the claims of a patent
try very hard to cover the range of those variations
without ever actually being specific about
*precisely* what is "preferred" ......because
that is for them to know , and for you to try to
figure out If you take the rote description
they give as your blueprint for duplication of
their proprietary technology , then you are
kidding yourself .
Don't despair over spinels ,
perovskites are just around the corner
[Edited on 13-12-2007 by Rosco Bodine]
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dann2
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Hello,
| Quote: | Originally posted by Rosco Bodine
@dann2
This is a *science* forum , not a let's all be copycats
of what patent xyz declares is the "ultimate truth" ,
being some witless coven of cauldron stirring drones .
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I can assure you, that only for the examples at the end of the patents there would be a mountain of mountains to climb to get to working (or close to
working) anodes.
If all patents put up to this board had the examples snipped out, there would not be much actual progress on the anode front. (It a war you know ). IMHO. Lots of discussion maybe.
Not trying to suggest I am some sort of scientist capable of an understanding of all the fields we are touching on here but I do know that at the end
of the day we need an actual working anode. Do you have a good enough understanding of the workings of possible recipts of baked on coatings on
different substrates, working in different mediums doing different jobs to suggest that worked examples (in for example the Diamond Shamrock patent)
are rubbish?
I have me doughts.
You know more chem. than I do, that's certain.
If people are actully using the examples to knowingly mislead, that is a different story. I do not think they do.
Experience from other people (amateurs where we are) is also very inlightening, irrespective of whether or not they or us understand the science.
I would be attempting to put LD on Graphite bare Ti, Iron and other attackable substrates and expecting a good result if I lisened to the 'science'
alone.
It can be done of course, so long as you wheel out the big tanks, lots and lots of equipment, lab grade chems., triple distilled water......
Perhaps I am droning on.........or am I bringing home the honey!!!!!!!!!!!!!!!!!!!
Naturally enough I will vote the latter
Dann2
I must admit:
PFP
<B>
This is a *science* forum , not a let's all be copycats
of what patent xyz declares is the "ultimate truth" ,
being some witless coven of cauldron stirring drones . </B>
PFP?? Pure f*^k)%£ poetry
[Edited on 14-12-2007 by dann2]
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Xenoid
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Glad someone's working around here...
Meet Gertrude, my latest anode. She's blue/black, smooth, very shiny and hard!
Gertrude has a double layer Co-spinel INTERFACE and 8 layers of beta-MnO2 on top!
Well, Gertrude say goodbye my beauty, because you are off to see the nasty perchlorate cell for several hundred days of exhaustive testing!
But before we do that!
Can someone verify my understanding of oxygen overpotential (OO) in relation to a perchlorate cell! As I understand it, a material with a high OO is
desirable because it allows one to use higher current densities generating perchlorate before energy starts being wasted making oxygen! When running a
perchlorate cell, should we increase the current density to a point just where oxygen starts to be evolved, or a little higher. In the past, with my
platinised electrode, I just turned up the juice to what I thaought was a suitable current density, and to hell with the amount of oxygen produced. In
retrospect I guess this was the wrong approach!
I'll follow up with details, after the exhaustive testing if it is warranted.
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Rosco Bodine
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@dann2
Patent examples are usually illustrative of general principle , a sort of proof of concept presentation , while the secret 11 herbs and spices they
keep to themselves .
I don't think the anodes described in shamrock or in many other patents are rubbish but their methods are not as advanced as those methods and
chemistry which we are
making the greater interest of investigation and experimentation . Never hurts to try applying newer information or more advanced methods to older
processes . You don't seem to understand why the methods being explored by us are more advanced and probably superior . What we are doing is a bit of
updating of some *old* methods .
I wondered why you seem to be playing the devils advocate a bit , maybe the idea was stirring the pot ??? Because I thought the aim here was to
"think outside the box" and try to come up with something more predictable in the way of a system for anode assembly from the substrate up . Applying
a spinel thin film MOS technology to the substrate / interface seemed like a reasonable "breakout" from the other stuff .
As for the applicability of the technology to perchlorate anodes , well no the scentific literature wasn't really specific nor excluding either in
that potential use , but
neither was it limiting or specific to *any* particular use .
So if you basically have a hermetically sealed metal and ceramic anode core , then it becomes a matter of what sort of working coating is applied last
that defines what
the completed anode is useful for electrolysing . The
core structure is pretty generic and could be overplated with just about anything you want , for making any sort of anode you want for whatever kind
of cell , perchlorate included . Some of the designations for these things
don't even get as specific as to call them anodes , but simply call these cores something like "electrodes for electrolysis" and say no more .
About the substrate glass versus titanium , it isn't
really what it appears because for the SnO2 coatings
the interfaces are SiO2 for glass and TiO2 for titanium ,
and silica and titania are not that disimilar , as would
account for any vast difference in coatings performance
including conductivity , which is the aim . Just because
Pytlewski didn't bake and test the conductivity for the
polymer coatings doesn't change the chemistry of the
polymer which would necessarily make it a precursor .
It already is a baked film precursor because of its chemical composition , not because I say so , but because the
elements are there compounded which exposed to heat
will decompose from there to the same end product
as will other precursors having the same elements ,
but arranged slightly differently . It's like how much difference in sweetening your coffee is gotten from
using sugar cubed or granular , if after it dissolves ,
it makes no difference in the end . In some situations
it is just that a different form for the material starting out ,
is more convenient to handle , even though it ends up being the same thing later when the heat hits it .
This kind of layer chemistry is thin film chemistry and is
semiconductor technology also . The substrate and spinel interface is a bona fide thin film "MOS device" of Schottky
titanium substrate architecture , " Zenerized " by special doping into having a zener voltage probably in the hundredths of a volt region . That's
probably what has Twospoons all stirred up , he probably smells a production
run of a new variant Schottky diode here ....never mind the perchlorate anode coating that can be wrapped around it
[Edited on 13-12-2007 by Rosco Bodine]
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Rosco Bodine
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| Quote: | Originally posted by Xenoid
Glad someone's working around here...
Meet Gertrude, my latest anode. She's blue/black, smooth, very shiny and hard!
Gertrude has a double layer Co-spinel INTERFACE and 8 layers of beta-MnO2 on top!
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Okay now , details please , plain MnO2 on top or did
you mix in the 5% Co(NO3)2 and 10-20% Pb(NO3)2 for a tertiary outer coating ?
| Quote: |
Well, Gertrude say goodbye my beauty, because you are off to see the nasty perchlorate cell for several hundred days of exhaustive testing!
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Hope springs eternal
| Quote: |
But before we do that!
Can someone verify my understanding of oxygen overpotential (OO) in relation to a perchlorate cell! As I understand it, a material with a high OO is
desirable because it allows one to use higher current densities generating perchlorate before energy starts being wasted making oxygen!
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Precisely . It is the unusual difference in voltage between what would normally be the span between perchlorate and
oxygen as the product , not an absolute voltage but the difference , a selectivity range broadened because the catalytic effect of the MnO2 on
lowering the potential
for perchlorate production . Plus the absolute overvoltage
may be there in selectivity reflected as a rise in oxygen evolution as compared with a platinum anode ....so you get the benefit of an additive effect
maybe up to 0.6 volts of
added range versus platinum , which allows you to really push the current up before hitting O2 effervescence .
That will tend to scour the coating off the anode also , so you don't want that .
| Quote: |
When running a perchlorate cell, should we increase the current density to a point just where oxygen starts to be evolved, or a little higher. In the
past, with my platinised electrode, I just turned up the juice to what I thaought was a suitable current density, and to hell with the amount of
oxygen produced. In retrospect I guess this was the wrong approach!
I'll follow up with details, after the exhaustive testing if it is warranted. |
Yep if your electrode looks like an airstone , that is wasted energy . You can actually use that as a marker of sorts ,
and back the current down to some percentage below that ,
like 85% or 90% of that evolution current . It should
follow a slope downward as the reaction proceeds to convert all the material in the electrolyte , gassing will
reappear , and the cell will need adjusting , monitoring as the batch proceeds .
[Edited on 13-12-2007 by Rosco Bodine]
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Twospoons
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Dammit Rosco! I thought I was going to be able to patent it and make millions!
Hey Xenoid, another awfully sexy looking anode - can't wait to hear how well it works.
Helicopter: "helico" -> spiral, "pter" -> with wings
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Xenoid
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| Quote: | Originally posted by Rosco Bodine
Okay now , details please , plain MnO2 on top or did
you mix in the 5% Co(NO3)2 and 10-20% Pb(NO3)2 for a tertiary outer coating ?
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Geez, Rosco, give me a chance! I finally decided to make the Mn nitrate from carbonate and nitric acid because I'm having trouble processing the stuff
from the sulphate route.
Sorry, it's just plain old garden variety MnO2. If it looks like holding together I'll try doping it next...
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Rosco Bodine
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Actually it's the porosity I'm worried about . I think MnO2 is like a sieve IIRC , so maybe even an intermediate layer of SnO2 to seal up the spinel
and act as a cement also for the MnO2 and PbO2 and spinel tertiary . That ought to do it , but I do think it will take the three layers , and the
tertiary outer coating . This is the one that needs a
little phosphate in the electrolyte also IIRC , as a catalyst
or an erosion reducer additive . If you got anything with
bismuth in it , throw in a little bit of that too , maybe 0.1%
as it is highly catalytic with the PbO2 component for perchlorate , same as is the Co catalytic together with the MnO2 . All these things together
should be there for long life and high efficiency , if the patent reported data is legit .
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