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chloric1
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LADIES PLEASE!
Ok, while dann2 and Rosco start another cat fight, I decided to get to work. Although I admire the subtle blue hue of cobalt oxide baked on Ti, I am
not going to do exactly what Xenoid did, I need to do different. First, I did my first ever anode with just (2) 10 minute Co3O4 coats follow by one
nickel oxide coat then 1 hour bake. His name is Nicolas. The next anode I am in the process of working up is being temporarly called anode X. So
far it has 3 coats of Co3O4 with no annealing 1 hour bake. Anode X is going to receive a SnO2 coat and then be annealed. This will hopefully close
the debate between the madscience devas.
@Xenoid- I have provided pictures of my horizontal setup.
[Edited on 1/27/2008 by chloric1]
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chloric1
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I wanted to show a picture of Nicolas also. You can tell the color is different. The blue hue of cobalt oxide is no longer seen instead you get more
of a steel grey look but more refelctive. Of coarse the picture is misleading because of diminished lighting.
[Edited on 1/27/2008 by chloric1]
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Rosco Bodine
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| Quote: | Originally posted by dann2
Hello,
I am not argueing that you cannot deposit SnO2 films using Sol-gel, Hydrosol.
You can.
Theses methods have never been used for anodes. Do you know any refs. that show theses methods being uses as working anodes (ANODES) in (Per)Chlorate
cells? (or waste water treatment tests/applications or brine electrolysis).
First paper mentions nothing regarding anodes.
Second paper mentions anodes by referencing Anodes that are made by the Pyrolysis technique (not sol-gel, hydrosol) using SnCl4 + HCl + brushing on
with a soft brush + Pryolysis.
There is nothing to support your claims that I have seen or have been shown (apart from the large volume of argument that you are generating).
I wish anyone here who wants to try the Sol-gel etc methods the best of luck. Be aware that they have never been used or studied as (Per)Chlorate,
waste water, brine/Chlorine anodes. This is a fact.
These's methods are being put forward here as being superior, far better, etc etc to the SnCl4 +HCl + Pyrolysis route. Nobody anywhere has shown this
to be the case.
The SnCl4 + HCl + dip and bake + Pyrolysis route is being condemed as not workable ('dip and bake..... no way').
This is untrue.
No amount of words will change this fact.
The best way to educate your wee humble student of anodes is to show him some examples of your wise words of wisdom being actioned.
If there are no examples to be had, that is just the way the stuff works. ie. The sol-gel hydrosol etc does not work for anodes in
(Per)Chlorate/brine/Chlorine etc applications.
The dip/brush + SnCl4 + HCl + Pyrolysis does work and has been shown to work.
Dann2 |
What a load of complete crap . You are doing the same thing here as in the cobalt oxide anode thread .
http://www.youtube.com/watch?v=7I2k3tITHzc
One trick pony wearing blinders .
Open your mind and rise to a higher plane
http://www.youtube.com/watch?v=ARNiv8MR4JE
Let's look at one example here in this thread which was discussed in part in the ATO thread ......and it relates to what you said above
| Quote: | Originally posted by dann2
Hello,
@Tentacles
While I do not want to be 'running down' your efforts I suggest you test A DTO coat(s) if you want to see if you have a coating that could be
described as viable. You will have to put a coat on Ti alone as the Spinel will only confuse the DTO test. |
Cobalt spinel doping of SnO2 as an intermediate layer
in a baked coating scheme on a Ti substrate anode
is superior to ATO . Co2O3 doped SnO2 is fully 3 times as durable as an intermediate layer than is ATO . See
Example 3 Table 1 , test runs #4 and #7 of US4584084 .
Would it really confuse the DTO test to any disadvantage
to produce an interface sealing coating which has three times the durability against passivation of a Ti substrate ,
by choosing deliberately to have a cobalt doped SnO2
intermediate layer , known to have improved durability
and better adhesion as compared with an ATO interface ?
If that's confusion , then I'd rather be confused all day
and have a sealed interface layer that is three times as
tough as ATO and a whole lot easier to implement .
Once you have this nicely sealed and durable *cobalt spinel doped SnO2* interface - intermediate layer , you can probably throw at it whatever you
want in the way of
subsequent layers , with regards to precursor flavors of
your liking , but Bi doped SnO2 added intermediate layers
would be the "armoring" which is indicated would be best
to use next . Here is where your SnCl4 + Bi(NO3)3 could
probably be used okay .
No matter what subsequent coatings are applied , this
scheme is going to be multiple times better than ATO
applied to a Ti substrate . It is technically superior and
that is what the literature indicates . If you see some
way around that conclusion or doubt its rationale , you
are welcome to it . But don't try to tell me that I am comparing apples and oranges here or merely arguing
when plainly I am very focused on what the data is telling me .
Attachment: US4584084 Co2O3 v Sb2O3 and other DTO dopant comparison tests.pdf (272kB)
This file has been downloaded 725 times
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Rosco Bodine
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@chloric1
You need to thermal break that supported anode
somehow and get it all the way into the furnace
as there will be a rapid temperature gradient along
its length the way you are doing it . It will tend to roast
at the tip that is deepest into the furnace , and be only
mildly hot where you have it clamped outside the furnace tube . Maybe some sort of fixture that could clamp it
by the end and fixture and all slide inside the furnace tube . Have a stiff wire handle on the fixture so you could
put it into and drag it out from the furnace .
About the nickel spinel , that's good too . I have every intention of using the mixed nickel - cobalt spinel like that article I posted because it
was reportedly even more durable than the cobalt alone , which is good by itself .
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Xenoid
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@ chloric1
Details please! Did you dip and shake, dry at low temperature, use an alcohol in your solution, etc.
With a horizontal system did you get solution running round to the lower part of the rod, did this cause a thick strip down one side?
What is the reasoning behind the nickel coat?
Ah!... Rosco partly answered, I thought that the zinc spinel was the more durable!
Keep it up, this is interesting stuff!
[Edited on 27-1-2008 by Xenoid]
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Rosco Bodine
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MadScience divas LOL .
I've had two red headed wives with some Scot and Irish
blood and buddy lemme tell ya , they mean business
and they know how the story goes  ...when they get
Hot!!! like a tube furnace they will put a big smile on your anode   
About that bimetal nickel spinel , or alternating Ni and Co ,
it goes back to the early part of the Cobalt Oxide Anode
thread where I posted a journal article about these spinels being compared and their mixture 50-50 was
reportedly even tougher than either spinel alone .
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chloric1
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@Rosco-Well I have been contemplating the same temperature gradient since I put this together. Incidently I measured my temperatures at the end of
the tube so I feel it is OK to leave a centimeter or two hanging out. This is helpfull in I don't have the rod right against the nozzle so nothing
should exceed 500°C.
I wanted the horizontal arrangement because my rod stock is 1/4" (0.8 cm)and it would be a chore to drill into it. That is if I can manage to do that
at all. When I hook up the anodes, we will see if this arrangement can work.
@Xenoid-No I did not use alcohol and when I withdrew the rod from the cobalt solution I gently tapped it on the 25 ml cyclinder I am using for
dipping. Yes, there seems to be some powdery residue on the bottom side of the rod. I use a wet paper towel and any oxide not adhering comes off in
2 or 3 wipes. I also rotate during bake runs so I can even the coating a bit.
Well, I have six year old stannous chloride which really is probably stannic oxychloride. I dissolve 28 grams in 100ml and added 300 ml of 29%
ammonia and I have a "tin milk" I will dip with this soon and we can see what comes of this.
[Edited on 1/27/2008 by chloric1]
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Rosco Bodine
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@chloric1 ,
That was probably not the best thing to do with the stannous chloride But
don't toss it .
Do you have any left that you didn't neutralize ?
Do you have an accurate temperature controlled warmer or hotplate , if you do , you should take a shot at the oxidative soak deposition , as it should
very evenly coat
the anode .
[Edited on 27-1-2008 by Rosco Bodine]
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chloric1
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Yes I have a hotplate. I neutralize all the 28 grams of SnCl2 I measure out. I got a few hundred grams left. The milk does seem to put an uneven
coat. I am doing a second coat with crem de leche right now. After this I wanted to try the 1 hour bake to seal it. For what its worth the tin oxide
wants to coat everything and it seems to like being suspended in solution.
This oxidative soak. You have peaked my curiousity. So, what concentration do I use? I use only stannous chloride and boil I take it. I can use
the anode as a stir stick since it would be in the way of a stir bar. I do not
want to use a bunch of tin so I need to heat a graduated cylinder. Possibly the 25 ml one I am using for dips.
Rosco-One last thing, once I do the long bake, am I going to be abe to add to an anode?
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Rosco Bodine
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Five posts up from the bottom of the preceding page ,
here's the link for the article
http://www.sciencemadness.org/talk/viewthread.php?action=att...
What's happening with the SnCl2 solution is that it is indeed doing its oxidative soak deposition but in an uncontrolled way which leads to a slime as
opposed to a hardcoating of the desired material . Sooo you have to follow the article to get it to do its thing in the narrow range of
concentration where the deposition rate is controlled . All you need is a thin coating and then to bake it onto the spinel maybe 10 minutes @ 450C ,
or a bit longer at a lower temp , and you have a sealed and
cobalt spinel doped intermediate layer on Ti . With any subsequent coatings you will probably have to add dopant to the SnO2 precursor , but that
first coat should pick up enough doping by diffusion from the spinel .
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chloric1
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Thank you so much. I don't know how I missed that reference. Actually, they give a wide range of concentrations of the SnCl2 and KNO3. So just
going within there range should suffice. Since my stannous chloride is practically no longer stannous, I am thinking of adding some to a mix of tin
metal and conc. HCl. I will also need to filter before I use the solution.
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Xenoid
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| Quote: | Originally posted by chloric1
..... I don't know how I missed that reference. |
Yeah! I have the same problem! I read a reference that has some good ideas, then something else comes along, and I immediately forget about it.
Maintaining a temperature of 60 oC. for +24 hours may be tricky. Why is it so important to only partly cover the soaking beaker?
I might try this with multiple layers of SnO2 with some Bi(NO3)2 thrown in the mix!
BTW won't SnO2 be converted to a stannate in the uncontrolled high pH environment of an amateur chlorate, and especially perchlorate cell, where the
pH hits 11.5.
[Edited on 27-1-2008 by Xenoid]
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chloric1
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Xenoid-I think the stannate only forms under the most grueling alkaline conditions. SnO2 is very persistent and wants to coat everything. I am
having a time getting residues off glassware. The milk dip is not the best way to get the SnO2 coating. I did a REALLy hot bake for 30 minutes on a
final thrid coat of stannic oxide. Incidently, I can no longer block three of the four baffles any more because the last two inches of the rod where
glowing dull red. Also, I want to try zinc dopant on my next anode. If I can manage a alkali fusion with zirconium silicate, I would like to make
zirconium nitrate to dope the cobalt spinel.
There is no white powder crust and my deposit is VERY tough although not as smooth as Nicolas is. Will test both soon. It appears my uneven SnO2
coat has reduced the streaking on the paper when wiped wet. I am thinking the cobalt spinnel absorbed most of the tin as no visible white coating is
seen.
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Rosco Bodine
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| Quote: | Originally posted by chloric1
There is no white powder crust and my deposit is VERY tough although not as smooth as Nicolas is. Will test both soon. It appears my uneven SnO2
coat has reduced the streaking on the paper when wiped wet. I am thinking the cobalt spinnel absorbed most of the tin as no visible white coating is
seen. |
That tracks *exactly* with what I expected and predicted about the solid solution mutual solubility of cobalt spinel
and SnO2 , which was guessed from the electrical properties chart of US4369105 in early study of the Dow patents .
It was clear that plain SnO2 picks up doping from cobalt spinel quite easily by diffusion when the spinel is overcoated
onto the SnO2 , and diffusion should have occurred equally well in the reverse order as is being used here . Dow had the right idea , they just had
the most desired order of application reversed I was reasonably certain that
was the case.
Actually there is a mutual solid solution solubility that should be high for MnO2 as well with both the Co2O3 and SnO2
in binary or tertiary system , and I think Bi and also Fe
follow that same pattern at least with regards to SnO2 .
All of these should diffuse pretty well and form well adhering
boundaries of variable diffusion between layers , particularly when SnO2 is predominating as the major component .
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chloric1
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Well, here is a tentative plan, I still have the remains of the tin milk in a beaker. I am going to let it dehomogenize and decant the supernatent
liquid probably after 2 or 3 days. I will then attempt to dissolve in nitric acid with specific gravity of 1.2 IIRC. If this works in my favor, I
will add a small portion of bismuth nitrate to this and develope a third anode.
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Rosco Bodine
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idea for a tube furnace
After pricing of some industrial grade heating elements
and getting sticker shock , I remembered something about
an incoloy sheathed hot water heater element being made
for hardwater service , and a manufacturers note that the
elements could withstand dry firing . So basically what it is
is a folded hairpin "calrod" sort of tubular element that is a whole lot like the heating elements on an electric kitchen range cooktop , or the oven
element , or the heating element
in an electric broiling grill , or an electric charcoal starter .....
it can be run actually glowing red hot ....probably even orange hot at the service limit . And best of all they are not
expensive . Here's what one looks like , and I think the element sheath is 3/8" diameter . The way I was thinking
of making use of the element involves splitting the mounting
plate with a saw , to separate the terminal ends of the hairpin so it can be spread apart slightly , and possibly also spreading apart the single
U-bend slightly , so the whole
12" of the heated section is sprung slightly against the inside walls of a 13" length of square stainless tubing ,
2" square stainless tubing looks right , with the longer
legs of the element seated against the inside corners and the folded back portions sprung slightly against the inside walls and clamped down with
small brackets or perhaps
with stainless lockwire through small drilled holes . The
tube furnace could be wrapped with rockwool or kaowool ,
and then fiberglass for added insulation , everything laced down with stainless lockwire or stainless zip ties like used for securing header wrap . A
sensing thermocouple and
a digital PID furnace controller would be used for controlling
the element , and using half the rated voltage the actual
power would be only 25% of the rating , which would be
1375 Watts actual and very safe for the element .
From an economics standpoint , I like it The heating
would be very even due to the heatsinking by the tube .
I am thinking maybe about a 3/16" to 1/4" vent hole in top
and bottom to allow it to breathe by chimney effect ,
and orient it vertically with the unheated 2" terminal ends
exiting the bottom , and the thermocouple sensor near the top .
$16.42 for the 5500 Watt rated incoloy element isn't bad
http://www.homeandbeyond.com/prod-0114176.html
[Edited on 29-1-2008 by Rosco Bodine]
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chloric1
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Yeh that might work but I think you are overengineering here. I am thinking Kanthal wire,which is not terribly expensive on ebay, wrapped around a
stainless mesh with kaowool,variac and a thermocouple. Athough there are inherent problems with the heat gun approach, I do like to think the air
flow is quite beneficial for what we are doing. It offers a constant fresh supply of oxygen. I just have to watch out and not block as many
baffles.
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Rosco Bodine
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Maybe over the top , but I already have the precision
digital programmable process controllers and sensors on hand ........besides , I love LED real time process monitoring
Takes the guesswork right out of the picture with regards to gradients and stuff , I can monitor not only the element
and air temperature inside the oven , but actually monitor
the substrate core temperature itself and watch the heating gradient and plateau , soak time ect .
I have some airhandling and flowmonitoring capability too but figure that is probably over the top for sure . But I like the other stuff . Using the
parts I already have , I can
put it together without too much expense . I mainly like
going that way because I won't have to babysit the
process like a blacksmith at a forge ......but just do a
"run program" and come back later when the cake is ready to come out of the oven .
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Twospoons
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Is that a ceramic terminal block on the end of that element? If not, you might be well advised to change it.
Helicopter: "helico" -> spiral, "pter" -> with wings
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Rosco Bodine
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It's probably bakelite and was expected to be toast
I was going to torch it and crumble it away with a few taps with a hammer and chisel or try crunching it away with vise grips . The screw tabs are
probably spot welded to the solid exit pins which are likely about 2 1/2" long .
Anyway I'll know soon enough cause I got one on the way .
When it arrives I will peform the "exploratory surgery"
and see what I've got after parting the plate , probably
bisecting the terminal block at the same cut , with a hacksaw . I'll probably leave the metal plates attached to the incoloy as heatsink flanges for
that terminal area .
[Edited on 29-1-2008 by Rosco Bodine]
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chloric1
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Well,Rosco, to put things in perspective, it is only over the top if the hardware is out of your price range and/or if you do not have it on hand.
Sounds like your setup wont take too much trouble. I, on the otherhand, of somewhat limited means, for now mind you, have to work a little bit to
compensate for a lack of the "latest and greatest" in technology.
It might go beyond sensibility but sometimes the technologically simple, more labor intensive methodology appeals to me.
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Rosco Bodine
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Please don't think I am dissing the heat gun furnace , no
not at all . I actually have some other need for a tube
furnace and have thought about building one for awhile ,
before the heat gun idea ever came up , so that's why
I already got the controllers before even knowing about the heat gun . There's nothing wrong with that so don't get me wrong . Some of the things I
want to do other than
anodes is beyond the reach of the heat gun , and the furnace can do both . I have the heat gun too so I have it covered either way . Anyway having
the readout data will
allow me to know exactly what the parameters are ,
if I should submit an article or go further .
Actually I have a variable speed linear actuator which I could use to duplicate dip coating withdrawal rates where
the precursor film is applied . But I probably won't use that either , not that it would be a bad thing for eliminating another variable . I'm an
old production line
worker so I tend to think along those lines so I know I can reproduce nearly exactly whatever was done before that turned out right Clones , reproducibility ....you know.
BTW that group of Irish ladies , the MadScience divas
are in my area and I checked the cost of tickets and got another case of sticker shock ...about $200 each for general audience seating and it gets
worse of course for premium seating ....so those girls are definitely upscale , there will
be a lot of valet limo parking at that concert . Well they may be high maintenance , but that's not really surprising .
I would definitely say those girls are some of Irelands national treasure .
[Edited on 29-1-2008 by Rosco Bodine]
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Twospoons
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I'd forget torching the bakelite - few things smell worse, and it is probably brittle enough that a sharp smack witha hammer will deal to it. Next
you'll want some high temp silicone wire for the connections.
I dare say you know all this already Rosco, but others might not.
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chloric1
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No offense taken. Actually, I am taking note of your statements for future use. If I was in a pinch I would like a precise furnace so I may heat some
potassium chlorate to EXACTLY 400°C so I can get perchlorate if I am unable to have an anode ready. At least with the heat gun, I can use it to
remove paint when I am not cooking anodes.
How about cryogenic bakelite? A nice dip in dry ice & acetone.
Well, if you bad mouth the divas, your just jealous thats all!
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Rosco Bodine
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ooops almost forgot , time for a diva fix
http://www.youtube.com/watch?v=KGpTkv713vQ&feature=relat...
or
http://www.youtube.com/watch?v=_H4TlDxXxVk
Just a bit of curiosity concerning the Bismuth explorations .
Anybody have any further developments with
Ti / Co2O3 / SnO2 / Bi2O3-SnO2 or
Ti / Co2O3 / SnO2 / MnO2-SnO2-Bi2O3 or perhaps
Ti / Co2O3-Ni2O3 (50/50) / SnO2 / SnO2-Bi2O3 (95/5) ?
I found some semiconductor manufacturing surplus
new old stock components which are furnace related bargains and I couldn't resist So I have some more components in shipment now for making a larger tube furnace as well as making the smaller furnace using the hot water heater
incoloy element . I got some strip heaters that are incoloy too , and some 40A solid state relays arrived yesterday that are way more than adequate
for the heating element control . More parts are coming in over the next week . Still tooling .
[Edited on 6-2-2008 by Rosco Bodine]
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