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Magnetite Anode

dann2 - 6-1-2008 at 15:08

Hello,

Though I would open a new thread on this. Alot of previous stuff was discussed in 'Electroplating Iron'.

Made 3 Magnetite anodes ( Ti substrate) using patent 3,850,701
Coated Ti with Iron using FeSO4 + Ammonium Sulphate + some Formaldehyde. Approx. 0.5 mm applied.
Baked at 500C for 7 hours, feeding in steam from a kettle controlled by a variac.
Tested one in an NaCl solution. It corroded from the start but it has been going for one week now.
Current density approx. 80mA per square cm. There is a very volumonus brown contamination in the cell.
Voltage is low at about 5.2 volts.
Next time will try higher temperatrue + Ferrous Ammonium Oxalate as used in patent.
The patent uses H2 + Steam but H2 is too much trouble for me.

Magnetite anode, anytime I tried it was hopeless for Chlorate making. (worse for Perk).
It may be a usable substrate for LD, either plated on or simple physically attached like I tried before.
The last time I tried it on a Magnetite anode (made by melting Magnetite with welder) it worked OK but the Magnetite anode broke at the top where the connection to PS was.

Dann2

[Edited on 6-1-2008 by dann2]

dann2 - 13-1-2008 at 05:12

Hello,

The Magnetite anode lasted for a total of 11 days.
I changed the cell after 7 days as there was no more brown appearign on surface of anode. The new cell was not coloured much by corrosion of Magnetite for the last 4 days of running.
Changed to new anode. This one has got a much thinner coat of Magnetite on it.

Dann2

chloric1 - 13-1-2008 at 05:44

Sounds like the magnetite anode coating is hit or miss. Using it as a substrate for LD may or may not work. Any indication that the magnetite is porous?
In your first run where you able to obtain a decent amount of chlorate after removing "brown crud"?

Depressing, isn't it?

jpsmith123 - 13-1-2008 at 07:49

For the time being I've given up on the Fe3O4, Co3O4, SnO2, PbO2, MnO2 etc., etc., etc., approach.

I think the diamond-like coating thing could go somewhere.

From what I've read so far, it's so promising and potentially easy to accomplish that I think it's worth spending some time on.

Member "arkansas" just uploaded some interesting papers I requested in the references section.

chloric1 - 13-1-2008 at 08:36

Welcome back jpsmith!

I thought you were hiding. Anyways Xenoid actually is making some headway on the baked anodes. Just had some technical problem being that the anodes CANNOT remain in the electrolyte when power is cut off. Once the basic insoluble anode can be proven to be durable and the production quality reproducable, the next step is the active catalyst layer of PbO2 or simular for perchlorate making.

This diamond thing still sounds far fetched AFAIK, it might very well prove to be the ideal material but production might be another matter for the amatuer chemist.

jpsmith123 - 13-1-2008 at 10:54

It's hard for me to keep up with Xenoid as he's got so many things going on.

AFAIK, as of today, between Dann2's experiments, and those of Xenoid, no one has yet made a "successful" perchlorate anode. Although in the person of "Hubert", it sounds like Xenoid does have a promising chlorate anode. And of course you're right, maybe PbO2 on top of a "Hubert" or some of Dann2's "DTO", will turn out to be a success.
(I'm thinking about starting an "anodes-miscellaneous" thread or something to try to summarize where we are in this quest).

Anyway, I hope I can convince Dann2 to get interested in this DLC stuff (hey Dann2, just think how much girls would like to be the first in the neighborhood to have a set of diamond-coated, perchlorate-capable earrings!

). But I don't want to hijack this Magnetite thread so I'll post the latest of what I've found out about the possibility of making DLC in another thread.

Almost there, just one more heave............

dann2 - 14-1-2008 at 15:03

Hello,

O lordy, lordy lordy!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!!
This anode thing has taken up more of my time (not to mention eveyone elses) than I had previously bargained for back in February last when I decided to become 'involved' again.
It's a long and winding road with a sure and definate (no doubt) outcome .......................we hope

Quote:

Originally posted by jpsmith123
Anyway, I hope I can convince Dann2 to get interested in this DLC stuff (hey Dann2, just think how much girls would like to be the first in the neighborhood to have a set of diamond-coated, perchlorate-capable earrings!

The guy with the pink cell will obvioulsy not be interested.............I'll mention no names

.

I started (attempted) to plate some Alpha Lead Dioxide on DTO yesterday without success.

About the Magnetite. All Magnetite anodes I have ever made were useless at making Chlorate (never mind Perchlorate). I think you actually NEED a pH controlled cell (guess). Therefor I am hopeing that it may make a substrate for a LD anode. It's a long shot as I have never seen it even mentioned in patents/ literature.
If it will not take a plating of LK then I am hopeing that it may make a possible LD anode where pieces of LD are physically attached to the Magnetite. This worked before for me but the Magnetite broke at the connection. It was a Mag. anode made with welder and had a crack at the top. I think (while the idea seems a bit crazy) it would be a workable LD anode.

Dann2

chloric1 - 14-1-2008 at 15:29

Quote:

). But I don't want to hijack this Magnetite thread so I'll post the latest of what I've found out about the possibility of making DLC in another thread.

Man you are really sold in this diamond anode stuff. Could you please demonstrate why this is of any use to us? I know diamonds are synthesized alot cheaper now but I don't understand how this can work in a home ab especially on a budget?

jpsmith123 - 14-1-2008 at 17:09

What I'm sold on right now is the need to investigate it thoroughly.

Given the fact that people are now making it by way of electrolysis of cheap, relatively non-toxic, commonly available chemicals, given the fact that it apparently doesn't require multiple layers, baking in a furnace, etc., and lastly, given the apparent performance, i.e., better than platinum, how can anyone not be interested?

I'm presently setting up to try to duplicate, as closely as possible, the procedure described in the paper by Gupta et al. Maybe I'll try it tomorrow. (I've already gotten some interesting results just fooling around).

It may turn out to be impractical, as the issues of substrate material and how to dope it with Boron may be show-stoppers, but I think it's worth trying to find out.

dann2 - 15-1-2008 at 22:19

Hello,

Coated one of my Magnetite on Ti anodes today. Used a Lead Nitrate bath. First coat was done at 70mA per square cm (Alpha LD) the second coat was done at 35mA per square cm (Beta LD). I put on too thick a coat of Alpha but it seems OK. The LD is very pitted from bubbles. Will have to organise glass beads/ceramic particles for to put into plating tank to keep them sweped off.
Will commence testing tomorrow.

I started to drill some strips of Ti for to start making anodes proper. The Ti I have drills OK.
Some time back I attempted to make some Magnetite on Ti anodes by plating with Iron and heating to 1000c for a few hours. The andoe failed and I was left with Ti that had sagged with the heat. I attempted to drill this stuff. It is as hard as the hobs of hell. When I tried to mark it with a (good quality) center punce it cabbered (made blunt) the center punch!!!!!!!!!
I also tried to straighten a piece of it by hand and it snapped like a piece of glass.

Dann2

chloric1 - 17-1-2008 at 19:02

1000°C!! You turned your titanium back too rutile!

Last weekend I did some hard researching on machine and working with titanium. Slow speeds,heavy feed rates, and lubricant to keep temperature down!! Titanium can be ignited just like magnesium. They don't call it a reactive metal for nothing.

dann2 - 1-2-2008 at 13:12

Hello,

My LD on Magneite anode failed about 3 days ago. Since it was not a very good effort (bad/quick LD coating) I will give it another go. I need to get Ferric Ammonium Oxalate for the Magnetite + drill holes in Ti for to hold LD better. May work, may not.

The picture of the LD on Magnetite anode is in the 'More on PbO2 Anodes thread'......... I think.

Later,

Dann2

dann2 - 23-3-2008 at 18:23

Hello,

Set up a Magnetite anode cell some days ago.
I measured the Magnetie anode cell CE (current efficiency) today. The anode is running at about 20mA per square cm. The CE is approx 3%,,,,, FFS or to be even more rude

I am going to attempt pH control to see if the reason for the very low CE is a home-made anode problem or just the fact that Magnetite cannot make Chlorate in a cell that is not pH controlled.
I set up a syringe pump at 0.2ml per hour (12% HCl).
The cell is 530ml with a current of 0.58amps.

I reckon that is plenty acid. We shall see.
According to here (bottom of page)
http://www.geocities.com/CapeCanaveral/Campus/5361/chlorate/...
approx. 70kg acid (35%) is needed per ton Chlorate produced.

Dann2

Magnetite Anodes need pH control

dann2 - 26-3-2008 at 14:53

Hello,

Following on from my adventures (or lack thereof) with the non pH controlled Chlorate cell using a Magnetite anode, I set up a syringe pump to meter 12% HCl (hardware store cement cleaner) into the cell.
The cell is 0.52 liters, current = 0.85 amps, temp approx. 21C.
Put cell to pH 6 by adding acid. It only took a few ml's.
Started pump with 0.2ml per hour of acid going into cell. pH was inclined to go towards 7.1 so I increased to 0.3ml per hour after about 12 hours. Ran cell for 54 hours.
pH was in the region of 6.7 to 7.0.
Measure CE (titrated Chlorate) and got a CE of 61%.
Not great but a big improvement on 3%!!!
It would appear that the following rule would apply for Magnetite anode:
If using Magnetite anode, you MUST CONTROLL pH or you will get a very poor CE.
I am going to let cell run and run to see how low the Magnetite can reduce the Chloride to. I have read that it cannot reduce it to a low conc.

Dann2

tentacles - 26-3-2008 at 15:39

dann: You should try this next with the LD anode in a perchlorate cell. I'm curious, also, how do you determine the initial "dose" to program, did you make up some equations to do this, or is it somewhat guesswork?

dann2 - 26-3-2008 at 17:00

Hello,

Perchlorate cells don't need pH control according to journals. I will try pH controlling my LD anode in the next cell it goes into. That will be a few weeks away.
Guestimation of acid needed came from here:
http://www.geocities.com/CapeCanaveral/Campus/5361/chlorate/...

Dann2

dann2 - 28-3-2008 at 18:12

Hello,

Pictures of anode. Not much to see. The anode has a brown colouration on it. The cathodes are Copper.

http://i168.photobucket.com/albums/u200/anodes_2007/mag1-1.j...
http://i168.photobucket.com/albums/u200/anodes_2007/mag2-1.j...

I had no idea the corrosing was so bad on one of the Cathodes untill I seen the picture.

Dann2

dann2 - 7-4-2008 at 12:41

Hello,

Firstly, post above should have said 'cathode connection' , not 'cathode'

The Magnetite anode cell seems to have come to some sort of 'end' today. The pH dropped down to 3.5 (adding the same amount of acid as per the last week) The current has gone up too for some reason or other. Using 5v of Computer PSU to run cell. Will titrate in a day or two and close down.
I am only running to see how low Magnetite can take Chloride to.

Dann2

[Edited on 7-4-2008 by dann2]

dann2 - 12-4-2008 at 17:21

Hello,

Got around to testing Chlorate level in cell today.
I just let the cell run after removing the acid supply some days ago. The pH stayed at around 6.7 without addtion of acid over 4 days now.
The level of Chlorate is now 270 grams per liter.

I was about to dump the lot when I decided to pop in some Methylene blue just to see if any Perchlorate had formed. I expected none. Wrong. lots of Perchlorate.
I nearly get a 'yogurt' ppt when I add some KCl solution to a sample!!
It would appear that Magnetite will make Perchlorate after all. Last time I tried to make Perchlorate (from pure Chlorate in a cell) I got no Perchlorate after a long time. The current density was up at 70mA per square cm. Perhaps it works this time because the CD is lower this time (about 23mA per square cm). Further experimentation is required I guess.
Just to recap. The cell is 530ml saturated salt solution at start. (say 2.7 mole approx.)
A total of approx. 450 amper hours has gone into cell, approx. 17 moles electrons.
A total of 130ml of 12% HCl has gone into cell using syringe pump. (average of 0.3ml per hour). pH of cell hovered from 6.7 to 7.0.

Perhaps Magnetite is not such a bad anode after all, if it will make Perchlorate (from Chlorate).
It NEEDS pH control to make Chlorate though as far as I can see.

Dann2

[Edited on 13-4-2008 by dann2]

tentacles - 12-4-2008 at 19:51

I wonder then about using magnetite for going from chlorate to perc? Would it simply be a matter of setting the initial pH and letting it go, or is there a 'ceiling' amount of perc it will produce into solution?

Iron-Oxide–Titanium Anode for Electrolysis

dann2 - 29-4-2008 at 14:00

Hello,

Some info on Mag. anode.

Dann2

Attachment: Fe Oxide for Chloride Electrolysis.pdf (71kB)
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dann2 - 15-5-2008 at 19:59

Hello,

The Magnetite anode does not appear to be capable of taking the Chlorate concentration to a low level though Chlorate concentration is continuing to fall.

The Chloride level is low at approx. 3 grams per liter.

Chlorate was at 173 grams per liter on 6 May. Today it is at 124 grams per liter.
The cell is approx. 0.5 liters with 0.8 amps going into it.
I added Sodium Flouride today to see if that will hurry it up. There is already Sodium Dichromate added from the start. It needs very little acid to keep pH around neutrat, approx. 1 cc per day.

Dann2

Dann2

MagicJigPipe - 15-5-2008 at 21:04

What is "perc" or "perk"? Is it perchlorate? Are "perk" and "perc" the same thing? It just sounds kinda k3wL to me... like "benz" or "annie".

Thanks, in advance.

dann2 - 16-5-2008 at 14:35

Hello,

Perk or Perc is short for Perchlorate as I use it. Slang really.

Dann2

tentacles - 17-5-2008 at 10:18

dann: Interesting! I suspect it's corroding much? How is the ATO/LD anode doing these days?

dann2 - 17-5-2008 at 14:38

Hello,

The Magnetite anode is not corroding at all as far as I can see. They are quite a good Chlorate maker anode but you must have pH controll as far as I can tell.
See the 'More on LD anodes' thread for the ATO/LD anode story so far.
It has make approx. 1.5 KG Na Perchlorate (from Chloride). I have it in a pure Perchlorate cell from today. A total of 0.3mm has wore off its surface.

Dann2

dann2 - 21-5-2008 at 16:15

Hello,

Ended the Magnetite anode cell today. It fell over by accident (thank goodness). I obtained a Perchlorate making CE of 8.7%. This was when the cell had a low concentration of Chloride in it (approx. 6 grams per liter) and from 173 to 118 grams per liter Chlorate.

The anode does not appear to have any wear but there is a quantity of brown sediment on the bottom of the cell.

To whom it may concern:
My adventures (or lack thereof) with Magnetite anodes are now at an end :-|

D2

Boron Trioxide - 22-5-2013 at 13:02

Magnetite Reloaded:

It seems to be quite a while since someone decided to try magnetite anodes, or at least a while since someone posted about it. So I decided to have a try.

Due to a lack of titanium, I used pure iron instead of the usual route of iron plated on titanium. The iron was heated to a orange heat, then exposed to steam, this produced a bluish-black coating. This coated rod was placed in a sodium chlorate cell, it ran perfectly at first, and continued for about an hour. However after a small piece had flaked off the anode was ruined since the iron was more conductive than the magnetite, and iron isn't a valve metal.

So this brings me to my question, is there a way to produce a thicker magnetite coating, because I don't think repeated heating and steaming will do it, once the iron is plated there is no more iron to react into magnetite?

phlogiston - 22-5-2013 at 15:41

So, you have discovered now why Ti is used as a substrate. It will passivate when a small flake of the coating falls off, allowing the rest of the anode to continue functioning.

Boron Trioxide - 22-5-2013 at 20:33

I had understood the reason for the titanium metal, it is just I don't have titanium metal or the chemicals to plate it with iron.

What puzzles me is how dann and various others had maintained the temperature for several hours, I only find it practical for a few minutes, propane and other gases seem out, though how would one go about building an electric furnace to maintain the temperature for so long. The prolonged heating seems to be the key to a thick and durable magnetite coating.

jock88 - 27-5-2013 at 06:00

http://www.sciencemadness.org/talk/viewthread.php?tid=8697

Since it was discovered by (Doctor?) pdfbdq over on AmateurPyro.Com that a piece of Platinum could be placed in contact with Titanium (probably any valve metal) as a current runner, the whole lot then placed underneath the liquid level in a Chlorate or Perchlorate cell and was seen TO CONTINUE TO FUNCTION AS A PERFECTLY GOOD PLATINUM ANODE WITHOUT ANY CORROSION. It should be possible to obtain some pieces of Magnetite and place them in contact with a Titanium strip and dunk this as an anode into a cell and have it work as an anode for Chlorate (or dare I say a Perchlorae cell since it has been written (in a patent) that you can make Pechlorate at a CE of 11% using Magnetite).
The current magically 'jumps' accross the Ti/Pt (or in our case) the Ti/Magnetite gap.

jock88 - 16-6-2013 at 02:57

15% current efficiency with magnetite as descirbed in the document.
On a weight for weigh comparison that will get you (nearly) the same KG of perchlorate per time as a chlorate cell going at 50%.

Attachment: Magnetite_ArmedServicesDoc.pdf (1MB)
This file has been downloaded 828 times