Sciencemadness Discussion Board - Tutorial:the poor man MMO anode

Tutorial:the poor man MMO anode

plante1999 - 22-1-2011 at 13:17

The poor man MMO anode

Material :
Aluminium rod ,I us 3/8 inch, can be found in any hardware store.
Beaker:approx 150-250ml
Tin solder,can contain pb or sb,can be fond in any hardware store
Distilled water
Sulphuric acid 10%
Aluminium paper
Hydrochloric acid 30%
Power supply 1.5v 0.3amp
Steel wool
Piece of clothe
drill
acetone
torch

Chloride
Aluminium
Take 10ml of HCl and ad 30ml of distilled watter and drop aluminium in and wait.

Tin:
Take 50ml of HCl and ad an exess of tin metal , wait.

When your tin chloride is maked ad around 150ml of 10% sulphuric acid , a large amount of tin dioxide will be produce.

Take your aluminium rod and rub it with steel wool then rub it with acetone.

Mix 10ml of your al solution and 10ml of your tin sulphate solution and pour it on a piece of cloth.

Take your al rod and rub it with your cloth, than take your drill and insert the rod.

Take your drill lite your torch and turn the drill to on , and spin it over the flame with linary movment. Make this 10 or 11 time.

Then for protect your substrat take it in 10% sulphuric acid as an anode and apply 1.5 volt for 1-24hours.

Your poor man MMO anode is complete!

for who want to know this is about 2 mont of search about anode, specialy with otc equipement.for this anode the spining of the drill and the heating uniformaly make a hard coat of Al + SnO2 when we make the electrolisis of sulfuric acid the Al oxidise to Al2O3.

Devlopement: find a way to better corode the al rod for better adherence, I am working on this, other devlopement will be a better ratio of AlCl3 and SnSO4 , pulverising the mix with a pulverisator like windex, because we use a clothe, some of the coat, decape when the friction is to high, later I will test all this think for a better coat , and a better price!

After 24hour in sulphuric acid solution the anode is dark gray,after this I made chlorate for abouth 2week without visible deterioration.the test result show that this anode could work in all conssentration of nitric acid, all consentration of hydrochloric acid, just at 5% hydrofluric acid and finaly all conssentration of sulphuric acid.in future I will test for hydrobromic , iodic acid.

[Edited on 22-1-2011 by plante1999]

[Edited on 22-1-2011 by plante1999]

[Edited on 22-1-2011 by plante1999]

[Edited on 22-1-2011 by plante1999]

[Edited on 23-1-2011 by plante1999]

[Edited on 23-1-2011 by plante1999]

plante1999 - 22-1-2011 at 16:57

this is a picture of the first anode i made after2week of intense use in very corrosive media.

i dont know why it is black because tin dioxide and aluminium oxide is very white.I think a intermetalic compound have been formed, but this layer is vey very very hard and chemical resistan.

[Edited on 23-1-2011 by plante1999]

[Edited on 23-1-2011 by plante1999]

[Edited on 23-1-2011 by plante1999]

plante1999 - 22-1-2011 at 17:20

after some search i find it can be this: http://en.wikipedia.org/wiki/Aluminium_antimonide

because in my solder i ave 50% antimony. wath do you think.

Xenoid - 22-1-2011 at 18:47

Noooooooo...... . Surely it can't be as simple as this

I can see how your coating is analogous to Beer's co-deposited, mixed crystal oxide coatings, RuO2/TiO2 on Ti (MMO).

You have SnO2/Al2O3 on Al. I believe the Beer system works, in part, because both RuO2 and TiO2 both have a tetragonal "rutile" structure. SnO2 also has a "rutile" structure, but Al2O3 on the other hand has a trigonal "corundum" structure. Difficult to see how they would form a "solid solution".

I can also see how it might work in an oxidising environment, but I am amazed that it would last 2 weeks in a chlorate cell. Did it actually produce any chlorate in this period. What voltage/ current were you using.

The grey/black colour may be due to the extremely small grain size of the coating material absorbing light rather than an antimony compound.

What is the flame temperature of your "torch", I assume you were heating the coated rod to about 500 - 600 oC.

Congratulations - this is an interesting development

plante1999 - 22-1-2011 at 19:01

Quote: Originally posted by Xenoid

I can also see how it might work in an oxidising environment, but I am amazed that it would last 2 weeks in a chlorate cell. Did it actually produce any chlorate in this period. What voltage/ current were you using.

What is the flame temperature of your "torch", I assume you were heating the coated rod to about 500 - 600 oC.

I run it at 3 volt 1amps.

I coated it at 600-800(my torch heat at 600to 1100degree c)

it producted arround 100 gram of potassium chlorate without degradation.

[Edited on 23-1-2011 by plante1999]

[Edited on 23-1-2011 by plante1999]

plante1999 - 23-1-2011 at 07:43

so my first anode is a 15 day in chlorate cell. I make a TiO2 ,SnO2 anode with titanium trichloride and this anode show this apect:
anode: alumina/titania
conductivity:good/medium
chemical resistan:good/very good
hardness of the coat:epic/good
solubility:epic/good

so this is the test result i made with same conssentration of coating.

edit: I wanted to see ow much voltage the anode take a 3amps and at 8volt it deterior rapidili at 12 volt the coating flake of and lets appear aluminium crystal.So dont do this with more than 5 volt.

[Edited on 23-1-2011 by plante1999]

[Edited on 23-1-2011 by plante1999]

dann2 - 23-1-2011 at 14:38

Hello,

That's one for the patents no doubt.

Any chance of a clear picture of the Anode?

Dann2

plante1999 - 23-1-2011 at 14:51

Quote: Originally posted by dann2

Hello,

That's one for the patents no doubt.

Any chance of a clear picture of the Anode?

Dann2

here a re-dimentioned picture.

later i will re-retake some picture of the 2 anode,titania and aluminia for demonstrating the variance of the 2 anode,some picture of the processe , more explanation and some improvement.

[Edited on 23-1-2011 by plante1999]

[Edited on 23-1-2011 by plante1999]

Tutorial: the Poor man MMO anode V 2.0

plante1999 - 23-1-2011 at 17:20

This is the version 2 of the guide

there is the material:
Material :
Aluminium rod ,I us 3/8 inch, can be found in any hardware store.
Beaker:approx 150-250ml and 50ml
Tin solder,can contain pb or sb,can be fond in any hardware store
Distilled water
Sulphuric acid 98%
Aluminium paper
Hydrochloric acid 30%
Power supply 1.5v 0.3amp
sand paper corundum
Piece of clothe
drill
acetone
torch

First you need to pour 30ml of 30%HCl and ad tin solder.

than take 25ml of water and 25ml of HCl and ad an essess of aluminium to it.

Cut your alu rod to the heigth desired.

than run your drill and use a sand paper to corod it:

Optional:rub the alu rod with HCl , this step help to harden the coat.

than rub it with acetone.

ad per small amont 10ml of sulfuric acid 98% to the tin solution, it will boil very readily.

than soak your cloth with 50/50solution.

than rub your rod with it,heat it re rub it re heat it ect, here is a picture but you cannot see the flame.

repeat this until you think you have a hard layer.

ther is it!

to harden the coat electrolise as an anode a 10%sulfuric acid solution .
[Edited on 24-1-2011 by plante1999]

[Edited on 24-1-2011 by plante1999]

[Edited on 24-1-2011 by plante1999]

[Edited on 24-1-2011 by plante1999]

[Edited on 24-1-2011 by plante1999]

Xenoid - 24-1-2011 at 17:09

Well, this is all so easy, I have to give it a go....

The reactions;

Aluminium chloride hexahydrate decomposes above 300 oC. to give HCl, water and Al2O3

AlCl3.6H2O --> 3HCl + 4.5H2O + Al2O3

Tin (II) sulphate decomposes somewhere above it's melting point of 378 oC. to give SnO2 and SO2. How come this procedure was not mentioned in the SnO2 anode and SnO2 doping threads!

SnSO4 --> SnO2 + SO2

I have prepared AlCl3 solution by dissolving scrap Al in concentrated HCl. Careful the reaction is quite vigorous and gets very hot! The solution was filtered hot and allowed to cool. The solubility of AlCl3 at 20 oC. is 45.8 g/100mls.

The tin (II) sulphate solution was prepared by reacting pure tin granules with hot copper (II) sulphate solution until the solution is colourless. The solution was filtered and allowed to cool.

Sn + CuSO4 --> Cu + SnSO4

The solubility of tin (II) sulphate at 20 oC. is 18.9g/100mls.

I gather the coating process puts a conducting mixed metal oxide layer of Al2O3/SnO2 on the bare Al. The low voltage "annealing" process in the dilute sulphuric acid then fills any cracks or weak spots in the coating with a layer of non-conducting Al2O3.

Well, I have had two attempts at this so far, both were total, unmitigated disasters.

Attempt 1. The Al rod was abraded with 150 sandpaper and etched with NaOH for 10 - 20 seconds, washed with water and wiped with acetone. The 50:50 coating solution was sprayed on using a small perfume sprayer, this produces too much coating, and after about 3 spray coats I had a thick, crusty, crumbly coating that was a grey/cream/whitish colour. I removed some of the excess material by rubbing with a cloth, and proceeded to the "annealing". Applying 1.5 Volts produced a current in excess of 1.8 Amps and increasing (the electrodes were close together, and the acid was not as dilute as I thought it was). I reduced the voltage to 1.0 Volts and the current stabilised at about 1.5 Amps. The anode was bubbling away, producing copious oxygen. Since it seemed stable, I left it for an hour or two, when I came back the container was filled with grey crud and the anode had been partly eroded away!

Attempt2. This anode was pre-treated as above, but the 50:50 solution was applied by wet cloth, any excess was wiped off. At least 12 coats were applied, with the rod allowed to cool between coats. This produced a coating of the purest, glistening, sapphire .... no, no, I digress. This produced a silky looking coating, which was a clear/grey/creamy colour. I gave it a bit of a polish and with high hopes put it in the (now more dilute) sulphuric acid for "annealing". This resulted in no current flow, right up to about 13 or 14 Volts. The coating was a very good insulator. This was confirmed out of the cell with a multimeter.

The obvious difference in my procedure is the use of "pure" tin (II) sulphate, made from CP tin granules rather than solder, so perhaps the presence of antimony plays a part here.

I used an old small wholly metal drill chuck, mounted in the "plasticky" chuck of my cordless drill. This avoids the possibility of melting the plastic on modern chucks, as it gets pretty hot.

I await input from others, before proceeding!

plante1999 - 24-1-2011 at 18:06

Quote: Originally posted by plante1999

after some search i find it can be this: http://en.wikipedia.org/wiki/Aluminium_antimonide

because in my solder i ave 50% antimony. wath do you think.

after your test , it show that antimony is probably the missing thing.

i will buy some pur tin and i will test tanks for the test i show to me that i need to change mi recipe.

plante1999 - 24-1-2011 at 18:20

Quote: Originally posted by Xenoid

Well, this is all
I have prepared AlCl3 solution by dissolving scrap Al in concentrated HCl. Careful the reaction is quite vigorous and gets very hot! The solution was filtered hot and allowed to cool. The solubility of AlCl3 at 20 oC. is 45.8 g/100mls.

wath is the conssentration of your acid mine is 30% dilued in half so it is 15%.

does antimony react with copper sulfate?

Can you post some picture of the 2 anode please it will help me a lot.

[Edited on 25-1-2011 by plante1999]

dann2 - 24-1-2011 at 19:15

Hello,

It's 2008 all over again??

Regading Tin Oxide from Tin Sulphate see US 4028215, example 13 (below)

EXAMPLE 13

A strip of porous titanium having a surface area of approximately 7 square inches (45 square centimeters) was coated with a solution of tin and antimony compounds by use of a vacuum to suck the solution through the porous material. The solution consisted of 5.27 grams of stannous sulfate, 2.63 grams of antimony trichloride, 10 milliliters of hydrochloric acid, and 20 milliliters of butyl alcohol. This was done four times with the baking of one-half hour at approximately 500.degree. C. between each pass through the porous titanium material. A 50 percent aqueous solution of manganese nitrate was passed through the material in the same fashion with a baking between each pass of 45 to 60 minutes at approximately 200 degrees centigrade until a weight gain in the range of 3.36 to 3.56 grams of manganese dioxide is contained therein.
[SNIP]

Tin Sulphate cropped up from time to time in patents but they always used porous Ti (whatever exactly that is) as the substrate, never smooth plate.
Just about all Tin compounds decompose to SnO2 when heated. Some give 'usable' SnO2 (for an Anode application) in certain situations, some don't.
(IMO)

@Plante1999
You used the Anode for two weeks at one amp and got 100 grams of Chlorate (say K Chlorate).?
That gives (by my calculations using Swede's formula) 39% CE.

(131.22 * (100 GRAMS))/(336 AMPER HOURS) = 39

Dann2

[Edited on 25-1-2011 by dann2]

Xenoid - 24-1-2011 at 20:26

Quote: Originally posted by dann2

Hello,

It's 2008 all over again??

Regading Tin Oxide from Tin Sulphate see US 4028215, example 13 (below)

Good grief, dann2 - do you have all those patents committed to memory. It even has aluminium listed as one of the "valve" metals

I presume the porous Ti is sintered Ti powder, very high surface area.
I have that patent in my collection, it makes interesting reading. I'm not sure why I never bothered with it though, probably because it mentions electro-winning rather than chlorate/perchlorate anodes.

I thought you were in West Africa, with a bag of salt, looking for a wife

@plante 1999 - I am surprised the SnO2 alone is not able to make the Al2O3 conducting. I have some pure antimony metal, and it would probably react with copper sulphate, however it is insoluble so that's not much use. I will investigate antimony trichloride.

Edit: Re-reading your post; I would have thought that antimony sulphate would have been precipitated when you added the sulphuric acid to the solder dissolved in HCl. Thus, your tin sulphate would be antimony free!

[Edited on 25-1-2011 by Xenoid]

Zaratukhshthra - 25-1-2011 at 02:32

wow! seems too good to be true!

maybe you've made some kind of Al-Sb doped SnO2
aluminum doped SnO2 is known. For example US3901067 gives some info on making semiconducting Al doped SnO2 for H2S sensing. They use a solution of Al(NO3)3.9H2O and SnCl2 in glycerol to coat the electrode and heat from 25 to 430^C over 30 minutes. The resistance of a film with 4000A thickness is reported to be 1.7x10^5 to 2.2x10^4 ohm/square at 130^C (it was measured along the film).

Quote:

after some search i find it can be this: http://en.wikipedia.org/wiki/Aluminium_antimonide

No Al2O3+Sb2O3 can't be reduced to AlSb by flame! in your link it's actually mentioned that AlSb burns to produce aluminum oxide and antimony trioxide.

Edit:
I dont have access to the fulltext of this articleBut in the abstract it's claimed that: The room temperature electrical conductivities of the films are obtained in the range of 0.21 S cm−1 to 1.36 S cm−1 for variation of Al doping in the films 2.31–18.56% (which is a satisfactory conductivity range in my opinion)

[Edited on 25-1-2011 by Zaratukhshthra]

dann2 - 25-1-2011 at 13:27

Hello,

Quote: Originally posted by Xenoid

Good grief, dann2 - do you have all those patents committed to memory. It even has aluminium listed as one of the "valve" metals

Yes. Chapter, paragraph and line No's. in my head :-|
Al is not very 'Valve' though. I tested it some time ago together with Ti, Nb and W. It could only withstand about a Volt or two before it started to corrode/conduct when used as an Anode. According to Wouters site it corrodes when used as a Cathode!
If it works as an Anode substrate it would be great.
Perhaps if people are getting it hard to get this Anode to work they could try the idea using Ti (you will get no corrosing if coating is a bit iffy). Get that to work and then migrate to Al. Then again perhaps it only works using Al at the starting substrate?

Quote: Originally posted by Xenoid

I thought you were in West Africa, with a bag of salt, looking for a wife

Just home. Wife secured. I am not 100% pleased as see is a bit old for me. Hard to have it all your own way. Her father is very very pleased (he got his 28 pounds of salt), and of course my (new)wife is very very pleased (she got ME). My older wife......... not so pleased.
I decided to include a picture of her (new wife). It depicts her happily keeping an eye and jotting down some pH readings from my latest Chlorate cell. This cell uses a MetaStanic derived poly Mono Metal Spinal combined with a Perskovite doped inverse Spinel containing strategic quantities of Zn, Bi, As, Co, Ni etc etc etc.

Dann2

tnphysics - 2-2-2011 at 07:34

Maybe Sb-doped SnO2 appears, and the Al2O3 is just for adhesion.

pyromaniac - 5-2-2011 at 17:32

Can you substitute lead metal from fishing weights for the tin solder?

plante1999 - 5-2-2011 at 18:33

no but you can buy tin solder at 5dollars search for 50/50 tin antimony and fallow this guide and you will have great anode for making , with your naame i think you will made chlorate or perchlorate.

tnphysics - 5-2-2011 at 18:56

AlSb may form by 3AlSbO4+8Al->3AlSb+8Al2O3. It would be doped with Sn and likely conductive.

plante1999 - 5-2-2011 at 19:04

yes i was thinking the same.

pyromaniac - 5-2-2011 at 20:05

nahh, I like electrochemistry mostly. I bought some Roebic drain cleaner for the sulfuric acid and I do not know to concentration. I tried pouring a pouring a little into a container and added about 3 times as much (by mass) sugar. It started soaking up the sulfuric acid and the sugar at the center turned dark brown gradually getting light brown as it went outwards. I guess that I added too much sugar to make the carbon and the drain cleaner is brown. I am guessing that it's not that pure but I am planning on boiling the sulfuric acid to 100% purity (untill white fumes appear) and then using that stuff. Will that work or will it not be pure enough?

pyromaniac - 5-2-2011 at 20:08

BTW this anode can make perchlorate? Is it basically a lead dioxide anode?

plante1999 - 6-2-2011 at 04:35

the acid after boiled will be good if you ad some hydrogen peroxide end boile it , basicaly this anode is a aluminium oxide doped with aluminium antimonyde and tin dioxide anode.

[Edited on 6-2-2011 by plante1999]

otonel - 15-2-2011 at 05:58

I try to make MMO anod but I failed to make tin sulfate using hydrochloric acid, what is the trick.

plante1999 - 15-2-2011 at 13:49

could you please say wat you use for source of tin wath you think is wrong etc?

thanks!

otonel - 17-2-2011 at 13:26

I use tin solder for electric circuits and it don`t react with HCl

plante1999 - 17-2-2011 at 13:52

go to the plumber section of the hardware store and buy 50/50 tin/antimony solder , it should work , also some heating should help.

Random - 18-2-2011 at 11:25

Maybe it doesn't react that you see because the bubbles of hydrogen are too small and evolving too slow. Just cut it into the smallest pieces as you can and then put it into HCl, it will dissolve after some time.

jussssssssstttttt wondering

PolarSmokes - 19-2-2011 at 04:43

Has anyone else got this to work? Just curious =)

plante1999 - 19-2-2011 at 05:55

yes , my.

PolarSmokes - 19-2-2011 at 21:35

Could you please measure the resistance of your electrode?

otonel - 20-2-2011 at 01:35

I make that reaction using sulfide of tin make by melting together tin solder and the black residue was treated with HCl.
Then add H2SO4 and I filtered and used the resulting liquid.
But unfortunately my first MMO anode was failure because when I make electrolysis with 1,5V I observe a porous surface with small hole.

plante1999 - 20-2-2011 at 04:11

does you electrolise a sulfuric acid solution?

otonel - 20-2-2011 at 08:11

Yes a 10% sulfuric acid solution with tap water

plante1999 - 20-2-2011 at 08:15

omg tap water you need to use distill water , tap contain chlorine ion witch corrod aluminium.

ElectroWin - 5-3-2011 at 09:50

Because the anode turns out black, is it possible that the Aluminum/Tin/Antimony oxides are being reduced with the torch through carbon monoxide?

plante1999 - 5-3-2011 at 10:01

i facts it is black because th so small particule of oxide.

ElectroWin - 5-3-2011 at 14:12

okay, so that likely would be the black, α-SnO, which has electronic band gap between 2.5eV and 3eV?

Also, is it verified now that antimony is also required in this process? I have Sn/Pb solder, but no access to Sb.

plante1999 - 5-3-2011 at 15:49

yes it is , i sertify it to you , you are sure that your hardware shop doesnt have 50/50 sn/sb , on the pakage it is wrigthed : Contain lead. but this is false , if you read the small script it will say 50/50 antimony / tin .

gregxy - 5-3-2011 at 18:02

There are dozens of types of solder.
From Wikipedia, this sounds like the correct one
95% tin 5% Antimony:

Sb5, ASTM95TA, Indalloy 133. The US plumbing industry standard. It displays good resistance to thermal fatigue and good shear strength. Forms coarse dendrites of tin-rich solid solution with SbSn intermetallic dispersed between. Very high room-temperature ductility. Creeps via viscous glide of dislocations by pipe diffusion. More creep-resistant than SnAg3.5. Antimony can be toxic. Used for sealing chip packagings, attaching I/O pins to ceramic substrates, and die attachment; a possible lower-temperature replacement of AuSn.[7] High strength and bright finish. Use in air conditioning, refrigeration, some food containers, and high-temperature applications.[16] Good wettability, good long-term shear strength at 100 °C. Suitable for potable water systems. Used for stained glass, plumbing, and radiator repairs.

Did anyone find out if this electrode can make ClO4?

ElectroWin - 5-3-2011 at 20:58

I found a company that makes 95/5 Sn/Sb but not the 50/50 kind.

What brand, product do you recommend?

ElectroWin - 6-3-2011 at 07:16

in another post, about antimony doped tin on titanium, on 21-7-2007
Rosco Bodine writes:
The black color with the antimony doping might be a bimetal oxide or oxychloride of titanium and antimony, and that might be forming an unidentified diffusion layer
[...].

so i guess, since this seems to happen on aluminum as well, it is not the titanium.

food - 18-3-2011 at 08:17

Quote: Originally posted by pyromaniac

nahh, I like electrochemistry mostly. I bought some Roebic drain cleaner for the sulfuric acid and I do not know to concentration.

This fellow has a couple of quite good videos on evaluating sulfuric acid.

quest - 28-5-2011 at 13:31

Some one did any new experiments with this anode? it's sound like a very promise anode for "poor man".

rabidmonkey - 8-6-2011 at 17:23

I have a ton of carbon electrodes laying about, would it work if i substituted the aluminum pipe for a carbon rod?

White Yeti - 27-7-2011 at 17:46

This is unrelated to tin/ antimony and aluminium oxides, but has anyone experimented with vanadium and nickel oxides? A solid coat of vanadium pentoxide can be deposited on the activated layer of a titanium electrode when an ammonium metavanadate solution is applied and heated to decomposition temperature.

I've always wanted to experiment with nickel oxide and possibly try to deposit a solid amorphous layer of nickel oxide onto the surface of a titanium electrode. However, I cannot think of any salts of nickel that can be dissolved in water and then decomposed onto the surface of a titanium electrode. Alternatively, is there a way to deposit nickel oxide electrolytically?

Any ideas?

plante1999 - 3-8-2011 at 18:06

Ok i will assume my failure , after 3-4 week , the anode was completly destroyed with production of grey mud. in fact after 20 day huge amount of gray mess was produce.

cyanureeves - 3-8-2011 at 18:38

plante which failure? after 3-4 weeks how much chlorate did you produce?how can an anode that lasts almost a month be considered a failure? i'm still peeling off 6volt batteries for electrodes and i got a heap of black mud. but the way i look at it is i got dirty chlorate instead of potassium chloride just sitting in a bag just being potassium chloride.i just unplugged my chlorate cell after 2 weeks of zapping left over bleach from hydrazine sulfate synth. now i got BLEACH and black mud but no chlorate. i'm gonna use it to kill a stubborn old hackberry tree in the alley. i'm still gonna buy tin/antimony solder this weekend and more muriate of potash.

[Edited on 4-8-2011 by cyanureeves]

White Yeti - 4-8-2011 at 05:59

Cyanureeves, He's probably calling it a failure because it isn't a true MMO anode. A true MMO can survive over 50 cycles in a chlorate cell.

Diablo - 24-6-2012 at 12:30

I wonder if this would make a good substrate for lead dioxide anodes?

plante1999 - 24-6-2012 at 15:17

Quote: Originally posted by Diablo

I wonder if this would make a good substrate for lead dioxide anodes?

maybe but sincerely go for a commercial MMO anode.

dann2 - 24-6-2012 at 16:36

Quote: Originally posted by Diablo

I wonder if this would make a good substrate for lead dioxide anodes?

Swede - 4-7-2012 at 09:05

Interesting thread I missed... yesterday I was browsing the internet looking for ruthenium chloride, thinking I'd try to roll my own MMO for fun, and the price was staggering, many hundreds of $$ for 5 to 10 grams.

It's hard to beat the "real deal" for chlorate. On that failed cell I made with the separate electrode chamber, when it jammed up, it ran overnight at 60 amps with just a couple of liters of volume, with the temperature near boiling, and no doubt took the liquor down to near zero chloride. The cathodes were horribly warped, but after I wiped off the anode, the MMO looked as good as it did before the run, no degradation at all that I could see.

It's a shame MMO won't make perchlorate. Or there's not some magic added catalyst that would help it along. Our problems would be solved, but then we'd not be faced with the fun and challenge!

jpsmith123 - 4-7-2012 at 14:06

Hello Swede,

There are a few things that seem promising (IMO) but haven't been tried yet. I was planning on doing some experimenting myself, but I just keep getting side-tracked (I never should have bought a lathe and a milling machine). Anyway, one idea is to electrodeposit a thin layer of Bi2O3 over MMO.

Bi2O3 occurs in several crystal phases and I don't know how important it would be for perchlorate purposes but the delta phase (supposedly the most desirable polymorph for some applications at least) has been electrodeposited at low temperature as per this paper.

Swede - 5-7-2012 at 06:17

Hi JP - cool find on that paper. I need to read it in some detail. I have a couple of Bi salts stashed away, but not the nitrate. Anything that shows promise, isn't a precious metal, is worth pursuing. Lead Dioxide has been done to death, with not all that much success, at least on the amateur level. And you end up with a toxic brew when you're done.

So you got sucked into the black void of hobby machining?

I've been doing it for years, and fine machine tools don't go well with chemicals, especially mineral acids. Any time I do anything with HCl or HNO3, I take it WAY outside, away from my tools, because otherwise they end up dusted with rust. Nasty stuff. I've had entire racks of tools rust because a jug of HCl was in the vicinity.

What are you making with your tools?

jpsmith123 - 5-7-2012 at 13:24

So far I've been mostly working with plastics and some brass. (I'm interested in high voltage pulsed-power stuff).

I got so frustrated trying to do simple things - without much success - that I finally went out and bought a mini lathe. And then later a mini mill.

I've made various coil formers, potting cups, coils, feed-through insulators, and complete high voltage, high frequency transformers. And also voltage multipliers.
(Right now I'm refurbishing some used high power spark gap switches I got from ebay).

Coil With Feed Thru Insulators.jpg - 57kB

##################################

Anyway I have some Bi2O3, some bismuth rod, and some SnCl2 and SnO2. I've been meaning to try a few things - coatings put on over MMO - but I just kept getting distracted...and I only have a small work area which is just overcrowded right now.

BTW for anyone working with lead compounds (or other heavy metals), I found a few interesting studies on pubmed, regarding getting rid of it from your body. There's some evidence that "modified citrus pectin" will mobilize and help excrete it. (Modified citrus pectin is avaiable as a nutritional supplement).

Phytother Res. 2006 Oct;20(10):859-64.
The effect of modified citrus pectin on urinary excretion of toxic elements.
Eliaz I, Hotchkiss AT, Fishman ML, Rode D.
SourceAmitabha Medical Clinic and Healing Center, 7064 Corline Ct. Ste A, Sebastopol, CA 95472, USA.

Abstract
This study was undertaken to evaluate the effect of modified citrus pectin (MCP) on the urinary excretion of toxic elements in healthy individuals. MCP is a reduced molecular weight pectin (weight-average molar mass = 15,400) that is mostly linear homogalacturonan with a 3.8% degree of esterification and approximately 10% rhamnogalacturonan II based on the presence of 2-keto-3-deoxy-octonic acid. Subjects ingested 15 g of MCP (PectaSol, EcoNugenics Inc., Santa Rosa, California 95407) each day for 5 days and 20 g on day 6. Twenty-four hour urine samples were collected on day 1 and day 6 for comparison with baseline. The urine samples were analysed for toxic and essential elements. In the first 24 h of MCP administration the urinary excretion of arsenic increased significantly (130%, p < 0.05). On day 6, urinary excretion was increased significantly for cadmium (150%, p < 0.05). In addition, lead showed a dramatic increase in excretion (560%, p < 0.08). This pilot trial provides the first evidence that oral administration of MCP increases significantly the urinary excretion of toxic metals in subjects with a 'normal' body load of metals. It is suggested that systemic chelation of toxic metals by MCP may in part be attributable to the presence of rhamnogalacturonan II, which has been shown previously to chelate metals.

Copyright 2006 John Wiley & Sons, Ltd.

PMID: 16835878 [PubMed - indexed for MEDLINE]

Altern Ther Health Med. 2008 Jul-Aug;14(4):34-8.
The role of modified citrus pectin as an effective chelator of lead in children hospitalized with toxic lead levels.
Zhao ZY, Liang L, Fan X, Yu Z, Hotchkiss AT, Wilk BJ, Eliaz I.
SourceDepartment of Medicine, Children's Hospital, Zhejiang University School of Medicine, Hangzhou, Republic of China.

Erratum in
Altern Ther Health Med. 2008 Nov-Dec;14(6):18.
Abstract
CONTEXT: Lead toxicity is an ongoing concern worldwide, and children, the most vulnerable to the long-lasting effects of lead exposure, are in urgent need of a safe and effective heavy metal chelating agent to overcome the heavy metals and lead exposure challenges they face day to day.

OBJECTIVE: This clinical study was performed to determine if the oral administration of modified citrus pectin (MCP) is effective at lowering lead toxicity in the blood of children between the ages of 5 and 12 years.

METHOD: Hospitalized children with a blood serum level greater than 20 microg/dL, as measured by graphite furnace atomic absorption spectrometry (GFAAS), who had not received any form of chelating and/or detoxification medication for 3 months prior were given 15 g of MCP (PectaSol) in 3 divided dosages a day. Blood serum and 24-hour urine excretion collection GFAAS analysis were performed on day 0, day 14, day 21, and day 28.

RESULT: This study showed a dramatic decrease in blood serum levels of lead (P = .0016; 161% average change) and a dramatic increase in 24-hour urine collection (P = .0007; 132% average change).

CONCLUSION: The need for a gentle, safe heavy metal-chelating agent, especially for children with high environmental chronic exposure, is great. The dramatic results and no observed adverse effects in this pilot study along with previous reports of the safe and effective use of MCP in adults indicate that MCP could be such an agent. Further studies to confirm its benefits are justified.

PMID: 18616067 [PubMed - indexed for MEDLINE]

[Edited on 5-7-2012 by jpsmith123]

Swede - 5-7-2012 at 15:58

jpsmith, that is some superb and high-quality work! The coils caught my attention right away. I am into miniature IC engines, and in need of a small, scale spark coil (primary and secondary), I decided to wind my own. The secondary wire is incredibly fine stuff, much smaller than a human hair, and breaks easily. And if broken in the middle of a wind, the coil is scrapped.

Anyway, I engineered a CNC coil winding machine using two stepper motors from old 5.25" floppy drives, and software written using Visual Basic. The Spindle turns slowly, and the laydown system drops the wire into a coil spaced exactly the width of the Cu wire itself.

The many layers of secondary were interleaved with sections of kapton tape. It worked nice, in the end:

Back OT a bit... I've found a machining capability to be a HUGE asset for electrochemistry. I've lost track of the number of unique fittings I've made from virgin PTFE and PET stock, delrin too. It gives one special capabilities, but it does come at a cost.

Re: Pb... I've got a few bottles of various chelators, and when I was working with kilos of Pb nitrate, I used them. Probably overly paranoid, but it's one of those things that when you think about it too much, it gets on your nerves. I even made some Pb detection swabs using Rhodezinic (sp?) acid that would turn magenta with the detection of Pb ions. When I wiped down my work area, I found lead all over the place. After that, I went at it with dozens of moist paper towels, put my Pb salts away, and haven't plated lead since. But I plan on it, eventually.

jpsmith123 - 5-7-2012 at 17:47

Wow! That's some intricate coil winding machine ya got there! (BTW I thought my OCD was bad until you came along, Swede

)

Anyway, with regard to anodes, one thing I'm doing (very slowly) is getting set up to do some electro-deposition experiments using an arbitrary waveform generator and an audio amplifier. (I just got the amplifier circuit board populated a few days ago - it's a simple LM3886 based circuit).

In his MMO patents, IIRC, Beer used low voltage AC (stepped-down mains AC I presume), but I've seen more recent papers where oxides were electrodeposited using non-sinusoidal AC voltages, e.g., high frequency pulses with a certain duty cycle. That's what I someday would like to try with Bismuth (and/or Bismuth & Tin) oxide over MMO.

I think Dann2 tried to put Bi2O3 & SnO2 directly over Ti, by way of the dip and bake method, but the Ti passivated, IIRC. I'm not sure if he tried it over MMO, but I don't think he did, as I don't recall any discussion of it here anywhere.

So, with regard to putting some Bi or Bi & Sn oxide over MMO, it's all a wide open area for experimentation, AFAIK.

watson.fawkes - 6-7-2012 at 05:25

Quote: Originally posted by jpsmith123

Anyway, with regard to anodes, one thing I'm doing (very slowly) is getting set up to do some electro-deposition experiments using an arbitrary waveform generator and an audio amplifier.

FYI. Certain commercial plating system use negative-going pulses. They're at low duty cycle and apparently they work by discharging the effective-capacitor formed by the polarization region of the electrode. If you want to do this, you can add an H-bridge circuit to the output and tie it to the sign of the waveform.

Swede - 7-7-2012 at 05:43

All of the "deposition" processes are fascinating, and traditionally only the realm of institutions. It'd be awesome to see something set up in a home lab. Press on, please!

ElectroWin - 1-10-2012 at 05:05

I have given up on this, and plan to go with platinized titanium