Titanium Chemistry

[Swede]

As part of an ongoing investigation into MMO, WSM and I have been going through some old patents from the 1970's on exactly how it's done. Something I was not aware of was that MMO is predominantly titanium oxides... elements like ruthenium iridium, tin, tantalum, and platinum, form only a small portion.

 

These are combined in an aqueous or alcoholic mixture of rare earth chlorides or nitrates, which are then coated onto a substrate, and thermally decomposed into mixed oxides.

 

Having not done a lot of this type of chemistry, I decided to take a whack at it and see how these materials handle.

 

The first step was creation of titanium chloride. It comes in a number of states, Ti II, III, and IV, but only Ti (III) chloride, TiCl3, is of practical use and interest. This is made by dissolving Ti metal in HCl. It takes a little heat to get it kick-started. I added 1 gram samples to two beakers. One was covered with a stoichiometric amount of HCl, the other, with a large HCl surplus.

 

 

http://www.5bears.com/mmo/tita07.jpg

 

Once the reaction starts, it proceeds steadily, with hydrogen evolution, and the HCl taking on a purple cast fairly quickly...

 

http://www.5bears.com/mmo/tita10.jpg

 

It takes on a deep purple cast after a few hours...

 

http://www.5bears.com/mmo/tita01.jpg

 

In use, this would be combined with other rare earth chlorides, or, some patents call for the conversion of Ti (III) chloride, to Ti2O5. This is easily accomplished with concentrated H2O2. Adding just two drops of peroxide to the sample above created a vigorous exothermic reaction, and the violet color changed instantly to a burnt orange. Quite a fun reaction:

 

http://www.5bears.com/mmo/tita03.jpg

 

I isolated samples of both the oxide and the chloride, and attempted to dry them. It actually worked, although the chloride, dried, is extremely hygroscopic, and also oxidizes under the influence of regular O2:

 

http://www.5bears.com/mmo/tita05.jpg

 

http://www.5bears.com/mmo/tita06.jpg

 

Interestingly, the oxide, or whatever the burnt-orange stuff is, is soluble in water, and creates a solution that is bright orange, very similar to a dichromate solution.

 

To do: figure out a way to store this stuff, if it is storable at all. If not, determine the best way to manufacture the necessary chlorides and oxides for some future MMO attempts. It may, just may be possible, to incorporate PbO2 and/or high percentages of iridium into an MMO and make an anode that can create perchlorate. We all know how sturdy a properly made MMO anode is in use... if we can replicate that, and make it electrocatalytic for perchlorates, we may be in luck!

[NightHawkInLight]

I have a ton of Ti sheet that I would love to be able to put to use making MMO anodes. I'm very interested in what you have going here. Thanks as usual for your efforts and excellent documentation.

[WSM]

http://www.5bears.com/mmo/tita06.jpg

 

Wait, Is that "cracked mud" I see?!! Now I wonder if the titanium part is more responsible for that effect or is it a combination of the oxides, or...?

It's interesting to see in the ingredients, rather than just the final product.

 

This will be an interesting journey, for sure!

 

WSM

[psyco_1322]

Pretty colors

 

So, never thought about this, but couldn't one take some chunks of Ti and dissolve them into HCl and redox back to Ti with a chunk of Al or Mg? Easy fine Ti powder?

[gregkdc1]

I brought this idea up on science madness but I didn’t get much of a response. I will bring it up again because I think it fits into your thread about Ti chemistry.

 

Why not make an alloy of titanium and some other metal like lead, bismuth etc that will oxidize in a cell to form the functional oxide layer? Lead and titanium both form the dioxide in a cell and the PbO2 will make perchlorate but it flakes off while the TiO2 doesn’t. The plan being you could get a compromise between the 2 oxides characteristics of tenacity and conduciveness. If this did work the anode may also be self healing, as the oxide layer erodes it would make more oxide to takes its place. Last I could see people making an anode like this by using a thermite type reaction of pre-weighed metal oxides. According to the net titanium will react this way if you have enough of another metal oxide to get it going.

[WSM]

I brought this idea up on science madness but I didn’t get much of a response. I will bring it up again because I think it fits into your thread about Ti chemistry.

Why not make an alloy of titanium and some other metal like lead, bismuth etc that will oxidize in a cell to form the functional oxide layer? Lead and titanium both form the dioxide in a cell and the PbO2 will make perchlorate but it flakes off while the TiO2 doesn’t. The plan being you could get a compromise between the 2 oxides characteristics of tenacity and conduciveness. If this did work the anode may also be self healing, as the oxide layer erodes it would make more oxide to takes its place. Last I could see people making an anode like this by using a thermite type reaction of pre-weighed metal oxides. According to the net titanium will react this way if you have enough of another metal oxide to get it going.

 

Too bad it's not that simple. The idea of an alloy sounds attractive, but the differences between the metals works against us in this case. The best approach is the proven "paint and bake" approach for MMO manufacture that industry uses. It's very controllable and we can get exactly what we want if we keep the variables in line with our goals. Even still, we need to carefully remove the oxide layer on the titanium before coating it, without letting it oxidize again before it's baked (we have techniques in mind to accomplish this).

 

The biggest problem with a thermitic approach (besides it being wildly uncontrollable), is the lead would vaporize away and we'd be left with a messy titanium oxide residue (not to mention the toxic cloud leaving our work space ).

 

Thanks for the input. It never hurts to look at other options.

 

WSM

 

edit: I believe titanium sponge starts as a mixture of titanium and sodium metal. The sodium is reacted out, leaving the sponge to be furthur processed into usable titanium materials.

Edited September 27, 2012 by WSM

[WSM]

Pretty colors

So, never thought about this, but couldn't one take some chunks of Ti and dissolve them into HCl and redox back to Ti with a chunk of Al or Mg?

Easy (?) fine Ti powder?

 

Possibly. Have you studied this out? If it is possible, what would it cost? Would the cost be more than other methods of production?

 

I don't know. I don't believe it's done this way by industry, but that doesn't mean it won't work (Swede made potassium perchlorate from potassium chlorate, and industry doesn't). Are you planning to try it? Let us know what you learn.

 

WSM

[WSM]

I have a ton of Ti sheet that I would love to be able to put to use making MMO anodes. I'm very interested in what you have going here. Thanks as usual for your efforts and excellent documentation.

 

Hi NHIL,

 

Is it CP titanium sheet? It already will make excellent cathodes . I agree making some into anodes is attractive, but the effort and expense may price it out of reach, UNLESS you're trying for something special. I think that's where we're headed with this. Not just repairing cut or damaged MMO mesh before plating with other materials; but making a proper substrait for other anodes (like a perchlorate anode). We intend to share our efforts and hopefully get to a point where we can make the higher salts as readily as we can make chlorates.

 

If you want chlorates, buy some MMO mesh, a good power supply and you're on your way...(if you mind the details, that is).

 

It appears the best way to progress is to reinvent the wheel, then see where we can go from there. (Hold my rootbeer and watch this... ).

 

WSM

[Swede]

Pretty colors

 

So, never thought about this, but couldn't one take some chunks of Ti and dissolve them into HCl and redox back to Ti with a chunk of Al or Mg? Easy fine Ti powder?

 

It's worth a shot, and I'll try some Al and/or Mg next time, but my gut feel is we'd end up with a mash of oxides and hydroxides. But if it DID work, you'd end up with some extremely fine titanium!

 

If anyone else wants to try this, I'd recommend Ti powder, atomized or spherical. Like i mentioned, not much happens until heat is applied, and even then, the reaction is pretty slow. Simple Ti sheet or wire would take quite a while to dissolve.

 

We're hopeful in doing this that we WON'T reinvent the wheel. It'd be nice to come up with some formulations that are electrocatalytic for perchlorate, but if not, I am confident that we are going to learn a lot about coating and plating Ti, which (in the end) we need to do correctly for PbO2. Another thing I'd like to experiment with are perhaps OTHER valve metals as a substrate. Ti is great, but there might be an advantage (with regards to perchlorate/PbO2) in using something different, like Ta, Nb, etc.

 

I would dearly love to figure out a methodology for lead dioxide that isn't simply yet another attempt at plating. I like the notion of thermal decomposition, but it may not form the correct variety of PbO2. But all that is in the future.

[Mumbles]

I was doing some reading on Titanium (III) Chloride. It sounds like you have indeed made it based on the color. I saw a few reference state that while it's soluble in water, it cannot be recovered from it. Trying to recover it probably yields mixed hydroxide and chlorides and well as some oxides. If you want to isolate titanium (III) chloride, there are a variety of apparatuses to do so, but most involve reduction from titanium (IV) chloride. It's nicknamed "tickle" for more than just the formula, but also what it will do to your lungs.

[NightHawkInLight]

Hi NHIL,

 

Is it CP titanium sheet?

CP? I'm not familiar with the abbreviation. I know it makes good cathodes, but I've got way more than I need for that purpose.

[WSM]

CP? I'm not familiar with the abbreviation. I know it makes good cathodes, but I've got way more than I need for that purpose.

 

CP stands for Commercially Pure, and usually has only very little amounts of other elements in it ( < 0.5%) if any. If that's the grade of sheet titanium you have, then you're in good shape!

 

WSM

Edited September 28, 2012 by WSM

[ANFO]

It seems that thermal decomposition of lead nitrate or lead carbonate produces lead oxide, not dioxide. I wonder if there is any possiblity of altering the conditions of the decomposition (O₂ rich environment/peroxide/catalyst) which would yield dioxide. The nitrate reaction produces spare oxygen, so the oxygen is already present there the question is why doesn't it form dioxide?

 

2 Pb(NO₃)₂ → 2 PbO + 4 NO₂ + O₂

PbCO₃ → PbO + CO₂

 

Only thing about the carbonate, if it's heated in an oxygen rich environment, we'll get lead tetroxide: 6 PbCO₃ + O₂ → 2 Pb₃O₄ + 6 CO₂

 

_{On the plus side, all these variations of lead oxides have distinctly different colours, so it would be easy to tell them apart if you did manage to get a different reaction.}

 

The only thing lead dioxide is soluble in is acetic acid (vinegar), so maybe it could be painted and baked on under certain conditions, but I doubt it.

 

The last thing I could think of, which is the long shot (very long) is attaching lead tetroxide to titanium, either by oxidation of lead carbonate, or melting the tetraoxide and dipping the titanium plate in it. Then dipping the coated titanium plate(if it works) in nitric acid, which leaves lead dioxide and dissolves the nitrate.

 

Pb₃O₄ + 4 HNO₃ → PbO₂ + 2 Pb(NO₃)₂ + 2 H₂O

 

Forgive my brainstorming

Edited September 28, 2012 by ANFO

[WSM]

It seems that thermal decomposition of lead nitrate or lead carbonate produces lead oxide, not dioxide. I wonder if there is any possiblity of altering the conditions of the decomposition (O₂ rich environment/peroxide/catalyst) which would yield dioxide. The nitrate reaction produces spare oxygen, so the oxygen is already present there the question is why doesn't it form dioxide?

2 Pb(NO₃)₂ → 2 PbO + 4 NO₂ + O₂

PbCO₃ → PbO + CO₂

Only thing about the carbonate, if it's heated in an oxygen rich environment, we'll get lead tetroxide: 6 PbCO₃ + O₂ → 2 Pb₃O₄ + 6 CO₂

_{On the plus side, all these variations of lead oxides have distinctly different colours, so it would be easy to tell them apart if you did manage to get a different reaction.}

The only thing lead dioxide is soluble in is acetic acid (vinegar), so maybe it could be painted and baked on under certain conditions, but I doubt it.

The last thing I could think of, which is the long shot (very long) is attaching lead tetroxide to titanium, either by oxidation of lead carbonate, or melting the tetraoxide and dipping the titanium plate in it. Then dipping the coated titanium plate(if it works) in nitric acid, which leaves lead dioxide and dissolves the nitrate.

Pb₃O₄ + 4 HNO₃ → PbO₂ + 2 Pb(NO₃)₂ + 2 H₂O

Forgive my brainstorming

 

Forgive it?

 

We invite it ! Thanks for the thoughts.

 

WSM

Edited September 30, 2012 by WSM

[Swede]

I think the chances of magically creating a paint & bake PbO2 MMO which works is near zero, but you never know. What makes these so interesting is that minute changes in composition yield wildly differing electrochemical characteristics. For example, in the early 1950's, they found that near trace amounts of iridium in titanium changed its chracteristics drastically. So, you never know. Apparently, a critical component of how MMO's work s the interatomic distances, and the types of crystals they make, If the xtals and distances are close, they can combine as if they were a single crystal form.

 

Like the perchlorate cell stuff, this is mostly for fun, and the thrill of discovery.Something else to keep in mind is that MMO as we use it is very, very light in precious metals, for economy. By possibly jacking up the amount of Ru and/or Ir relative to the TiO2, we may see something not new, but rejected by industry as being uneconomical... for THEM. No one here is pretending we are going to discover cold fusion using mixed metal oxides.

 

I left a solution of HCl over a gram of Ti over a week or so, and 100% of the Ti was gone. Just to be sure, I ran it through a syringe flter and gathered the liquid:

 

http://www.5bears.com/mmo/tita12.jpg

 

The acidified/aqueous TiCl3 seems to be quite stable. The beaker with the sol'n in it sat exposed to air the whole time, and visually, there was little change. As part of a follow-on experiment, I placed 1/2 gram of Ti spheres in a tiny bottle, covered it with HCl, and put the cap back on loose. No heat. I'll see what happens.

 

The fun NurdRage YouTubes had a video on purifying HCl by simply enclosing two open containers in a third. One has distilled water, the second has crappy muriatic acid. Over a week or two, the HCl gas migrates to the water and dissolves in it. Kind of a poor-man's slow-motion distillation. I'm giving it a try right now. By having a huge surplus of crude HCl and just a little water, the concentration of the pure HCl should be pretty high, and with this process, all we need is a few ml.

 

Through much hassle, we have obtained 25 grams of RuCl3 hydrate, which should in theory create 2.5 square meters of MMO. Not much to look at, almost like iodine in color.

 

http://www.5bears.com/mmo/ru003.jpg

 

The TiCl3 seems relatively easy. Sn is also a possibility, as is Iridium, but the latter is about like platinum in cost.

Edited October 6, 2012 by Swede

[Swede]

As a bit of a follow-up to last night's post, WSM and I have been going through dozens of old patents, and the history behind MMO is fascinating. We owe much of it to a chemist named Henri Beer, who did a bunch of work in the late 1960's and subsequently ROCKED the chlor-alkali world with his discoveries. Before DSA (MMO), graphite electrodes were standard, and we all know the drawbacks of graphite. But importantly, besides the mess and loss of anode material, the power requirements for the graphite systems were much higher than they were for Henri's new MMO anodes.

 

Overnight, the cost to produce chlorine, oxygen, hypochlorites, chlorates, chlorine dioxide, plummeted. And for many of these processes, the MMO outperformed Pt by a significant margin. Anode losses went from dozens of grams per ton of product, to milligram losses.

 

What made it all work was years of testing various rare-earth oxides in differing proportions, and they found that even tiny changes in formulations produced huge differences in electrocatalytic action. And the MMO we see and use today... it's not some cosmic electron gun sputtering deposition in a Xenon/Helium atmosphere, it's a dude with a paint brush,.some liquids, and an oven. Temps are less than 500 C. Interestingly, Mr. Beer went on to work for deNora, a huge firm, and it is from them that I bought a 2' X 4' section of MMO detailed in the "MMO for the masses!" blog I did years ago.

 

I REALLY need a good book on electrochemical theory. I was never good at it, preferred organic chem, and need to brush up on it. What we are looking for are formulations that promote oxygen evolution vs. chlorine evolution.

Edited October 7, 2012 by Swede

[WSM]

As a bit of a follow-up to last night's post, WSM and I have been going through dozens of old patents, and the history behind MMO is fascinating. We owe much of it to a chemist named Henri Beer, who did a bunch of work in the late 1960's and subsequently ROCKED the chlor-alkali world with his discoveries. Before DSA (MMO), graphite electrodes were standard, and we all know the drawbacks of graphite. But importantly, besides the mess and loss of anode material, the power requirements for the graphite systems were much higher than they were for Henri's new MMO anodes.

Overnight, the cost to produce chlorine, oxygen, hypochlorites, chlorates, chlorine dioxide, plummeted. And for many of these processes, the MMO outperformed Pt by a significant margin. Anode losses went from dozens of grams per ton of product, to milligram losses.

What made it all work was years of testing various rare-earth oxides in differing proportions, and they found that even tiny changes in formulations produced huge differences in electrocatalytic action. And the MMO we see and use today... it's not some cosmic electron gun sputtering deposition in a Xenon/Helium atmosphere, it's a dude with a paint brush,.some liquids, and an oven. Temps are less than 500 C. Interestingly, Mr. Beer went on to work for deNora, a huge firm, and it is from them that I bought a 2' X 4' section of MMO detailed in the "MMO for the masses!" blog I did years ago.

I REALLY need a good book on electrochemical theory. I was never good at it, preferred organic chem, and need to brush up on it. What we are looking for are formulations that promote oxygen evolution vs. chlorine evolution.

 

One of the better books I collected (though all are dated and usually discuss graphite or platinum on titanium for anodes) is, "ELECTROCHEMISTRY, Theoretical Principles and Practical Applications" by G. Milazzo, 1963. I also have books by Mantell, Hampel and Pletcher. Of those, "The Encyclopedia of Electrochemistry" by Hampel, 1964; is more likely to have some useful information.

 

The better information on the state-of-the-art are usually in papers published by various symposia dealing with electrochemistry after the 1970's to the present.

 

I wish I could just pull a book off the shelf, digitize the pertinent information and send it.

 

WSM

[gregkdc1]

I don't know if you guys have seen this patent but if the techniques it uses are true it may be beneficial to what you are trying.

http://www.freepaten...om/3730857.html

 

Finding anhydrous ethanol can be a problem but I wonder if 99% isopropanol could work instead? Could you make a bismuth doped manganese dioxide anode more stable by adding an additional metal oxide? There is a patent out there that we have all read that said adding silicon increased the lifespan of manganese dioxide anodes but it wasn't making perchlorate and it was in an acid environment. I wonder if iron or perhaps just more titanium would make the oxide layer more stable, as these oxides seem to perform better in basic environments.

I know you have all probably thought of similar ideas before and even read the patent that I posted. If this process works it seems like an easy way to produce hard to find chemicals.

Edited October 11, 2012 by gregkdc1

[Swede]

I downloaded that patent and added it to my growing pile of them. Patents can be dry reading but are great sources of basic information.

 

If you need a true anhydrous solvent, I don't think 99% iso will work. There are chemical methods to make anhydrous alcohols that aren't too bad. If isopropanol will work, it'd be easier taking 99% to 100% rather than taking 90% everclear or similar and trying to get that massive amount of water out of it. But I'll bet there are threads on some other sites that discuss this.

 

Metal oxides are really interesting, and there is a lot of room for experimentation. Not many amateurs have given it a serious shot, and when the pro's do it, they are often looking only for anodes and mechanisms that are economically viable, so they may bypass otherwise promising formulations and the like.

[Swede]

I forgot to mention - the TiCl3 chemistry is interesting. I've tried a few more variations on the theme, and one that I think is promising is HCl over a massive surplus of Ti. Placed in a plastic bottle with the cap screwed on loose, the TiCl3 evolves, the acid concentration decreases, and eventually we end up with a mildly acidic solution of TiCl3 rather than one that is strongly acidic. Excess acid may not be desirable with MMO coatings.

 

The entire process takes place without heat over 3 or 4 days. The solution can probably be stored as-is... aqueous, acidic TiCl3 over Ti metal. This method may also work for other metals.

 

Bi₂O₃ + 6 HCl → 2 BiCl₃ + 3 H₂O

 

MnO₂ + 4 HCl → MnCl₂ + 2 H₂O + Cl₂

 

etc

[frank]

http://www.ebay.co.uk/itm/titanium-tetrachloride-100grms-cas-no-7750-45-0-reagent-grade-min-assay-99-5-/271072695705?pt=UK_BOI_Medical_Lab_Equipment_Lab_Supplies_ET&hash=item3f1d311599

 

 

Titanium Tetrachloride available here. It appears in some MMO patents.

[Swede]

That guy also has sodium azide... I'd be all over it if it was USA-located.

 

I have two varietites of TiCl3 stored right now... one of them was formed by having a huge surplus of the Ti metal under HCl over a period of days, allowing any equilibrium to develop. The solution is still acidic, but not strongly. My understanding is that this will store and the acidity is necessary for stability. The other variety used a surplus of HCl, so it is lighter purple and much more acidic. I have also been playing with Tin, and the production of tin chloride, but nothing to report there yet.

 

I've acquired some oxalic acid (cheap, $3 lb) for etching/stripping of Ti oxides prior to coating. I have a full range of mineral acids as well. The plan is to attempt "MMO" that uses no ruthenium, to get the process down, before unleashing the expensive Ru salts. If the fake MMO will conduct over time in brine, it means that the etching/surface prep,.and the bake, went successfully.

[taiwanluthiers]

Can you make Ti chloride with TiO2 and HCl?

[Swede]

Possibly... I honestly don't know. It's worth a try, titanium dioxide is not expensive, that's for sure.

 

Just for fun - some pictures of a 500ml bottle of T-butanol

 

HO-CH2-CH2-CH2-CH3

 

This stuff his an interesting smell, and a relatively high freezing point of 25 C, about room temperature. It freezes into a waxy solid which, like most frozen compounds, is more dense than the liquid, thus sinking. When I first saw it, I thought "Oh no, the bottle will break because it'll expand!!"

 

http://www.5bears.com/mmo/tbut01.jpg

 

http://www.5bears.com/mmo/tbut03.jpg

 

T-butanol is miscible with water, and is the solvent of choice for carrying Pt-group and Ti chlorides, for coating bare titanium for MMO.

Edited November 2, 2012 by Swede

[Mumbles]

All the t-BuOH I've ever seen in the lab have come in plastic bottles for that very reason. Good luck with this. The formula is actually (CH₃)₃COH. You described n-butanol.