Titanium Chemistry

[WSM]

Can you make Ti chloride with TiO2 and HCl?

 

I don't think so. According to Brauer (Handbook of Preparative Inorganic Chemistry), TiCl₃ is typically made from TiCl₄ in complex and expensive lab equipment. It is SO much easier to dissolve titanium powder in HCl...

 

WSM

[Swede]

Got a new toy today. Besides pyrotechnics and chemistry, I have a little machine shop, and do a lot of abrasive blasting. Since it's mostly aluminum I need to blast, glass beads are the media of choice. Glass beads on aluminum creates a lovely matte finish. Abrasives like aluminum oxide are too aggressive, so my blast cabinet is full of beads, and will remain that way.

 

I do have some ALOX for use outside the cabinet, but my guns are all big, industrial jobs. For fine use, I sprung on a Paasche "air eraser". What this has to do with chemistry is that an abrasive-blasted surface is going to plate or coat better, and have better bonding between the substrate and the coating, be it lead dioxide or MMO.

 

http://www.5bears.com/mmo/ae02.jpg

 

It's little different from an air brush... it simply blows abrasive instead. I filled it up with ALOX:

 

http://www.5bears.com/mmo/ae03.jpg

 

...and tried it out on a scrap of titanium. This titanium was a cutoff of the 0.050" thick shanks that I had made dozens of in the past, and I have a lot of the little buggers. These will be ideal for home MMO and plating tests.

 

http://www.5bears.com/mmo/ae06.jpg

[Swede]

The results - the Paasche air eraser is an extremely fine tool. I wish it had a bit more "oomph" but it will work fine for this task. It's so fine that you can easily write with it, so to cover an area even 1" x 1" takes a bit of time.

 

http://www.5bears.com/mmo/ae07.jpg

 

It can use other media besides ALOX... even corn starch. A good abrasive for moderate use is baking soda. I tried it out, and it works fine, but baking soda isn't ALOX, and I'd not use anything else for plating prep.

 

http://www.5bears.com/mmo/ae08.jpg

 

I've got some Tin (II) chloride inbound, as well as some manganese sulfate, which can be used to electrolytically plate Mn in various forms, as well as one lonely gram of palladium chloride. I've been deep into the patents, and should be set for some interesting experiments soon.

Edited November 17, 2012 by Swede

[taiwanluthiers]

You know I read your blog regarding your frustration with various "good neighbor policies" of chemistry suppliers...

 

You could come to Taiwan, here we have chemical stores, open to the public where anyone can walk in and buy ANY chemical out there (perhaps not U-235 or other more restricted poisons such as Potassium Cyanide), and nobody here has a "good neighbor policy".

[Algenco]

You know I read your blog regarding your frustration with various "good neighbor policies" of chemistry suppliers...

 

You could come to Taiwan, here we have chemical stores, open to the public where anyone can walk in and buy ANY chemical out there (perhaps not U-235 or other more restricted poisons such as Potassium Cyanide), and nobody here has a "good neighbor policy".

 

that would be nice, I can't imagine "one stop shopping" for chems

[WSM]

that would be nice, I can't imagine "one stop shopping" for chems

 

I can, but sadly not nearer than twenty years ago. In these post- 9/11 times it would be amazing to find a one-stop science and chemical supplier.

 

WSM

[Algenco]

I can, but sadly not nearer than twenty years ago. In these post- 9/11 times it would be amazing to find a one-stop science and chemical supplier.

 

WSM

 

I remember when cases of dynamite were stacked at the end of the counter at the hardware store, but that was a long time ago

[taiwanluthiers]

I don't "one stop shop" for chems either, but there's a street block with no less than 10 science/chemistry suppliers where I can just take a trip and get all the chems and glassware I need just by walking around the block. This is probably impossible in America now due to all the meth makers. I shop around because they have wildly varying prices on chemicals. For example one will sell strontium nitrate at 12 dollars a pound but another will sell for more than 20 dollars a pound.

[Algenco]

while it might not be as convenient in the US, I get high quality strontium nitrate for $2lb

[taiwanluthiers]

I'd like to know where you get it as the best prices I can get (by buying it in larger quantities) are 12 dollars per Kg.

[WSM]

I'd like to know where you get it as the best prices I can get (by buying it in larger quantities) are 12 dollars per Kg.

 

Even if you can get it for $2/pound in the US, the shipping to Taiwan would drive the price to well over what you could buy it for locally. Can you buy from China or is that not even an option for you (would politics prevent it)?

 

WSM

 

edit: If China can't be a source, what about Japan?

Edited December 1, 2012 by WSM

[taiwanluthiers]

I can probably buy from China, if I want 100 metric tons (they have listings all over Alibaba.com for anything, but all of them have a minimum order of anywhere from 100 to 1000 metric tons). Same problem with Japan, high shipping cost too. If anyone here knows of a retail Chinese pyro supplier just like Skylighter, I am all ears, but it looks like in Asia they do not like selling raw materials to individuals. I am having the same problem in Taiwan, no one is willing to sell raw materials, just finished products to individuals. There's really no DIY culture here.

 

When I try to buy them from Bangkok pyro the price is still 13 dollars a Kg... just no getting around that. In any case I will be switching over to organic homemade chlorate based color stars.

Edited December 1, 2012 by taiwanluthiers

[Swede]

I found a couple of interesting patents.

 

I started this thread to explore MMO, primarily just for fun, but also for the slight possibility of developing an MMO with a high oxygen overvoltage, favoring oxygen and O3 evolution rather than chlorine. This generally means an anode would be perchlorate capable.

 

We have, for now:

 

1) Pt - expensive, and slowly erodes

2) PbO2 - fragile, toxic

3) Boron doped diamond - makes Pt look cheap

 

That's about it. But there's a 2011 Patent that describes a material that is electrocatalytic for perchlorate. It does require ruthenium, but ruthenium chloride isn't too bad compared to Pt or Iridium; I was quoted $8/gram from a Chinese source, and a little goes a long way when doing MMO.

 

I have downloaded the PDF and posted them to my web site, so the links are directly to a PDF document.

 

First Patent: Bismuth metal oxide pyrochlores as electrode materials for electrolytic ozone and perchlorate generation. Describes the creation of a Bi2Ru2O7, which is the active catalyst. Incorporation onto a substrate is not well described, and the pyrochlore does require a furnace... which I fortunately have.

 

Implication - Bismuth + a Pt group metal as oxides is active, but does it have to be a pyrochlore? Does the simple addition of Bismuth to an MMO formulation make it somewhat active? remember, industry demands high efficiency. We'd be happy with lower efficiency so long as the anode remains reasonably intact. It also makes me wonder about my lead dioxide anode #1 which remains untested... it was formulated with Bi.

 

Most of the Bi salts are NOT soluble in water. They ARE soluble in HCl and other mineral acids. Thermal decomposition of almost any Bi salt results in Bismuth oxide.

 

Second Patent: WSM, this one is for you! Continuous process for the direct conversion of KCl to KClO3 by electrolysis. Describes a unique setup and includes some excellent data. Note that the patent uses KCl rather than sodium, completely in contrast to industry.

 

I'm still studying and gathering data for this attempt at home MMO. I want to replicate the original Henri Beer patents which is what we use now to make chlorates, and then play with the proportions of oxides, looking at Bi (obviously), Mn, Co, others.

Edited December 4, 2012 by Swede

[taiwanluthiers]

So can you confirm if the MMO you buy from Laserred can be used to produce perchlorates? One thing I was thinking of was just buying so called "Platinized Titanium" mesh on ebay and use it for perchlorate production. They're Ti mesh coated in Pt, not sure how long they'll last in a cell. I am not sure about LD just because it looks as though I need to coat the MMO myself and could end up with a toxic mess...

[Swede]

The Laserred MMO will NOT produce perchlorates... it wasn't formulated to do so. The patent above describes the addition of Bismuth to MMO as a pyrochlore, which is a discrete molecule.

 

For now, the best bet to get going quickly is a platinized Pt over Ti anode for perchlorate. Start with chlorate as clean as can be, because Cl- ions are more erosive to Pt than chlorate. Keep the current density down as well.

 

Perchlorate is, IMO, about 10X as hard to make and purify. The latter (purification) is especially important, because unless it's clean, it may as well be chlorate.

 

MMO has spoiled us. I wish there was something as inexpensive and effective for home perchlorate production. But we'll keep plugging away. It's a fascinating process.

[WSM]

The Laserred MMO will NOT produce perchlorates... it wasn't formulated to do so. The patent above describes the addition of Bismuth to MMO as a pyrochlore, which is a discrete molecule.

For now, the best bet to get going quickly is a platinized Pt over Ti anode for perchlorate. Start with chlorate as clean as can be, because Cl- ions are more erosive to Pt than chlorate. Keep the current density down as well.

Perchlorate is, IMO, about 10X as hard to make and purify. The latter (purification) is especially important, because unless it's clean, it may as well be chlorate.

MMO has spoiled us. I wish there was something as inexpensive and effective for home perchlorate production. But we'll keep plugging away. It's a fascinating process.

 

I agree, Swede. The thought of something that can turn chlorate into perchlorate as easily as MMO turns chloride into chlorate is definately attractive, but how? That's the problem we face.

 

If we can get or make a bismuth pyrochlore, is there a process to fix it permanently to a titanium substrate? Could we use standard MMO as a substrate in any way, the way it's used for a lead dioxide foundation?

 

Lots of questions, too few answers,... yet...

 

WSM

Edited December 9, 2012 by WSM

[taiwanluthiers]

But if there is something that works as easily as MMO making chlorate they would have used it in industry. The fact that they're using Platinum for perchlorate production says something.

[pdfbq]

What I would like to know is how they (industry) rewins the platinum. I think I have not red something about it here on Apc.

 

Like getting gold out of cpu's.

 

Say buying for 500 euro Pt anodes, fry them to get 50 kilos of perc and extract the Pt and sel it for say 400 euro.

 

Anybody knows how industry rewins the Pt?

Edited December 9, 2012 by pdfbq

[taiwanluthiers]

So you can only get 10kg of perc out of a single platinum anode? that's not a lot considering the price of the anode.

 

I think the way to get gold out of CPU is you would dissolve the gold from the CPU, then you get them back out with electrochemistry or something. Thing is for getting platinum out of a solution you would need a way of isolating the platinum compound out of the mother liquor, and then you would plate them onto something. I've seen instructions out there on how to get gold out of computer components, but the amount of gold you get wouldn't be worth the trouble.

[Mumbles]

He was just throwing out random numbers for an example. Those are almost certainly not real values.

 

To isolate platinum in during refinement, it's isolated as ammonium hexachloroplatinate. You basically make this by adding ammonium chloride to solutions containing hexachloroplatinic acid (H2PtCl6). I'd bet, this is where the platinum goes after it dissolves in a chlorate cell. Before you get too excited, even as insoluble as this compound is in the presence of excess ammonium chloride, a 20L cell would still hold over half a gram of platinum still in solution.

 

If you really had any chance at ever recovering the platinum, you'd have to concentrate all the cell liquor as much as possible and go at it then. Even then, you'd have to have multiple grams of dissolved platinum to really get much of a meaningful recovery.

[WSM]

But if there is something that works as easily as MMO making chlorate they would have used it in industry. The fact that they're using Platinum for perchlorate production says something.

 

The "Patent" is from 2011 and is actually a patent application and disclosure, and hasn't been awarded yet. This technology is too new to be common industry practice yet. If it proves to be practical, you'll see it more and more as industry adopts it in the future.

 

For our purposes, this patent application discloses an alternative to the standard industry practices, that limit our ability to easily produce experimental quantities of perchlorate. If we can get or make the bismuth pyrochlore and successfully apply it to our anodes, it holds the promise of affordable and easily made perchlorates at home (i.e., a perchlorate MMO)!!!

 

When MMO first came on the scene, it took the chlor-alkali industry about a decade to adopt it. Now it's the industry standard.

 

WSM

[Swede]

Picked up some n-butyl titanate, which thermally decomposes and forms part of the titanium dioxide/ruthenium dioxide (plus Sn) in traditional MMO.

 

The Bi pyrochlore is formed at high temperatures. It may be possible (referencing the 2011 document) to form the pyrochlore in situ in a way similar to the classic MMO process, getting excellent adherance.

 

One of the beauties of the "paint and bake" MMO process is that one can vary the composition over a substrate. For example, one half of the area can be "MMO formula A" and the other half "MMO formula B", and they all form solid solutions in a similar and wide range of temperatures, 350 to 500 degrees. So it may be possible to compare two formulas on the same substrate to see which one lasts longer, and/or get different functionalities from one anode, i.e. electrocatalytic for chlorate and perchlorate.

 

I'm getting close to trying this... we'll see how it goes.

[taiwanluthiers]

I do not have a full chem lab, so there is no way I am going to try and replicate this... even your LD plating is a bit out of reach for me because it requires expensive equipment. So I was wondering if you'd be willing to sell some of those pyrochlore thing if you managed to make them, or at least plated LD anode...

[WSM]

Picked up some n-butyl titanate, which thermally decomposes and forms part of the titanium dioxide/ruthenium dioxide (plus Sn) in traditional MMO.

The Bi pyrochlore is formed at high temperatures. It may be possible (referencing the 2011 document) to form the pyrochlore in situ in a way similar to the classic MMO process, getting excellent adherance.

One of the beauties of the "paint and bake" MMO process is that one can vary the composition over a substrate. For example, one half of the area can be "MMO formula A" and the other half "MMO formula B", and they all form solid solutions in a similar and wide range of temperatures, 350 to 500 degrees. So it may be possible to compare two formulas on the same substrate to see which one lasts longer, and/or get different functionalities from one anode, i.e. electrocatalytic for chlorate and perchlorate.

I'm getting close to trying this... we'll see how it goes.

 

There's been some concern about Swede's and my absence here lately, but don't worry. We're both busy pouring over related Patents and studying processes to make MMO and things that can make perchlorates easier than using either platinum or LD.

 

Both of us are gathering the knowledge and equipment to try these things and will report our progress as we go, but for now we're doing our homework.

 

WSM

[WSM]

I do not have a full chem lab, so there is no way I am going to try and replicate this... even your LD plating is a bit out of reach for me because it requires expensive equipment. So I was wondering if you'd be willing to sell some of those pyrochlore thing if you managed to make them, or at least plated LD anode...

 

At this point we're still in the research phase (and the material and equipment gathering phase), so there's nothing to share...yet. If we're successful, we may just make a run of electrodes for others to try.

 

One step at a time !!!

 

WSM