Sciencemadness Discussion Board - Titanium From TiO2

Titanium From TiO2

Chemistry Alchemist - 6-8-2012 at 20:43

Ive got another Elemental Extraction i want to discuss with you guys.

Titanium Dioxide is reasonably available and not that hard to buy, but it is a really unreactive element, it seems pretty hard to dissolve.

in 2006 a topic was posted to make Titanium Sulfate and a post was made on it saying this:
Titanium dioxide is soluble in molten KHSO4 (this is used for etching TiO2 surface) but i am not sure if this can be used to prepare titanium salts.

What id like to know is if NaHSO4would be able to react with it to produce titanium sulfate and from there be able to react with aluminium to produce the metal... 2 salts would be combined in a crucible and torched at a high heat till molten... and then mixed with water and then add the aluminium... Does all this seem right?

(sorry if it desnt make any sense, only had a few hours sleep)

If all that doesnt work, could reducing the oxide with lithium produce Elemental Titanium?

plante1999 - 7-8-2012 at 00:12

Making a melt of TiO2 with NaHSO4 and extracting with water will make TiOSO4 or titanyl sulphate. you cant reduce to titanium in aqueous solution.

If you have powdered lithium it might work but blogfast have made a classical preparation using potassium chlorate boosted aluminium-titanium dioxide Goldschmidt reaction.

@ChemistryAlchemist: I'm unable to do exactly the introduction you want, If you want I can make a simpler one.

[Edited on 7-8-2012 by plante1999]

[Edited on 7-8-2012 by plante1999]

Chemistry Alchemist - 7-8-2012 at 00:15

So could lithium and titanium dioxide be a possibility?

plante1999 - 7-8-2012 at 00:17

Quote: Originally posted by plante1999

If you have powdered lithium it might work.

[Edited on 7-8-2012 by plante1999]

a_bab - 7-8-2012 at 00:36

An interesting fact: any agricultural soil contains at least 3 kg of Ti / 1T of soil (0.3%).

Actually you can make Ti with a thermite type reaction, starting right from TiO2: http://www.popsci.com/node/30347

MrHomeScientist - 7-8-2012 at 05:25

Not sure about the fusing with KHSO4 method, but I've tried the thermite reaction with (some) success. As mentioned above, this was also following blogfast's procedure. Titanium is really a beautiful metal - very white, shiny, and lightweight.
Mine was a very "sputtery" burn, so I didn't get large pieces of metal unfortunately. I'm thinking that is from additives in my plaster of paris (listed as CaCO3 and SiO2). I'm trying two avenues to fix this: make my own CaSO4 from CaCl2 and H2SO4, and treating the plaster with H2SO4 to convert one of the impurities and hopefully improve burn performance.

Some raw footage of one of my trials with raw plaster can be seen here: http://www.youtube.com/watch?v=KfqKOaZyllQ

a_bab - 7-8-2012 at 06:07

These thermite reactions need large amounts of reactants, otherwise most of the resulted metal is boiled off and vanishes in the fumes and dropplets.
With a large amount (I'd say at least 1 kilo) you'll have your pool of molten metal form easier. Also using the double vessel like in the link helps to contain the metal.

Needless to say, I wouldn't want to be anywhere near the reaction, and I'd do it in a remote place, with no fire hazards around.

blogfast25 - 7-8-2012 at 06:14

Thermiting TiO2 to obtain Ti and then Ti salts really is a bit of overkill but here’s my procedure again for those who want to synth some backyard Ti metal:

http://developing-your-web-presence.blogspot.co.uk/2008/10/o...

BTW: Lithium WILLNOT DO, not even by a long shot. Forget about that: ΔG > 0 ! Also Mg doesn’t really work either.

But for salts, dissolve TiO2 in a molten excess of NaHSO4 or KHSO4. Also boiling conc. H2SO4 does it. You can also increase the BP of H2SO4 by adding NaHSO4 or (NH4)2SO4 to it. In all cases, be prepared to have some patience: calcined TiO2 is very inert and takes time to dissolve in these acids. All this leads to titanyl sulphate (TiOSO4).

Diluting this carefully (while staying acidic) and then adding aluminium foil or sheet reduces Ti (IV) to beautiful deep blue Ti (III).

blogfast25 - 7-8-2012 at 06:18

Quote: Originally posted by a_bab

These thermite reactions need large amounts of reactants, otherwise most of the resulted metal is boiled off and vanishes in the fumes and dropplets.

Total baloney :mad:

: I've run reactions as small as 20 g with yields of 60 % and I can assure you the missing metal hadn't vaporised.

Ti has a BP of just short of 3,300 C, a well designed Ti thermite reaches just about 2,500 C or a little higher.

Careful with spreading misinformation!!

If anything with Ti thermite it's making them run hot enough.

[Edited on 7-8-2012 by blogfast25]

a_bab - 7-8-2012 at 06:27

Very nice writeup blogfast!

BTW, the boosting can be done with some iron oxide; in this case ferrotitanium alloy is obtained, up to 70%Ti (it's in fact an industrial procedure, besides melting iron and titanium together)

blogfast25 - 7-8-2012 at 06:35

Yes, ferrotitanium is industrially produced that way, as are ferrochromium, ferrovanadium and ferroniobium.

But ferrotitanium is still quite resistant to dissolution and of course you only obtain a mix of Fe and Ti salt, which is difficult to separate, if Ti salts are the purpose.

hyfalcon - 7-8-2012 at 17:53

blogfast25, where are you sourcing your titanium dioxide and fluorspar?

I'm getting ready to purify some calcium ammonium nitrate double sale fertilizer. One of the byproducts will be calcium sulphate. I just can't figure out where to get some fluorspar, other than taking a hammer to some of my mineral specimens.

[Edited on 8-8-2012 by hyfalcon]

blogfast25 - 8-8-2012 at 05:25

Quote: Originally posted by hyfalcon

blogfast25, where are you sourcing your titanium dioxide and fluorspar? And eBay...

I'm getting ready to purify some calcium ammonium nitrate double sale fertilizer. One of the byproducts will be calcium sulphate. I just can't figure out where to get some fluorspar, other than taking a hammer to some of my mineral specimens.

[Edited on 8-8-2012 by hyfalcon]

TiO2: I sell it myself! Pottery shops often do too.

CaF2 is trickier: I've been trying to source that w/o much success. But I have a small stockpile of 'offcuts' bought from a mineral shop and grind these down as and when I need it.

[Edited on 8-8-2012 by blogfast25]

hyfalcon - 9-8-2012 at 16:18

Fluorspar ceramic grade http://www.standardceramic.com/Materials.html#FF . Will this work? Also, have you ever tried a cobalt oxide thermite?

If the target was a ferro titanium alloy then could this be used?
Ilmenite Powder (200 mesh) FeO•TiO2

[Edited on 10-8-2012 by hyfalcon]

Waffles SS - 9-8-2012 at 21:33

Interesting!!
I like to try this method but as you wrote below website info:
http://developing-your-web-presence.blogspot.de/2008/10/on-t...

Its better to use KClO3 + aluminium (as booster) than calcium sulfate + aluminium.It seems Titanium purity is better by this booster.But i dont know how we can purify more final Titanium(it seems it turn to black when contact with air).I want to make it shiny.What is best ratio for booster?(KClO3 + Al)

I have access to Hydroflouric acid here(its just 2$/litre here) and i can make CaF2, also i can easily buy anatase Titan.I will share my result here.(i will do this reaction on Earthenware pots).
blogfast25 , do you have suggestion for me?

[Edited on 10-8-2012 by Waffles SS]

hyfalcon - 10-8-2012 at 04:25

I just mixed up a batch of thermite.
To 7.5lbs. of thermite, I added another .5lb of a 50/50 mix of 5u aluminum and home made potassium chlorate/perchlorate. The c/p mix wasn't reduced to fine material. I just added it in the crystalline form. We'll see later today how it goes.

[Edited on 10-8-2012 by hyfalcon]

[Edited on 10-8-2012 by hyfalcon]

blogfast25 - 10-8-2012 at 05:47

Quote: Originally posted by hyfalcon

Fluorspar ceramic grade http://www.standardceramic.com/Materials.html#FF . Will this work? Also, have you ever tried a cobalt oxide thermite?

If the target was a ferro titanium alloy then could this be used?
Ilmenite Powder (200 mesh) FeO•TiO2

[Edited on 10-8-2012 by hyfalcon]

Yes, cobalt is easy. Nice regulus. No booster but you do need CaF2 as a flux...

Yes, that Fluorspar would work perfectly.

Yes, Ilmenite should work: it’s used industrially to produce FeTi. But it may need a little boosting…

Quote: Originally posted by Waffles SS

Interesting!!
I like to try this method but as you wrote below website info:
http://developing-your-web-presence.blogspot.de/2008/10/on-t...

Its better to use KClO3 + aluminium (as booster) than calcium sulfate + aluminium.It seems Titanium purity is better by this booster.But i dont know how we can purify more final Titanium(it seems it turn to black when contact with air).I want to make it shiny.What is best ratio for booster?(KClO3 + Al)

I have access to Hydroflouric acid here(its just 2$/litre here) and i can make CaF2, also i can easily buy anatase Titan.I will share my result here.(i will do this reaction on Earthenware pots).
blogfast25 , do you have suggestion for me?

[Edited on 10-8-2012 by Waffles SS]

The metal IS shiny: just after production the skin’s a little dark, that’s all…

Yes, read this: http://developing-your-web-presence.blogspot.co.uk/2008/03/t...

Quote: Originally posted by hyfalcon

I just mixed up a batch of thermite.
To 7.5lbs. of thermite, I added another .5lb of a 50/50 mix of 5u aluminum and home made potassium chlorate/perchlorate. The c/p mix wasn't reduced to fine material. I just added it in the crystalline form. We'll see later today how it goes.

[Edited on 10-8-2012 by hyfalcon]

[Edited on 10-8-2012 by hyfalcon]

It never ceases to amaze me how some are willing to try something for the first time in such huge quantities! What’s wrong with a starter of 200 g or so, eh?

Finer c/p would be better I feel. But the size of the batch may be very forgiving of that… I'm very interested in your results. Do you have the overall formulation?

[Edited on 10-8-2012 by blogfast25]

[Edited on 10-8-2012 by blogfast25]

hyfalcon - 10-8-2012 at 14:55

I was going for an ingot of smelted metal to take in to my foundry buddy and see what he says about it. I managed an ingot about the size of a yard dart.

I save all the iron out of my thermite reactions. This is the largest so far. I added all the iron that I've collected and put it in the bottom of a clay pot with the drain hole sealed with some aluminum tape. I was only able to get 5lbs. in the pot for this firing. I use a 3:1 iron oxide/5u aluminum thermite mix. With the extra .5lb p/c aluminum mix the reaction seamed to run much faster and hotter with better separation of slag from metal. I should have preheated the slapdash mold I threw together to catch the molten metal in. Half the pour stayed in the bottom of the pot, but a pretty good amount made it in to the mold. Seems I could have used half again as much booster on top of what I did use to get a good fluid pour. Only another batch could tell and I'll need some more iron oxide before I can do that again.

I've done the regular thermite reaction in these quantities before the only difference is the .5lb booster.

Only thing left of the clay pot was the bottom. I was wondering where all the slag came from and now I believe the reaction melted the terracotta pots I was using. I've got to fire a real mold for doing this reaction. This ingot is uuugggllyy.

[Edited on 11-8-2012 by hyfalcon]

[Edited on 11-8-2012 by hyfalcon]

[Edited on 11-8-2012 by hyfalcon]

blogfast25 - 11-8-2012 at 05:30

Quote: Originally posted by hyfalcon

I was going for an ingot of smelted metal to take in to my foundry buddy and see what he says about it. I managed an ingot about the size of a yard dart.

I see: Classic (ferric) Thermite, eh? Booster will indeed improve yield.

Other ways of improving yield are:

• Pre-heating reactor.
• Use a slag fluidiser. CaF2 is a proven one but CaO (quicklime) should also have some effect because it forms low meting calcium aluminates with alumina: http://en.wikipedia.org/wiki/File:CaAluminatesPhaseDiagram.J... , in particular 12CaO.7Al2O3 has an MP of only 1415 C. But adding 1 mol CaO for every 6 mol Al2O3 anticipated would already decrease the MP of the melt to about 1800 C, thus allowing more time for the iron (or any metal) to coalesce.

The (molar) formulation would then be:

Fe2O3 ………………….. 1
Al …………………………. 2
CaO ………………………. 1/6

I’ve never tried quicklime as a slag fluidiser but it’s well worth trying, IMHO. And of course you could still boost too:

The general formulation for x mol KClO3 booster would be:

Fe2O3 ………………….. 1
Al …………………………. 2 + 2x
KClO3 ……………………. x
CaO ………………………. 1/6 (1 + x)

[Edited on 11-8-2012 by blogfast25]

HugeToughGuy - 5-2-2014 at 09:14

Hey guys, this thread is old so hopefully someone can reply to this with some useful info.

How would one go about using a thermite reaction to obtain a completely pure product? So basically, by using the whole TiO2 with drywall and the like reaction, will I be getting somewhat pure Titanium metal pouring from my vessel, or will it be a dirty metal full of slag? And naturally if I'm using a mold, do I need to allow a lot of headspace for slag produced as the metal settles at the bottom?

I'm also looking to make a titanium alloy, so if I alloy other metals in with the TiO2, will I need to still go the full fluorspar route and the like, or would that be reduced or even eliminated? Also, there is the concept of thermate, which is a super hot burning form of thermite where sulfur and other chemicals are added to increase burning temps - keeping this in mind, would it be smarter to use a sulfate of titanium instead of an oxide? I would appreciate any suggestions or info anyone can offer on these points, thank you.

I have some rather "ambitious" castings in mind with titanium such as engine part replacements and the like, but I have to know it will function and work as a castable metal or alloy that I can rely upon to not fail on me or be a waste of time, lol. I'm sure you know what I mean! Thanks in advance.

blogfast25 - 5-2-2014 at 09:53

@HTG:

Metal obtained from thermite reactions almost always contains small amounts of slag and requires 'deslagging' if the pure metal is what you need. Ti is no different. BTW, Kroll process Ti also requires deslagging. Thermite Ti also contains small amounts of alloyed Al, I'm not sure this can be avoided.

Casting thermite Ti directly into a mould is possible and is called 'drop casting' but it's rarely used for artefacts because that metal hasn't been deslagged. The crucible would contain a hole, blocked off by thin Ti foil. On reaction this melts and the contents of the crucible flows into the mould (below the crucible).

Alloys of Ti would be created by replacing parts of the TiO2 with the relevant metal oxide(s) in the desired molar ratios, adjusting also the Al content of the mix. I've made several alloys like that, like ferrotitanium.

There is no 'sulphate of titanium', only titanyl sulphate (TiOSO4) and I think you can't buy it as an anhydrous solid.

Thermite Ti has also one BIG disadvantage compared to Kroll Ti: the former is brittle, not malleable like the latter. That limits the applications of thermite Ti enormously.

Don't take this the wrong way but I think you're trying to punch above your weight.

[Edited on 5-2-2014 by blogfast25]

[Edited on 5-2-2014 by blogfast25]

Fantasma4500 - 8-2-2014 at 04:13

about booster.. what about Ba(NO3)2 as used in thermate?

blogfast25 - 8-2-2014 at 06:31

Barium nitrate would work but no better than its mol equivalent in, say, KNO3. 2 moles of KNO3 would be equivalent to 1 mole Ba(NO3)2.

[Edited on 8-2-2014 by blogfast25]