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Rosco Bodine
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Bismuth and tin are both used as lead substitute fishing sinkers , you can get 'em at WalMart .
| Quote: | Originally posted by chloric1
That international patent you posted was pretty blatant on stating the significance of bismuth doped tin oxide coating. In fact line #9 and #13 had
the same word for word statement that the preferred undercoating is tin oxide doped with bismuth oxide. It was odd like it was jumping off my
computer screen. |
Yeah that patent was almost like somebody at Diamond Shamrock got overexcited , ran to the patent office with the rough draft instead of going to the
usual company law firm , and just spilled the beans.... before the technical mystery writers could work their special editing magic on it to make it
more cryptic so the technology couldn't be easily understood or copied . I read this patent and thought it may be a nugget having dislodged and
tumbled downstream from the usual mystery mountains .
The paragraph I found to be interesting was line 33 page 2 :
| Quote: | | In one preferred embodiment of the invention , the electrode coating consists essentially of the SnO2-Bi2O3 solid solution applied in one or more
layers on a valve metal substrate. This type of coating is useful in particular for the electrolytic production of chlorates and perchlorates, but for
other applications the coating may desirably be modified by the addition of a small quantity of one or more specific electrocatalytic agents .
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The very next paragraph section (d) covers the case of the MnO2 coated anode , in my opinion reading down through line 29 of page 3 . This then
skips to page 11 where the
first and last paragraphs of page 11 are pertinent .
Sooooo...
I'm looking over a four leaf clover that I overlooked before ...
Now everybody sing
Sing louder dann2 ! ....I can't hear you 
[Edited on 14-1-2008 by Rosco Bodine]
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dann2
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ZZZZZZZZZZZZZZZZZZZZZzzzzzzzzzzzzzzzzzzzzZZZZZZZZzz
BUMP
Did someone mention my name?
oh Hello,
A yea, the old SnO2/Bi2O3 chestnut.
RongPeng mentioned it back about 40 posts ago.
It may be the way forward no doubt.
I'm still stuck with the Alembic anode and intend to stay stuck on it untill I have a reproducable HOLY GRAIL anode.
A lost cause or total glory? we'll have to wait and see.
Will have to leave the SnO2/Bi2O3 to someone more skilled in the art etc etc.
Dann2
and anyways I can't sing, krokes only.
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JohnWW
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| Quote: | Originally posted by Rosco Bodine
Bismuth and tin are both used as lead substitute fishing sinkers , you can get 'em at WalMart . |
At the prices they are asking, compared to the price of fish, you might as well use good old Fe, although to obtain the same weights the sinkers have
to be about 45% larger in volume than Pb sinkers. Besides, Bi is too rare and valuable a metal to be used for sinkers or shot, and it is only about
25% denser than Fe anyway.
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Rosco Bodine
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@dann2
Heck listening to you , now I have a Kilo of reagent grade Sb2O3 , when I should've ordered Bi(NO3)2
Oh well , maybe it will be useful for something ....for sure for sunshading float glass , even if it isn't much good for perchlorates  The jar of Sb2O3 I can always use for a paper weight . I said I had a suspicion
about the Bi ...
of course I would be more comfortable with the whole thing if it wasn't in a shamcrock patent Could be
they are both wrong .....in which case I may become an international fugitive as opposed to an international hazard
BTW ..
Rong Peng has been challenged by Rite Pong to a friendly game of back and forth .....Rite ??? - Rong !!!
Peng ??? - Pong !!! This will be known as the
Rite-Rong Peng-Pong Tournament
[Edited on 14-1-2008 by Rosco Bodine]
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tentacles
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Guys, I'm not sure if the Bi sinkers are availible here in Canada. I know you can get a lb of 99.99% on ebay for $17 - plus about $20 shipping, and
then customs will take their cut - minimum $7. There's also the fact that a lot of ebay sellers won't ship from USA to Canada, etc etc. It's not
like I need a lot of it (I'll probably eat those words!). I WILL check walmart later tonight. Are they actually labeled as being Bi or Sn, or do I
have to try and guess?
[Edited on 14-1-2008 by tentacles]
Also, an update on ugly betty: I wasn't getting good conductivity with the anode, so I sanded off the coatings - a much more difficult proposition
than I had expected. The new coating - I'm up to 4 coats of MnO2 after 5 coats of Co - looks MUCH better. I added more ethanol to the solution and the
coatings are sticking better. Conductivity is much better (as compared by reading with an ohm meter). I'm getting readings as low as .5k ohm vs
megaohms with the original try.
On another note: after sanding most of the coating off, a dip in hot HCl removed the rest of the CoO/MnO2 as well as providing a fresh etch.
[Edited on 14-1-2008 by tentacles]
Checked Walmart, picked up some non-lead sinkers, they appear to be tin. I may try and hit a sporting goods store tommorow for the eagle claw brand
sinkers.
Also, I tested out Less Ugly Betty after 6 coats of MnO2 - got the same low readings despite a much nicer coating. Turns out my PSU had burned up a
couple caps (so THAT was the burning smell!). I stole some Rubycons out of my old PSX and it's cranking out power again. With one cathode (so only
current from one side of the anode) it was drawing about 1.7A at 5V. That's about 110mA/cm2. Got a dash of pink permanganate coloring, same as Xenoid,
but I prepared for that and am testing it in a throwaway NaCl beaker. If I can find Bi tommorow I will try a couple coats doped with Bi. If not, I
will make up a splash of Pb doped MnO2.
I've filtered my gouging rod cell and now have 4L of urine water that I'll be boiling down tommorow. It was supposed to run another 3 or so days but
the gouging rods "ran out" so I tossed the stubs and decided to collect the chlorate and reuse the liquor with Ugly Betty.
[Edited on 14-1-2008 by tentacles]
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The_Davster
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Go to a gun store that caters to those that reload their own ammunition. Can buy bismuth shot, nontoxic for waterfowl or something. I have never seen
bismuth elsewhere in Canada.
EDIT: Mind you, I have never extensively looked through walmart.
[Edited on 14-1-2008 by The_Davster]
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Rosco Bodine
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Edit : Not Eagle Claw but Gremlin Green
The Bi or Sn fishing weights will definitely be labeled and the price will tell you something too . The brand name on the Bi egg sinkers is Gremlin
Green , the split shot are Tin .
Water Gremlin is the tackle manufacturer name , but they also make lead weights so check the label for Gremlin Green
which is their environmentally friendly lead-free product line .
The big outdoor outfitters and tackle vendors probably have these too . Also some lead free solders are Bi-Sn alloys .
For a pound ingot of Bi or other metals
http://www.rotometals.com/_c_36.html?gclid=CKal3-2gr5ACFRAgQ...
IIRC the Bi shot for waterfowl is alloyed with Cd or something else , it isn't pure . But maybe easy enough
to use anyway if you could buy a few Bi duck shells and just
cut 'em open for a few ounces of shot , rather than having to buy a huge bag of shot .
On second thought a box of 10 Bi shotshells is more expensive than a pound ingot of Bi .
http://www.cheaperthandirt.com/21013-51145-2362.html
A box of 5 Bi shotshells is less and about the minimum
for this source of Bi .
http://www.cheaperthandirt.com/21031-16528-2445.html
Cabellas has some of the Bi fishing sinkers
http://www.cabelas.com/cabelas/en/templates/links/link.jsp?c...
Both pure Tin split shot and Bismuth sinkers are sold
under the Gremlin Green product line name of Water Gremlin
as the manufacturer name . Gremlin Green should bring up plenty of search hits .
http://cgi.ebay.com/WATER-GREMLIN-Non-Lead-Egg-Sinkers-1-2-O...
[Edited on 15-1-2008 by Rosco Bodine]
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tentacles
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I procured some Bi today - tried dissolving in ~30% nitric... It doesn't seem to work very well. CRS says that Bismuth Nitrate pentahydrate is
reactive with water. JTBaker's MSDS says "Solubility: Slowly decomposes in water to form subnitrate." So I have a pile of subnitrate in the bottom of
my beaker, it would seem, as the subnitrate is listed as being insoluble in water (and unfortunately, EtOH). I will try and dissolve a small piece in
my 80% nitric.
I tried dissolving a small piece of Bi in my 80% nitric - at room temperature, there is no visible erosion, but the Bi does turn dark/black. I also
tried a Cu(NO3)2 displacement - with success, in acetone. Bi(NO3)2 is listed as soluble in acetone (who knows to what degree!). I have a slow
precipitate of clear/white crystals and the copper is confining itself (mostly) to simply replacing the bismuth metal.
I suppose the next question is - is Mn(NO3)2 soluble in acetone?
I am trying a solution using the white precipitate (subnitrate?) from my first attempt at dissolving the Bi - it's up to 4 coats. Making a total of
5/6/4 on Less Ugly Betty (but getting uglier all the time!)
[Edited on 15-1-2008 by tentacles]
Apparently the subnitrate is soluble in nitric acid, forming the nitrate. I don't really fancy drying out a high strength nitric acid solution to get
crystallized nitrate. I attempted this and it does seem to be the case. I can't find any information on the decomposition temperature of the
subnitrate. edit: The subnitrate decomposes at 260C, so it should be suitable for our uses - it may be possible to simply use it in suspension. It is
soluble in "mild HNO3 and HCl solutions" so it may just need a splash of the good stuff in the plating solution.
ref: http://www.sciencelab.com/xMSDS-Bismuth_subnitrate-9927341
[Edited on 15-1-2008 by tentacles]
[Edited on 15-1-2008 by tentacles]
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chloric1
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Oh yes. Last time I dissolved bismuth in nitric acid was 2003. IIRC I used nitric acid full strength and applied some heat. The subnitrate is
soluble in HNO3 and it is available from pottery suppliers. The property of bismuth nitrate hydrolysis should be of no major concern. Manganese
nitrate needs a slight excess HNO3 to ensure stability so manganese and bismuth in the right ratios should go together hand in hand. Suspensions of
subnitrate may not give even distribution unless some serious stirring and super fine particles of subnitrate are used.
Fellow molecular manipulator
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tentacles
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By full strength you mean 68%?
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Xenoid
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I did not forsee any problems with bismuth dissolving in nitric acid!
My Mellors states; "... is readily attacked by dilute and concentrated nitric acid, forming the corresponding salts."
"Bismuth nitrate can be made by the action of nitric acid on the metal itself, or on the trioxide or carbonate. It is a colourless, crystalline,
deliquescent substance, soluble in water. With a large excess of water it forms bismuth subnitrate."
Bi(NO3)3 + H2O ---> BiO.NO3 + 2HNO3
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tentacles
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It's probable, then, that I should have used an excess of HNO3 rather than an excess of Bi!
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Rosco Bodine
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Bismuth nitrate should be straightforward , using five times the weight of granulated Bi as d 1.2 HNO3 to dissolve .
Attachment: Bismuth Nitrate.pdf (125kB)
This file has been downloaded 959 times
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Rosco Bodine
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Here's some more concerning Bi nitrate and subnitrate ,
as well as Bi(OH)3 Milk of Bismuth from an old pharmacy text .
BTW I have a half kilo of Bi in transit .
Attachment: Bismuth Nitrate Bismuth Hydroxide related.pdf (206kB)
This file has been downloaded 1904 times
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Xenoid
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| Quote: | Originally posted by Rosco Bodine
BTW I have a half kilo of Bi in transit . |
Half a kilo, half a kilo..... I laugh at your half kilo! I have ONE kilo in transit ....
Aaaand one kilo of antimony, aaaand one kilo of tin.
They were the minimum amounts I could purchase, actually the antimony was dirt cheap only NZ$14 a kilo. The bismuth was NZ$40 a kilo, luckily I have
other uses for these metals, and should be able to offload the excess online at prices high enough to cover my costs.
I guess the antimony was so cheap because the bottom has fallen out of the tin oxide doping market ...
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JohnWW
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Let me know when it arrives, Xenoid, - I might want some. I am thinking of experimenting with alloys of Bi, for example, as in types of solder which
do not contain Pb. However, Sb is comparable with As in toxicity.
BTW Other uses for Bi are:
(a) Oxidized to the +5 oxidation state, which is done electrolytically, results in, among other things, sodium bismuthate, NaBiO3. It is an extremely
powerful oxidant, and is used in the colorimetric method of analysis for Mn in water by oxidation to MnO4- and spectrophotometric measurement of
that; although because it also oxidizes Fe(III) to FeO4--, which has a very similar color, Fe interferes with the analysis.
(b) The Russians use Bi-209, the only stable isotope, to make, via Bi-210 by irradiation with neutrons and beta-emission, Po-210, an intense
alpha-emitter with a half-life of 183 days. They use it for murdering defected KGB agents, by slipping it into their food or drink.
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Xenoid
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Yeah, bismuth is kind of interesting, I've never had any before. What I'm interested in, is it's strong diamagnetism (repelled by magnets). I have a
bunch of RE magnets so the effect will be very noticeable.
It also forms various sub-100 oC. melting point alloys, Newton's (94.5), Rose's (93.75) and of course Wood's (60.5).
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chloric1
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Let us not forget about Bismuth's legendary crystallizing behavoir and the irridescent interference type oxide coating. "OOOO look at all the pretty
colors!"
One thing I remember from my bismuth nitrate endeavor was that the solid pentahydrate began decomposition REAL easy on heating. IIRC it starts NOx
evolution at 30°! So a slight HNO3 excess is highly recommended especially if
you leave the solution to dry and you need to redissolve it to add to other oxide precursors.
@Xenoid-The antimony should be of some use for making alloys or as a fuel with some of the perchlorate you'll soon be making. I believe it is brittle enough that you could grind it pretty fine or maybe freeze
in dry ice/acetone mix and grind. I would think it could be part of some blue flame compositions.
[Edited on 1/16/2008 by chloric1]
Fellow molecular manipulator
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Rosco Bodine
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Bismuth Subnitrate ,
Bi(NO3)(OH)2 ,
is stable in contact with H2O plus HNO3 at a concentration of one-half molar . At lower acidity hydrolysis to the hydroxide Bi(OH)3 occurs .
[Edited on 16-1-2008 by Rosco Bodine]
Attachment: Bismuth Subnitrate.pdf (60kB)
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Rosco Bodine
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Bismuth Nitrate , Bi(NO3)3
Preventing first stage hydrolysis of Bi(NO3)3 requires the presence of 9 molar HNO3 .
Attachment: Bismuth Nitrate Hydrolysis Reactions.pdf (118kB)
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Xenoid
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@ tentacles (or anybody else)
We seem to be following the same lines of reasoning. I am also going to try plating some LDO over a Co3O4 and/or MnO2 coated Ti rod.
I have a small quantity of Pb nitrate made using nitric acid, and some Pb acetate made from the Pb/Cu vinegar process. I would like to make larger
quantities using your Pb/Cu nitrate process. I made a bulk amount of Cu nitrate (no problems, I am familiar with this technique).
The problems started when I put the Pb in the Cu nitrate. I've tried 3 times now with all sorts of strange reactions going on!
My last try was with about 400 mls of Cu nitrate. I hung 4 large strips of brushed Pb sheet over the edge of the glass container. Immediately Cu
plated out, there were a few bubbles and some insoluble Pb compound ppt. out (may be Pb sulphate from residual Ca sulphate in the solution). Cu and
other "crud" fell to the bottom. More bubbles, smell of nitrogen oxides (nitric acid). Left it for a few hours when I returned, Pb strips all
encrusted with white "stuff", solution was greenish. Filtered the whole lot, solution now blue! Solution pH=4.2 Hung cleaned up Pb strips from side of
container, immediately coated in choco-brown (?PbO2). Brushed Pb strips again, shiny Pb underneath, hung in container again, immediately coated again,
repeated a couple of times more and gave up! Solution had turned greenish again.
I heated some of the ?PbO2, on a SS strip, it swelled up and then melted, the melted product (when powdered) was yellowish brown ?PbO (massicot).
What the hell is going on here! Why am I getting nitric acid forming! Why is PbO2 plating out! Why doesn't it work.... 
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JohnWW
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I wonder why, though, nature intended that Bi-209, having as it does one proton outside the "doubly-magic" filled shells of 82 protons and 126
neutrons in Pb-208, the most common Pb isotope of its stable four, should be the heaviest known completely stable isotope (not counting the very long
lived Th-232 and U-238, which owe their half-lives to a filled sub-shells effect). However, it has been suspected that Bi may decay with a half-life
of about 10^17 years, many times longer than the universe is old. This is in spite of the fact that even-numbered elements usually have more, and
more stable, isotopes, due to spin-pairing of protons, making it surprising that something like Po-210 or Po-212 should not be the heaviest stable
isotope. But then, if it were stable, for what could Po be used chemically or metallurgically that Te or Bi could not be used?
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chloric1
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Xenoid-I am not sure what is going on here. I know that lead is only a couple levels up from copper on the electromotive force scale so I am not sure
if this is even efficient way to make lead nitrate. If you can sacrifice some 35% nitric acid then I would heat this and put your lead strips into
this. Tne nitric readily digest this and lead nitrate,being low solubility in HNO3, will settle as very fine glistening crystaline granuals. THe
process needs to be as sulfate free as possible. By the way lead sulfate is soluble in strong alkali if that helps in cleaning.
Fellow molecular manipulator
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Xenoid
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@ chloric1
Yeah, I know about making it with nitric, it's just that I didn't want to sacrifice my valuable, limited supply. I have heaps of cheap Ca nitrate and
Cu sulphate is readily available.
Tentacles claims this procedure works well!
Possible variations from his procedure are;
1) It's summer here in NZ, so solution temperature may be 5 - 10 oC. warmer
2) I used molar quantities for the Ca nitrate / Cu sulphate reaction and ended up with somewhat less than a mole of Cu nitrate in about 400 mls. So Cu
nitrate solution was roughly 2 Molar, this may have been stronger than tentacles used.
It's as though some sort of nitric acid producing electrochemical cell is operating at first and then PbO2 forms on the Pb plates (but not where there
is still some plated Cu adhering). I'll have to experiment further with this, I really want it to work!
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jpsmith123
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Patent #6777477
A while ago Rosco uploaded patent #6777477.
http://www.sciencemadness.org/talk/viewthread.php?tid=8592&a...
Supposedly bismuth can be used in this process as well as antimony.
Has anyone tried anything with this?
I'm curious about the chemistry of what's going on here. Anyone know what would be the precipitates described in Example 1 that apparently
subsequently dissolve in the ammonia solution?
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