Sciencemadness Discussion Board

Anyone interested in buying some zirconium?

IndependentBoffin - 19-4-2011 at 12:37

Through my work as an independent defence contractor I buy and use lots of high purity zirconium. The metal is extremely reactive and can burn in water, nitrogen, carbon dioxide, etc. Sources vary but the heat of combustion of the metal is around 10kJ/g.

Some example prices:
Zirconium rod, 99.5% pure, 50mm diameter. USD160/kg excl. shipping
Zirconium powder, 100 - 150 microns, 99% pure, USD320/kg excl. shipping
Zirconium machine swarf. USD100/kg excl. shipping.

Other forms can be supplied upon request.

I can also sell zirconium missile components which I hold patents on, subject to British export licenses. Production capacity is in the region of thousands of parts a year.

Bot0nist - 19-4-2011 at 12:39

Interesting.

Should this go in reagent and apparatus acquisition?

IndependentBoffin - 19-4-2011 at 12:43

Quote: Originally posted by Bot0nist  
Interesting.

Should this go in reagent and apparatus acquisition?


Hmm I am new to this forum but I don't think zirconium classes as a "common chemical" ;) but I defer to the more experienced regulars here.

Also it is the buyer's responsibility to check that they don't need additional permits to import the stuff.

FWIW the stuff is pretty quiescent unless it is in forms of high specific surface area, see "Review of zirconium-zircaloy pyrophoricity." Great bedtime reading :D
http://www.osti.gov/bridge/servlets/purl/5791423-14Pgn9/

[Edited on 19-4-2011 by IndependentBoffin]

The WiZard is In - 19-4-2011 at 13:37

Quote: Originally posted by IndependentBoffin  

Also it is the buyer's responsibility to check that they don't need
additional permits to import the stuff.


You cannot export it from the US of A without a permit.

Think cluster bombs.

IndependentBoffin - 19-4-2011 at 13:44

Quote: Originally posted by The WiZard is In  
Quote: Originally posted by IndependentBoffin  

Also it is the buyer's responsibility to check that they don't need
additional permits to import the stuff.


You cannot export it from the US of A without a permit.

Think cluster bombs.


I am based in the UK. Restrictions will certainly apply to the finished forms ready for incorporation into missiles, i.e. British export licenses.

My finished zirconium products are not used in cluster bombs, although in theory they can be.

Whether restrictions apply to the raw material probably depend on the country the buyer is in, and who they are.

The WiZard is In - 19-4-2011 at 13:56

Quote: Originally posted by IndependentBoffin  

FWIW the stuff is pretty quiescent unless it is in forms of high specific surface area, see "Review of zirconium-zircaloy pyrophoricity." Great bedtime reading :D
http://www.osti.gov/bridge/servlets/purl/5791423-14Pgn9/

See also —

DOE-HDBK-1081-94
DOE HANDBOOK PRIMER ON SPONTANEOUS HEATING AND PYROPHORICITY.

The Primer on Spontaneous Heating and Pyrophoricity is approved
for use by all DOE Components. It was developed to help DOE
facility contractors prevent fires caused by spontaneous
combustion. Spontaneously combustible materials include those
that ignite because of a slow buildup of heat (spontaneous
heating) and those that ignite instantly in air (pyrophoricity). The
scientific principles of combustion and how they affect materials
known to be spontaneously combustible are explained. The fire
hazards of specific spontaneously heating and pyrophoric materials
are discussed as well as techniques to prevent their ignition.
Suitable fire extinguishing agents are included for most materials
as well as safety precautions for storage and handling.

http://www.everyspec.com/DOE/DOE-HDBK/DOE-HDBK-1081-94_3259/

And other URL's.

quicksilver - 20-4-2011 at 06:48

I'm going to move this thread to "Reagents & Apparatus Acquisition" : as it's more appropriate at that section.....

However there IS a source for Zirconium that you may find available; especially if you have a photography oriented store near-by.....Flashbulbs. Certain brands have Zirconium wool and do still exist if you know where to look.



flash-zirconium.jpg - 56kB

[Edited on 20-4-2011 by quicksilver]

Fleaker - 20-4-2011 at 08:40

These prices are much lower than that available from Alfa, Goodfellow, and Advent RM.

Unfortunately, the powder is pyrophoric and would be difficult to import/export, and that's about the limit of its restrictions.

The bulk metal is really tame, nothing much etches it except HF. You have any other valve metals, preferably in crystal rod form?

How much Hf is in these?

IndependentBoffin - 20-4-2011 at 12:59

Quote: Originally posted by quicksilver  
I'm going to move this thread to "Reagents & Apparatus Acquisition" : as it's more appropriate at that section.....

However there IS a source for Zirconium that you may find available; especially if you have a photography oriented store near-by.....Flashbulbs. Certain brands have Zirconium wool and do still exist if you know where to look.



OK no problem quicksilver.

Getting zirconium from flashbulbs would be a very time consuming and expensive exercise ;)

IndependentBoffin - 20-4-2011 at 13:17

Quote: Originally posted by Fleaker  
These prices are much lower than that available from Alfa, Goodfellow, and Advent RM.


I was going to charge even more but decided that this forum is probably not flush with rich corporates but scientists, engineers, technicians, etc. like yours truly who just enjoy the work we do. So I am giving you all a discount :D

Yes I know how much those guys cost, and also Allegheny Technologies metals. I scoped them out when I was sourcing for the metal for my work ;)

Quote:

Unfortunately, the powder is pyrophoric and would be difficult to import/export, and that's about the limit of its restrictions.


Haven't had much problems importing it. It comes in tubs with distilled water over it. Please keep under 60 Celcius :)

Quote:

The bulk metal is really tame, nothing much etches it except HF. You have any other valve metals, preferably in crystal rod form?


I can also supply Ni, Ti, Mo, Ta, Co and Nb. However I do not routinely use these materials in my company's products so a minimum order size and some waiting time would apply.

Some other example prices of high purity (usually >99%) materials:
Titanium sheet, 2mm thick: USD$35/kg
Niobium sheet, 2mm thick: USD$390/kg
Cobalt sheet, 2mm thick: USD$539/kg
Nickel sheet, 2mm thick: USD$87/kg
Zirconium sheet, 2mm thick: USD$302/kg

Rod forms are usually cheaper per kg, e.g.
Titanium rod, OD 150mm: USD$41/kg
Molybdenum rod, OD 150mm: USD$100/kg
Tantalum rod, OD 150mm: USD$1034/kg
Cobalt rod, OD 150mm: USD$302/kg
Nickel rod, OD 150mm: USD$62/kg
Zirconium rod, OD 150mm: USD$140/kg (bigger OD rod is slightly cheaper than smaller OD)
Niobium rod, OD 150mm: USD$345/kg

Quote:
How much Hf is in these?


In the rods and powder, under 1%. It is the most significant impurity.

Polverone - 20-4-2011 at 14:07

Courtesy of IndependentBoffin:

The Combustion of Titanium and Zirconium

This is intended as supplementary information for prospective buyers of zirconium and the merely curious.

Arthur Dent - 20-4-2011 at 15:46

Quote: Originally posted by quicksilver  
Certain brands have Zirconium wool and do still exist if you know where to look.


:o

I have a crapload of those antique flashbulbs!!! Now I don't know if these are Magnesium wool or Zirconium... The ones I got have a General Electric red logo on top of the bulb.

Robert

IndependentBoffin - 20-4-2011 at 16:04

Quote: Originally posted by Arthur Dent  
Quote: Originally posted by quicksilver  
Certain brands have Zirconium wool and do still exist if you know where to look.


:o

I have a crapload of those antique flashbulbs!!! Now I don't know if these are Magnesium wool or Zirconium... The ones I got have a General Electric red logo on top of the bulb.

Robert


I think they are most likely magnesium or aluminium based thermites.

http://en.wikipedia.org/wiki/Flash_powder

Although highly electropositive, the reaction rate of zirconium is not as fast as one might think it would be. This is because the metal has a high melting and boiling point - one of the reasons why it is used as nuclear reactor fuel rod cladding, apart from its neutron transparency.

The high BP means that combustion of zirconium metal happens via oxygen diffusion into solid or liquid metal (the exact phase depends on heat losses and reactant transport rates). Compare this with magnesium or aluminium, whose boiling point is well below the flame temperature.

Therefore magnesium and aluminium boil, turn into metallic vapour and burn in a gaseous phase. The boiling process increases the surface area dramatically.

One advantage of the way zirconium burns is that because the metal doesn't vapourise, the reaction rate can be a lot more controlled and predictable. Magnesium or aluminium powder's reaction rate can start slow but accelerate as more and more metal is boiled off.

Wizzard - 21-4-2011 at 05:13

I would be rather interested in spare chunks of these (pass-around the classroom sized samples, at least 1"):
Molybdenum rod, OD 150mm: USD$100/kg
Tantalum rod, OD 150mm: USD$1034/kg
Cobalt rod, OD 150mm: USD$302/kg
Nickel rod, OD 150mm: USD$62/kg
Zirconium rod, OD 150mm: USD$140/kg
Niobium rod, OD 150mm: USD$345/kg

So long as the price is educator-salary friendly :) It's much easier to buy from somebody who works with and may have spare parts, rather than a person selling samples and full pieces.

IndependentBoffin - 21-4-2011 at 05:38

I have immediate stock of zirconium forms as described in my OP.

Even very small samples of some of the metals would be very expensive.
E.g. tantalum's density = 16.69gcm-3
A 2.5x2.5x2.5cm cube would weigh about a quarter of a kg.

Don't chemistry supply shops sell metal specimens in glass tubes for educational purposes?

Wizzard - 22-4-2011 at 05:10

Yes, I'm looking for somewhat less expensive, unsealed samples of any small shapes- They are to be handled and passed around in a classroom setting.

IndependentBoffin - 22-4-2011 at 06:52

Alright, if you want any metals on that list let me know and I will see if my networks can provide a sample (sample meaning it will still cost money but it is not subject to a minimum order quantity).

Also, thoroughly research the necessary precautions with the metals. E.g.

http://en.wikipedia.org/wiki/Cobalt

Quote:
After nickel and chromium, cobalt is a major cause of contact dermatitis and is considered carcinogenic. In 1966, the addition of cobalt compounds to stabilize beer foam in Canada led to cardiomyopathy, which came to be known as beer drinker's cardiomyopathy.


If there is interest in pure magnesium billets, let me know too and I can make enquiries. We all know how useful magnesium is as a reducing agent!

IndependentBoffin - 22-4-2011 at 09:50

One of the board members wants to buy 10g of swarf. Here's what 10g looks like.

With some very careful measurements you can check the density is ~6.52 g/cc, not a conclusive test of purity but a readily available one.

If you burn a filament of the zirconium swarf you will see it burns slowly with a white hot flame, producing little smoke unlike magnesium or aluminium which produces white vapours of the oxide in the gas phase. Not to be confused with the burning oil coating it will come in, to prevent further atmospheric oxidation (this burns first with a yellow flame).

If enough people are interested I will put up some still pictures or a video of the zirconium burning :)

100_3753.jpg - 234kB


IndependentBoffin - 23-4-2011 at 07:11

This is a picture of a ~30cm long Zr swarf burning. It burns steadily with a bright flame and little smoke.

zr_burning.jpg - 133kB

Fleaker - 23-4-2011 at 08:59

How much would a kilogram of swarf be?


IndependentBoffin - 23-4-2011 at 09:03

Quote: Originally posted by Fleaker  
How much would a kilogram of swarf be?



The main cost will be shipping. 10g occupies about 200ml without compaction. I won't compact it unless the buyer specifically requests, because it would result in broken filaments. Longer filaments are always nicer ;)

PM me with your general location to estimate shipping.

Fleaker - 23-4-2011 at 09:08

Oh, I don't really care about broken filaments. I merely wanted it for making Cs from its dichromate salt. I've often wondered how well it worked. Calcium granules cost about $200 per kilo sans shipping.

IndependentBoffin - 23-4-2011 at 15:40

Do you know if the oxidised zirconium (either from the air or once it reduces the Cs+) will dissolve in solution? I can send you a smaller sample first to see if it works well.

Fleaker - 24-4-2011 at 07:26

The alkali metal is distilled off, and it's supposedly better than Ca for making gas free metal.

IndependentBoffin - 24-4-2011 at 07:41

OK I'm always happy to have customers that place larger orders but my concern is that you end up with a product you can't use and become unhappy, hence my offer to send you a small sample first.

But if you're 100% sure I can try to compact a kilo as much as I can and then send it to you.

IndependentBoffin - 25-4-2011 at 00:06

Hi guys,

Please see pictures of a short Zr bar, 4.5kg of swarf (fills a 25kg polybag) and 100 - 150 micron Zr powder attached.

Surprisingly a pile of moist Zr powder is not as flammable compared to swarf.

Early on when I was assessing the safety of handling micronised Zr powder, I brought a blowtorch to the Zr powder and it needs to glow red hot before a self-sustaining reaction happens (it looks like a bright white spot moving around under a dark pile), although bits which were blown off from the pile by the blowtorch's airflow and flew into free air burned like bright sparklers.

The swarf however once lit keeps burning like when you light steel wool, only with a more incandescent flame.

I'm sure the Zr powder behaves differently if you put a dry quantity in a container, shake it around to aerosolise it and then ignite it :D, but I would prefer not to upset the neighbours ;)

I'm buying some heavier digital scales (up to 50kg). I'll then put the short pure Zr billet on the scales with some linear scales so you can roughly estimate the density by pictures to be 6.52g/cm3, thus providing evidence of the material and the purity.

100_3770.jpg - 270kB100_3771.jpg - 331kB100_3772.jpg - 240kB

The WiZard is In - 25-4-2011 at 08:16

Quote: Originally posted by IndependentBoffin  
One of the board members wants to buy 10g of swarf. Here's what 10g looks like.

If you burn a filament of the zirconium swarf you will see it burns slowly with a white hot flame, producing little smoke unlike magnesium or aluminium which produces white vapours of the oxide in the gas phase.

Speaking of Smokeless

This from Bennett I 1933, P. 392

Smokeless Flashlight Powder

Zirconium 28 pts.
Zr hydride 7
Magnesium 7
Barium nitrate 30
Barium oxide 25
Rice starch 5

Sorry to say - Bennett does not supply the original
source.


---------
Industrial and manufacturing chemistry: organic, a practical treatise
By Geoffrey Martin
1913

3. Smokeless flashlight mixtures giving an intense light consist of magnesium or aluminium
powder + nitrates of rare earths (thorium, zirconium). See German Patent, 158,215; see also
English Patent, 27,267 (1904), where rare earths are added to Mg or Al flashlights. \

-------

Two parts of magnesium or aluminium powder are mixed with two
parts of cerium or thorium nitrate, and with one part of zirconium
nitrate ; the double salt of these nitrates with other nitrates may
also be employed. These flashlights are said to burn with
practically no smoke, giving a flash of great actinic power, and of
much shorter duration than have been prepared with chlorates
peroxides.

Photographic Flashlight Powder. Act-Ges. f. Anilinfabr. Fr. Pat. 340,459, Feb 15, 1904.

In:— The Journal of the Society of Chemical Industry. 16 [23] 836. Aug. 31, 1904.

watson.fawkes - 25-4-2011 at 18:18

Quote: Originally posted by The WiZard is In  
Smokeless Flashlight Powder

Zirconium 28 pts.
Zr hydride 7
Magnesium 7
Barium nitrate 30
Barium oxide 25
Rice starch 5
Reminds me of U. S. Pat. 6848366.

IndependentBoffin - 25-4-2011 at 23:09

Hi guys,

Some of you have PM'ed me asking for small samples of metals I don't have in immediate stock - e.g. Ni, Co, Ta, Mo, Nb. My supplier isn't interested in small sales the size one might use in a chemical elements collection. The smallest samples they can supply for these are 100x100x1mm plates. If enough of you pool together for such an order we can probably work something out.

Re: the zirconium and titanium plates, which some others asked for as well. I can get 99.5% pure 2x1000x1000mm titanium sheet for USD$40/kg and 99.5% pure 2x1000x1000mm zirconium sheet for USD$302/kg.

Normally I'd use sea freight for my orders of zirconium because the orders are fairly large and there is enough time for me to wait between my separate orders. However for such a small order air freight is faster and more appropriate. I have to pass on the air freight costs to you guys.

So to summarise here is the situation:
1) If you want Ni, Co, Ta, Mo, Nb samples - you must be willing to either buy a 100x100x1mm plate, or pool together to find enough people who want to.

2) I can still supply Zr swarf, billets cut from 50mm rods and 100 - 150 micron powder, subject to any applicable regulations.

3) If you want to buy Zr or Ti plate, you must be willing to either buy a 1000x1000x2mm plate (material cost of plate excl. shipping: USD$360 for 9kg Ti, USD$3938 for 13kg Zr), pool together to find enough people who want to, or be willing to pay much higher prices/kg for a smaller 100x100x1mm sample.

The WiZard is In - 26-4-2011 at 08:37

Quote: Originally posted by quicksilver  

However there IS a source for Zirconium that you may find available; especially if you have a photography oriented store near-by.....Flashbulbs. Certain brands have Zirconium wool and do still exist if you know where to look.


Old flash bulbs can still be had. I bought these at the sadly now
defunct Alexanders Hardware.

NEW YORK TIMES
STRICTLY BUSINESS; A Cluttered Treasure-Trove Closes
By DOUGLAS MARTIN
Published: January 11, 1993

A customer might wander into Alexander's Hardware, peruse its marvels for a wondrous lunch hour, then pick up a couple nuts and bolts from one of thousands of bins.

"No charge," Arthur Alexander would say. "I'll get you next time."
No more next times. After 83 years, the bafflingly cluttered emporium at 60 Reade Street in lower Manhattan is in the final spasms of closing. It is going the way of other old-fashioned Manhattan hardware stores, places like Kamenstein's on Third Avenue at Ninth Street, Tinker's Paradise over on Park Row, several places on Canal Street. [“Radio Row” done in by the WTC which needed its land.]

Rents are too high, hours too long, profit margins too slim. His two grown children shun working 60 hours a week in a family business. Mr. Alexander will soon be 68, the age at which his father, who never retired from the store, died.

The future, Mr. Alexander says with no rancor, belongs to outlets selling nuts and bolts in cellophane bubbles for a dollar or so a throw, not mom-and-pop joints that think nothing of giving a couple away.

Alexander's was officially closed Jan. 1 to make way for a shoe store, but the doors are still open for a couple days to get rid of as much stuff as possible. So devotees continue to wander in, looking for that last bargain, a suddenly remembered necessity, an inconceivable about-face in the march of time.

There was Richard Genovese, a research analyst, who once found a period lock for a 60-year-old closet on a dusty shelf. "The city has lost one of its treasures," he said.

"It's like digging around in my grandfather's attic," said Chris Piazza, a sculptor who has been spending her days -- and around $2,000 so far -- buying interesting things. One find: 200 foot-shaped treadles for old-fashioned sewing machines she intends to use in a whimsical model of the Eiffel Tower.

The place has been so much more than a hardware store. In sorting through things, workers have found snakeskins, brassieres from the 1940's, a few mottled fur coats. They have sifted through thousands of flexible screwdrivers used to screw around corners, tens of thousands of mother-of-pearl buttons for old-fashioned high-topped shoes for women, bayonets from the Spanish-American War.

Amid the ball-bearings and washers, they have stumbled upon inexplicable surprises. What did anyone ever want with lipstick that looks and tastes like eggnog?

"This has always been more than a hardware store," Mr. Alexander said.

Mr. Alexander has followed firmly in the footsteps of his father, Samuel, in buying big quantities of things nobody wants, then finding novel ways to market them. Customs auctions, bankruptcy sales and the like were the Alexanders' hunting ground.

Samuel Alexander once latched on to 250,000 World War I wooden ammunition boxes and sold them as any number of things. Many went as shoeshine boxes after he hammered cast-iron stands on top.

Arthur Alexander acquired 10,000 pounds of body trim intended for 1939 Chrysler Airflow automobiles. A sign over a huge pile of them suggested the strips would make terrific stakes for tomato plants. Another time he became the proud owner of 45,000 aluminum heating elements used in making crock pots, which had come and gone. The elements moved briskly as refrigerator defrosting coils.

Currently, he is scrambling to unload 70,000 hinges for the music holders on pianos. Clearly, the perfect thing for doghouse doors.
Sprouting from a successful pushcart, the store has occupied several downtown locations. "America's Smallest Hardware Store in America's Largest City," said an early advertisement. In 1949, its reopening after a fire prompted a loyalist to write that he "would certainly have missed his daily browsing of the very interesting store."

Though Mr. Alexander is going to make more money as a landlord than he ever made as a merchant, he acknowledges that he is saying goodbye to a piece of his family. Both his parents worked in the store, as did his younger brother, Lawrence. Tears flow down his face when he tells of Lawrence being diagnosed as having what proved to be fatal polio on the same day they moved into their present store in 1945.

One of the storekeeper's stories concerns a pair of suspicious characters who for an extended period came in on Friday evenings to buy crowbars. Finally, Mr. Alexander informed the police.

The men were arrested with a trunkful of used crowbars just after knocking off a safe. Fearful that the burglars might find out who fingered them, Mr. Alexander began carrying his licensed pistol everywhere.

He has also gained wisdom, including the unshakeable conviction that vacuum cleaners can always be fixed, no matter what. "They're built to last forever," he said.

But it is Mr. Arthur Alexander's human touch that will be most sorely missed by his regulars -- how he would know the history of each item, the patient and intricate way he would instruct a customer in the use of some esoteric object.

"It was wonderful to know you all these years," Pearl Heller of Washington Heights told him, recalling the slender candleholders on which he years ago gave her a good price.

Photo: Arthur Alexander, 67, posing with vintage military paraphernalia in his hardware store, which is closing. (Jack Manning/The New York Times)

Here dobe some output info on flashbulbs.

The "B's" (Blue) ones were for colour photo's.

http://www.flashbulbs.com/flash_info.htm

The pics are of la 3B's and SM's. It had occured to me that I
could have sold the SM's to the IRA! The SM's were photo'd
through the glass, notice the bridge wire. When I have the time
I'll remove the glass and get out my Nikon PB-4 bellows for a
better/closer shot. And find out if the wire in la 3B's is zirconium.

The SM's are 'bout the same size as the popular #6 flashbulb.
The one in the photograph in held in ring stand clamp.

Google yields 311 000 hits for flashbulbs - try this one —
http://www.darklightimagery.net/flashbulbs.html


Flashbulb-3B.jpg - 226kB Flashbulb-SM-1.jpg - 219kB

Trivia - Connection? The IRA stopped making bombs and
Polaroid stopped making film.

[Edited on 26-4-2011 by The WiZard is In]

#3 (B) Flashbulbs

The WiZard is In - 27-4-2011 at 12:23

Stopped raining... so back from the acid storage. Walked up
on the first garter snake of the season, the maggots are at
work on my fisher (Martes pennanti) - it didn't look both
ways before crossing the road back in February. I hope it gave its
soul to God — for its bones are mine. Well except its missing
a rear leg.....

The metal mesh in #3 flashbulbs weighs on my reloading scale
0.30 gram's. It reacts vigorously with conc. HCl at ambient
temperature (15.5o C.) Most likely magnesium, however, could
be aluminium. Will sacrifice another and test it w/ NaOH.

Interesting - the bulb is coated on the outside like most
flash bulbs with plastic. These are also coated in the inside
with a thin plastic film. Could be all #3's are inside coated
the "B's" on the outside as that is were the Blue
for colour photography comes from.

a_bab - 27-4-2011 at 14:02

WiZ, the Zr flashlight bulbs are quite rare actually. They were among the first ones. Once it was discovered Al does the trick just as well, all the rest were made with Al filament in an oxygen atmosfere. Mg was also used for a short period of time.

What you've got is likely Al. Do a sacrifice and grab your salad dressing for a quick test.

Some relevant links:

http://www.darklightimagery.net/flashbulbs.html (an introduction)
http://www.dlbrittain.com/FlashCollect.htm (metal use specification)

IndependentBoffin - 3-5-2011 at 10:30

Fleaker, I'll post a small sample of Zr to you for free to test whether it is suitable for your purposes. Please check your U2U's.