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barnacle
3-Feb-2016, 08:56
Or so the legend has it. But I'm curious about R09... I have some one-shot here which I've been slowly using, and of late I have felt that the negatives have been underdeveloped - very thin in the highlights, even with the development time pushed 25%. Most recently I have had a batch of negs with an odd reddish mottling around the edges of the negatives.

Inspecting the remaining half-bottle of the R09 I heard rattling. The soup is a nice dark red after five or six years, but there are great chunks of crystal in the bottom. Which, if as seems likely are the active components crystalising out of solution, would rather explain its lack of activity and generally strange results.

I guess it's past its eat-by date...

Neil

LabRat
3-Feb-2016, 09:19
I have replied here that I have seen Rodinal failures happen a few times, in different labs, with old/not so old stock... (No reason not to work if it worked last month, right!?!!!) Here today, gone tomorrow...

With ANY old liquid stock developer, I at least stick an undeveloped strip of 35mm film into the working solution before use (in roomlight), and wait for the strip to darken to a dark grey/black before proceeding (for about 3 or 4 minutes) as a crude test...

Steve K

plaubel
3-Feb-2016, 10:49
R09, and the other newer products from Maco, Impex and Tetenal, are not original Rodinal per formula, so we should not expect the longlife quality of the good old Rodinal.
Par example, highly toxic ingredients were substituted.

Some chrystals will fall out over the time, but in my experience this says not much about further lifetime.
But latest after one year, my bottles are empty, so I can't speak for longer times.

Ritchie

Taija71A
3-Feb-2016, 10:56
The 'Original' Rodinal Laboratory Formula (from 1891)... Hasn't been available since 1893.

http://www.digitaltruth.com/articles/historic-rodinal.php

AuditorOne
3-Feb-2016, 13:39
Forever is a very, very, very long time. I'm not sure anyone has tested to ensure Rodinal, or any of the resulting variations, actually lasts forever.

barnacle
3-Feb-2016, 13:51
Hmm. Either way it looks like I'll have to put my hand in my pocket and buy some more developer!

koraks
3-Feb-2016, 14:04
I don't think anything lasts forever, and even with Rodinal's alleged longevity, I think 5-6 years would already be pushing the boundaries under the best conditions. I know I haven't gone beyond about 9 months, but haven't had any issues so far.

As to the crystals: I get that too with Rodinal concentrate as I work my way through the bottle. Part of the developer crystallizes, which makes sense if you realize that it's a (near-)saturated solution to begin with. The crystals should remain where they are (i.e. don't decant) so that the solution remains saturated. I hear that it may help to heat the bottle a bit to nudge some more developer to go back into solution, but I wouldn't count on it bringing your tired developer back to life. Reversing oxidization isn't feasible. To prevent oxidization, I usually try to squeeze as much air as possible out of the plastic bottle (I use Adonal, which comes in a plastic bottle). It'll never prevent oxidization entirely, but maybe it helps just a little bit.

Of course, the only proper solution is to shoot film a bit more often and use up that bottle before it goes bad ;)

barnacle
4-Feb-2016, 01:05
Time to get onto Ag photographic and see what they have in stock, then! I just hate throwing half a bottle of the stuff away...

500cc at 40cc/tank is only 72 negatives... I'm *sure* I've shot more than that in the last five years... time also to get busy, it seems.

Neil

ruilourosa
4-Feb-2016, 01:25
It does not lasts forever! After 6-7 years, stored in a brown glass bottle, failure stroke in some important negatives!

BetterSense
4-Feb-2016, 05:43
I used the dregs of a plastic bottle of "R09 one shot" from Freestyle and more or less ruined the roll of 35mm negatives. I had always had good luck with old Rodinal but that taught me there is a limit.

HMG
4-Feb-2016, 11:30
I wonder to what degree the Rodinal packaging plays a role. I.E. the old glass bottles vs. the later plastic bottles.

Randy Moe
4-Feb-2016, 11:45
I'm sure glass was better.

I have a few bottles of photography chems in factory sealed plastic bottles that are collapsing inwards, which must mean something is leaving the sealed plastic bottle.

Which also means my air is being contaminated.

And I could decant to all glass, but I drop a lot of things...

LabRat
4-Feb-2016, 12:27
I'm sure glass was better.

I have a few bottles of photography chems in factory sealed plastic bottles that are collapsing inwards, which must mean something is leaving the sealed plastic bottle.

Which also means my air is being contaminated.

And I could decant to all glass, but I drop a lot of things...

No Randy, the "bottle squeeze" thing is from changes in atmospheric pressure at night as the air gets heavier... (I know as I use 2 ltr soda bottles as chem bottles, and nearly empty ones start making clicking/snapping sounds overnight, and sometimes I find crunched empty ones in the morning... Even dented metal paint cans...)
And I sleep on an air mattress and it gets much harder and softer at times...

Sounds mad, but exhaling CO2 from my lungs into a half-filled bottle with a drinking straw before capping does extend the life of stock & highly diluted solutions... My dilute one-shot film developer starts to discolor a within a day in half filled bottles, but takes over a week after I exhaled into it... Grab a handful of straws the next time you do fast food...

Steve K

plaubel
4-Feb-2016, 12:58
After every usage I cover my chemical liquids with Propan/Butan gas to protect the liquids against O2. This works well..

mihag
4-Feb-2016, 14:07
Par example, highly toxic ingredients were substituted.



Such as?

plaubel
4-Feb-2016, 17:01
I don't know.
If you really want to know, I may ask my good friend who worked at Tetenal and who has sold for years the new Rodinal stuff.
He once told me that toxic chemicals has been substituted, maybe he knows.

But I remember another thing he told me last year, because I have had problems with the surprisingly short lifespan of my last charge of Adotol.
Developers have ingredients which will guarantee the lifespan. But they are the most expensive part of a developer, so if a producer want to safe money, he probably will safe this ingredients first.
Just an information, nothing to say against any producer at this time..

Ritchie

SMBooth
4-Feb-2016, 17:06
Had same issue the other night, chunks of crystal in a bottle of R09 (which i ignored) that I estimate being 12 months old. Stripped all three rolls. Wish I seen this thread earlier....

Jac@stafford.net
4-Feb-2016, 17:17
Developers have ingredients which will guarantee the lifespan. But they are the most expensive part of a developer, so if a producer want to safe money, he probably will safe this ingredients first.

That's what happens when accountants f*ck with science.

Randy Moe
4-Feb-2016, 17:23
No Randy, the "bottle squeeze" thing is from changes in atmospheric pressure at night as the air gets heavier... (I know as I use 2 ltr soda bottles as chem bottles, and nearly empty ones start making clicking/snapping sounds overnight, and sometimes I find crunched empty ones in the morning... Even dented metal paint cans...)
And I sleep on an air mattress and it gets much harder and softer at times...

Sounds mad, but exhaling CO2 from my lungs into a half-filled bottle with a drinking straw before capping does extend the life of stock & highly diluted solutions... My dilute one-shot film developer starts to discolor a within a day in half filled bottles, but takes over a week after I exhaled into it... Grab a handful of straws the next time you do fast food...

Steve K

Disagree. These bottles are doing something else, I like the straw CO2 idea.

barnacle
5-Feb-2016, 01:42
If I get chance today, I'll try a dish development with some of the old R09 and a sheet of film in daylight; it ought to come out flat black, but we'll see.

Neil

ruilourosa
5-Feb-2016, 01:52
Toxic or highly toxic is a no question. Original Rodinal was never mild... hidroxides are highly corrosive, the developing agent is toxic and bromides added (not present in the original formula) are also poisonous. Things were added and removed from the formula several times but the poisonous or toxic nature of the concentrate was constant! The generic brands of rodinal work all well, but when when i now see some red tint on the concentrate and a lot of cristals (too much cristals) i throw away and open a new bottle. PC-TEA never failed me though...

The darkening of the leader of the film is a good test as the failures i had were complete!

cheers!

Greg
5-Feb-2016, 16:30
Have used Rodinal since the early 1970s. Never had a problem with it but then every 5 or so years I would replace my bottle of stock solution with a new bottle. Last year mistakenly used a 1:50 dilution from a stock bottle that I had saved from the 1970s. Negatives looked great! By the way, I immediately threw out that old bottle of Rodinal.

Greg

mihag
6-Feb-2016, 12:11
I don't know.
If you really want to know, I may ask my good friend who worked at Tetenal and who has sold for years the new Rodinal stuff.
He once told me that toxic chemicals has been substituted, maybe he knows.



Hi Ritchie, that would be great.

plaubel
6-Feb-2016, 13:02
Mihag, after a short phonecall I now can give the information, that Agfa Vaihingen, the oldest chemical company worldwide, had produced Rodinal until 2006.
Since decades, the formula often has changed, depending on knowledge and on the laws, which became continiously more stringent here in germany.
Which components exactly were substituted is not known to my friend.

As Randy said, the best quality concerning a longer life was given by the glass bottles, which once were substituted by Agfa with HD-PE bottles, not as bad as PE, but not so good as glass.

Around 2006 Agfa have had to give up and they had sold the formula of Rodinal, which seems to be the basic of each follower.
I want to say "seems to be", because one seller says, we are original, and other sellers say we are more original, then you can hear something like original-original, and so on.

I don't care, I love this stuff, I do not care red coulor, which sometimes comes a few days after opening the new bottle, I ignore some chrystals ( never have had thousands of them in the bottles, only a few ones); I protect the liquid with Propan, and I don't expect a lifespan more than one year.

Ritchie

AuditorOne
6-Feb-2016, 20:44
For me I felt it was a good idea to decant the Rodinal to a brown glass bottle that I bought from Photo Formulary.

Of course, if you have a habit of dropping glass bottles then the plastic one will probably survive better. :)

mihag
7-Feb-2016, 05:02
Thanks Ritchie.

barnacle
8-Feb-2016, 13:17
Well that was an interesting experiment: two sheets of film - from the same batch as the ones that had the edge speckling problem; same RO9 developer; same time; same concentration; same temperature.

The difference was that I did these in a Patterson orbital tank (which could use some roughing up of the base to let things behind the film, but that's another story) with continuous agitation - the only option with the Patterson - instead of ten seconds every minute, and with a much smaller amount of chemicals - 150ml instead of 1050ml for my usual tank.

One sheet was straight from the film holder in which it has been from the original load a month ago; the other was from the same holder but exposed to a 50W light for five seconds at six inches (we're dead scientific round 'ere!).

The result (based on a quick inspection while still wet) is one sheet of pure sheet, doesn't look like *any* fog, and one sheet a damn sight blacker than my negatives have been of late. Which suggests if nothing else that I'm insufficiently exposing the film, or there's a *huge* difference between the agitation methods. I'd expect the continuous agitation to increase the contrast, so it's going in the expected direction.

There was however no sign of the coloured speckling on either of these negatives.

I need to try this approach with a proper picture.

Neil

Jac@stafford.net
8-Feb-2016, 14:51
I also decant Rodinal into small brown bottles that have the expressed cap that displaces developer leaving no air in the bottles. I got a case of the bottles and they are small enough to use-up in a couple sessions.

barnacle
11-Feb-2016, 02:05
I'm beginning to wonder if the issues I had were down to disturbing the sediment in the bottom of the bottle - those crystals I heard and saw moving around.

After the black/white negative test I did a couple of days ago, I've just cooked a handful of negatives. The weather didn't play, but never mind: using a Paterson rotary tray with the mushrooms in to do four at a time, one minute prewash to shift the antihalation backing, 3.5ml of R09 in 160ml water (~50:1) at 20C for 8 minutes, continuous agitation. Then 1 minute wash and 4 minutes Ilford rapid fixer, 16 minute wash in four changes of water and a drop of fairy liquid. The film is out-of-date Adox CHS-50; both it and the R09 are the same as previous discussion.

The result is a scan that is immediately usable; the Xsane histogram shows a full spread with zero gain and contrast, and a gamma of 1. The Gimp indicates that the actual black is around the mid-40s and peak white at around 250 (with an eight bit scan).

As scanned:
146406

With gamma set to 0.65 and black and white point adjusted as above:
146407

Perhaps one should treat R09 the same way as a decent claret?

Neil

Fr. Mark
11-Feb-2016, 21:39
There are lots of formulas for Rodinal and similar stuff made from acetaminophen and they last a long while in my hands especially unopened and even work when dark colored but not forever. I did not see the magic with Rodinal and switched to other developers that are easier to mix or keep as well or better and for which there's a defined recipe. (D-23 and Pyrocat HD) but ymmv.

I've thought about getting a tank of Argon and a regulator but until I buy one for welding I'll hold off. I can buy another of film and processing chemicals for the same price. Longevity of developers ought to go way up of oxygen could be excluded. It's standard practice for storing chemicals in an organic synthesis lab but it won't pay with photo chemicals in my basement.

Donald Qualls
14-Feb-2016, 08:24
When last I was able to process film (my darkroom has been out of service for about eight years), I was using my own mix "Parodinal" made from acetaminophen, sodium sulfite, and sodium hydroxide (nothing else but water), and found it would keep about six months with an inch of liquid in a pint glass jar (i.e. a lot of air relative to the volume of developer). I used to test before mixing by putting a drop of the concentrate on a film scrap in the light; if it didn't turn maximum black in about fifteen seconds, it was time to mix a new batch.

I also had some Dektol stock that I'd made up with half the usual amount of water; it was the color of Coca-Cola, but worked perfectly last time I used it, three years after mixing. I did backfill the jar with butane lighter fuel, every time I reclosed it, however.

I would expect that the "collapsing bottle", at least as encountered in chemical storage, is due to oxygen (20% of the volume of air) being taken up in oxidizing the developing agent or antioxidant -- of which, given relative densities of liquid solutions vs. air, you can do rather a lot before your developer dies. I had a bottle of Diafine Solution A that had taken that bottle collapse about as far as possible, and hadn't even visibly yellowed.

Randy Moe
14-Feb-2016, 08:44
Thank you for a logical answer to my collapsing plastic bottles.

I am not a chemist, but understand this explanation.