grommi
Hello everyone,
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Given the circumstances, I’d like to know more about this. Time and again, I’ve ended up with negatives covered in masses of tiny dots (white in the positive). After ruling out all other possibilities, I identified a cheap, no-name fixer from a 3-litre canister as the culprit. I can now only use it as a one-off fixer for films; then it works reasonably well.
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My Adofix concentrate went off after about a year, with a disgusting stench and cloudy sediment. The bottle was still half full. The same issues with Adofix are currently being discussed in another forum, and I personally know two people who also had Adofix that had gone off. For that reason, I’m afraid I can’t recommend this fixer.
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I was once given a bottle of Tetenal Superfix that had been opened for about 15 years, and after filtering out some sulphur sediment, the fixer and the results were flawless. At the moment I’m using Agefix that’s over 30 years old; I had to filter that too, but afterwards it was as fresh as on the first day and it smelled spotless as well. With this ancient Agefix, I get the cleanest negatives I’ve ever had. No, that’s not an exaggeration. Staining is a thing of the past! I’m amazed, if not appalled, that ancient fixers work so much better than many of the current ones. Was there ever some ‘secret’ substance in there that’s now banned, similar to cadmium in film and paper? So have the formulas changed over the decades? It’s much the same with modern paper: after two or three years, many start to get really covered in fog, whereas ancient paper is often still (almost) as good as new.
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I would never have thought that something as mundane as a fixer could cause such problems. When it’s time to buy a fixer again, I’ll definitely only go for a well-known brand, but which one?
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Regards – Reinhold
piu58
Fixer – regardless of the brand – contains either sodium or ammonium thiosulphate. The effect on film and paper should be the same. I don’t believe that white specks are caused by the fixer. How would that work chemically? It’s more likely to be air bubbles.
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Fixer must be stored in a warm place to prevent it from breaking down.
Photux
My half-full bottle of Superfix has gone off after less than a year – I suppose that can happen with any fixer. I’m going to give Adofix a go now… at least it’s nice and cheap, so if I end up having to throw away the residue, it won’t be quite so annoying.
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Are you sure the white spots are caused by the fixer (in which case it would be far too ‘strong’), and that the film base or the water used aren’t a factor?
grommi
Hi Uwe, these are definitely not air bubbles, but sharp-edged, irregular, tiny spots. I suspect contaminants in the raw chemicals used, which form insoluble compounds with the dissolved excess silver and settle on the emulsion. It did get worse and worse the more films were developed in the working solution. With single-use, there were only a few spots.
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PS: As I wrote above, I have ruled out all (!) other possible causes of the fault. This went as far as using only A. demin from the developer batch right through to the final wash. I switched to Uralt-Agefix and everything is suddenly fine. So, if that isn’t telling enough...
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PPS: The fact that the fixer was to blame was never a question on my part, but rather a statement of fact. I know from numerous discussions that there are often problems with contaminated negatives, and normally nobody thinks of the fixer. Of course, there are many other possible sources of error, but the fixer isn’t the first thing that springs to mind. What a lot of work and frustration I could have saved myself .......
Renate
Hello,
Air bubbles appear black in the positive. I’ve had similar ‘UFO’ spots in films before. The spots found here are small, round yellow marks, which are also referred to in the literature as ‘gold spots’. These spots then appear as white marks in the positive, which require quite a lot of work to remove. I’ve just come across a negative with this problem. However, I only have this problem with a few films.
The spots are probably colloidal silver, which is formed through oxidation. The oxygen involved can come from the emulsion or from the atmosphere. I once accelerated the formation of such spots using hydrogen peroxide. I’ll try to analyse the spots using a mass spectrometer.
I suspect the cause is less to do with the fixer and more with the washing. Fixers are all quite similar. The base substance today is exclusively sodium or, more commonly, ammonium thiosulphate. All other substances are additives. Depending on the pH value and additives, the fixer is washed out at different rates. The pH values of fixers vary significantly. I take plenty of time for the washing-out process and I will be expanding the procedure to include Wash Aid and Sistan.
I have so far used A300 for films and paper. It worked very well, although sulphur flocculates over time. However, the formula seems to have been changed repeatedly without the label on the bag being updated. I won’t be using it for paper anymore, as it now gives off a dangerous stench. When A300 is freshly prepared, an additive breaks down massively and forms sulphur dioxide. In a room without forced ventilation, the concentration of sulphur dioxide in the air can become dangerously high. As the films are fixed in a closed container, this isn’t so noticeable there.
Best regards
Renate
jochen53
Hello,
The classic formula for A 300 (Agfa 300 or Orwo A 300) contains only 200 g of sodium thiosulphate pentahydrate and 20 g of sodium (or, according to some sources, potassium) metabisulphite Na₂S₂O₅. Stability against sulphur precipitation can be further improved by adding 10 g of anhydrous sodium sulphite. I have never experienced the kind of decomposition described here with liquid concentrates based on ammonium thiosulphate when using this classic sodium thiosulphate fixer.
piu58
Hello,
Something like that
Air bubbles turn black in the positive.
Dear Renate,
Those in the developer, but not those in the fixer. Unfixed film remains there, and that tends to turn out light.
grommi
I still find it remarkable that Tetenal Superfix, which had been opened for 15 years, worked brilliantly, and that Agefix, which is now over 30 years old, has produced the cleanest negatives I’ve ever seen.
Renate
Hello,
I was thinking more along the lines of air bubbles in the emulsion – in other words, coating defects, strictly speaking. But those are quite rare. I’ve never heard of or seen air bubbles in the fixer, and I can’t really picture them either. I’ve never noticed the fixer foaming when tilted. But even developer that foams when tilted doesn’t leave any undeveloped patches for me. Nor have I ever observed my fixer forming gas bubbles at any point.
The classic composition of A300 hasn’t been used in its original form for a long time. Even the host’s shop now specifies a different composition. The switch to ammonium thiosulphate took place several years ago. However, the problem with strong sulphur dioxide fumes only arose for me with the new batch. The older batches did smell a bit, but it was within tolerable limits.
The yellow spots I’ve noticed on a few of my films develop over time (months to years). They are therefore not visible immediately after drying. They do not appear to be comparable to the spots observed by Grommi. Unfortunately, Grommi’s description is also very vague. A clear photograph of the defects would be very helpful here. I have not yet used the fixers described by Grommi.
Renate
Urnes
Hi Renate,
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Glad you’ve joined in. Well, I can confirm what you said about the spots. I was annoyed by it again just the other day. But I suppose it’s my own fault. It always happens when the solution has been left standing for too long. So, longer than four weeks in a half-full bottle; sometimes I’m just too lazy to make a fresh batch. Colloidal silver would certainly be a possible oxidation product. In my case, it wasn’t a no-name product either, but Hypam from Ilford.
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Regards, Sven.
grommi
Well, that’s how it looks for me with the fixer from the 3-litre container. Just imagine – if I’d used Agéfix, it would have stayed completely clean. And no, that’s not dust or limescale.
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To make it clear once again: I’ve developed a few hundred films over the last six years and know what I’m talking about, at least in this regard. Any cause other than the fixer can be ruled out. The fixer wasn’t used up either; I always (!) do a clarity test and replace used fixer in good time.
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A discussion about the cause of the stains isn’t necessary in this case either; I simply wish to point out the sometimes considerable differences in quality between fixers. Some definitely cause stains, others seem to have issues with shelf life. The fact that a fixer concentrate goes off after just three months of being opened is highly unusual, and I’m only aware of this happening with one product in such extreme frequency. Actually, everything has already been said in my first post.
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Something must be amiss here, be it the quality of the raw materials used or the formulations themselves. I can’t think of any other explanation for why 15- or 30-year-old fixers from plastic bottles(!) deliver the best results, whilst current fixers can cause massive problems.
michael-kielgmxnet
It looks similar to an Efke KB50 I developed recently. In my case, though, it definitely wasn’t the fixer, as other films I developed afterwards and fixed using the same solution turned out fine.
So I suspect it was down to the water I used to make the developer. I developed the film in Rodinal, which I had mixed using tap water.
bernhardmangelsgmxde
Adofix also went off quite quickly for me – I’m not sure if it was down to the temperature... Impex offered to refund the purchase price and return postage if I sent the bottle back... or did they want to send me a new bottle? But I had other things on my plate at the time... then the indicator stop bath obviously showed no colour change and the R09 bottle (still the 1:40 version) could only be opened with force and a right mess... since then I’ve preferred to steer clear of ADOX liquid chemicals.
If I remember correctly, Adofix was also quite often mentioned in the relevant forums when it came to problems with fixing. I’ve only had good experiences with other products (including cheaper ones) so far... (except for once, when the last residue (less than 100ml) in a bottle had some sediment... I can live with that)
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jochen53
Hello,
The chemistry of thiosulphate solutions is very complex. Here’s a link for anyone who just wants to have a quick look before closing the page again; manufacturers of fixers might also want to take a closer look:
http://edoc.hu-berlin.de/dissertationen/miethe-gundel-2003-03-04/PDF/Miethe.pdf
grommi
"Have a quick look... then close it straight away." That’s exactly what I did. Chemistry is the stuff that goes bang and stinks. Physics is the stuff that never works out. Well, my half-baked knowledge of science isn’t quite that bad, but this assignment is still a tiny bit ;-) too much for me.
Renate
Hello,
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A basic understanding of chemistry and physics is certainly helpful in photography. It allows you to avoid certain mistakes or better identify their causes. Simply following ‘recipes’ to the letter does not always lead to the best results. It’s more like fishing in murky waters.
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In that sense, Miethe’s thesis is very interesting. If you skip the analytical section, the work is a quick read. Whilst there is plenty of literature on developers, there is very little to read about fixers. In that respect, this thesis is a goldmine.
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Incidentally, I once had a fixer that gradually turned into a direct sulphur toner. I haven’t had any problems with the A 300 so far. I’m not familiar with the spots that Grommi shows. The films with the gold spots date back to a time when I was using different fixers and didn’t rinse the films as thoroughly as I do today, and even from that time, most of my films are still in quite good condition.
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Best regards
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Renate
jochen53
Hello,
I hope no one gets the idea of injecting A 300 or Adofix intravenously – you might end up getting addicted.
Bonderer
Fixer: the great unknown. Never caused any stains, but poor fixing (probably) took its toll after decades. Ilford Hypam was completely useless after less than a year (5-litre canister); Kodak Fix, about 15 years old and sourced from a newspaper office that was winding down, was still usable, but I only used it for paper. Sometimes you’re lucky, and sometimes you’re not – just like in real life. I think it also has to do with the volume and throughput that manufacturers have nowadays. Large volumes can be mixed much more precisely, and if it sells quickly, you’re always buying very fresh fixer. That’s certainly no longer the case these days. Smaller batch sizes in production, which certainly leads to greater variation in quality and longer storage times because demand simply isn’t as high anymore. For manufacturers, it’s surely a balancing act: should the last 150 bottles of a batch that are actually too old be disposed of, or would it be better to sell them? And what if the warehouse manager has forgotten a pallet that then turns up much later? I’d rather not know.
Incidentally, Kodak used to have a best-before or production date on the packaging, though I can’t remember which. It’s rarely found in photographic chemistry, but it’s standard in the chemistry I deal with professionally, in testing and also in consumer chemicals. It would certainly be helpful in photographic chemistry too, to avoid ending up with dead stock.
It may also have been necessary at Kodak because the stuff was apparently used in many newspaper labs, and they probably placed great importance on it. Anything that was past its time was simply no longer used there.
ADOX Adofix – there were sometimes issues with the canisters, but since then they’ve only been in bottles and have always been fine so far.
