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  1. #21

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    Eric,

    I just want people to understand the chemistry of FO so that they don't go around quoting Mathias's numbers as some sort of proven fact. His entire study is flawed, as my post above indicates. I never say you, or anyone else practices bad science. I'll leave that claim strictly at the feet of Jeffrey Mathias. But his complicated fan dance might mislead some otherwise well intentioned folks.

    I have no idea what the discussion was on the alt-photo-list back in 1994. And I don't slag anybody who uses any materials that work for them. Notice in my original post I mention that I'm sure artcraft, PF, B&S or even homemade FO is fine for printing. But that doesn't mean JM can use horribly flawed methodology to beginning organizing them in different levels of purity, and then have folks quote his research as meaningful.

    Your exact quote was "Experiments were being done by my ex business partner John Rudiak and David Michel Kennedy to try and improve BA&S powder or at least make it in line with the conversation." That is what I am referring to. Is this first hand information, second hand, third hand, etc.? Obviously you weren't there personally, so don't take offense. Sorry if I didn't quote it directly, I was summarizing. But its just false, DMK and Rudiak both wasted a ton of time on their experiments, and we would cheerfully explain to them how it worked and why, but they kept chasing their tails. Like I said, Rudiak eventually understood.

    If anything, Mathias' test shows that there is a very wide range of acceptable ferric oxalate powder and percentage mixes. His optimized solutions are all over the map and yet, they all seem to make decent prints.

    I'm not out to tell anyone where they should or should not purchase their chemistry, or how to mix, or even how to manufacture it themselves if they wish. That's all fine. But the fact that Mathias has horrible info on his web site which denigrates our product, and refuses to correct what are basic errors, is just plain silly.

    I'm being fairly hard on Jeffrey because I know he's aware of the flaws in his study, yet refuses to correct them. But otherwise, I like Jeffrey as a person (even if I'm a bit annoyed...) and his website does have some decent, useful info in there. He says some nice things about B&S. I just want the larger world to be aware of the flaws in his study before someone runs off saying "JM has determined such and such..." when in fact no such determination has been made.

    Eric says:
    "I am not in the business of selling alt process chemistry as my main endeavor, but I will not have my name dragged through the BS of B&S marketing. Because I stand up for alternative sources for information, chemistry and methods not being sold through the B&S pipe line does not give the good people at B&S the right the suggest I practice bad science."

    Hmmm, again Eric, where am I marketing? Where did I accuse you of bad science? Methinks you doth protest too much. I said you left the wrong impression about Rudiak's and DMK's experiments. I set the record straight in that circumstance, no big deal. You can buy and or make anything you want, I never challenged that, nor would I. The only thing I'm doing is protecting our product from false (some would say malicious) claims. I have not defamed my competitors products at all. I think the marketing is on the side of the folks who want to promote one product over the other based on fake purity tests. Why would they continue to post such misinformation if it is knowingly false?

    I notice you don't address my science at all, you neatly side step that issue and go straight into accusing me of having commercial motivations. This is why I rarely comment on these web boards (as I noted in my very first paragraph in the first post), because someone will undoubtably say that I am merely pimping our product (congrats on being the first!). I think most folks understand that in this situation I am perfectly entitled to defend our products against false claims and defamation. I'm sure you would do the same in the reverse case.

    So, for the record, do you stand behind JM's study, or do you agree with my explanation of specific gravity in relation to non-stoichiometric compounds? Please, I'd like to know. Because that is the issue I am pursuing here.

    Thanks for your concern,
    Kevin Sullivan
    Bostick & Sullivan, Inc.

  2. #22

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    Quote Originally Posted by Kevin Sullivan
    Eric,

    I just want people to understand the chemistry of FO so that they don't go around quoting Mathias's numbers as some sort of proven fact. His entire study is flawed, as my post above indicates. I never say you, or anyone else practices bad science. I'll leave that claim strictly at the feet of Jeffrey Mathias. But his complicated fan dance might mislead some otherwise well intentioned folks.
    Kevin,

    I think you are given this matter more time than it deserves. I am the one who quoted JM's numbers, but I did not present his findings as fact, only as something he tested and reported in the early 1990s, and which I was careful to say, may or may not pertain to current supplies.

    The knowledge that ferric oxalate is a molecular structure is undefined is well understood, as is the fact that people can make good prints using ferric oxalate produced in a wide range of ways. All of which agrees with your own suggestion that "purity" may not be relevant.

    I have used ferric oxalate from Artcraft, B&S and Formulary and they all worked fine. The only reason I brought up the test data from JM's site was because someone in an earlier message questioned the consistency of the ferric oxalate distributed by Artcraft, which in my experience is not a fact since I have been using it for going on ten years with nary a problem. I certainly did not assume anyone would take my commentes as critical of B&S since I have high regard for the quality of your products.

    Sandy

  3. #23

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    Thanks Sandy,

    I understand your position and agree with you that there are plenty of fine sources of FO powder out there. But the problem is not so much a batch-to-batch variation question as it is a testing methodology question.

    I tried to avoid dragging you into this personally, because I know you are reasonable and you didn't mean any harm by your comments. (Obviously, I didn't come out railing against you personally) Still, they leave the impression that Mathias had some sort of meaningful data, which is not the case.

    My responses are quite lengthy because its a tough technical topic and it needs to be thoroughly explained. I feel I did a good job describing it in common english with analogies people will understand, so that there will be no more confusion. If JM's percentages are so far off for B&S materials, then using that same method as proof of Artcraft's purity is equally dubious. I'm not saying their stuff is bad, I'm just saying the numbers mean nothing.

    I agree that we've devoted sometime to this topic. But I guess the detrmination of how much time is appropriate is dependent upon your motivation. For me, there is a good deal of motivation to protect B&S product from fairytale science. I don't do it often, only when it's an egregious and strictly unfair problem.

    I also want to make a correction: I said that Rudiak had a degree in chemistry from RISD. This is incorrect, as Eric Neilsen kindly points out, Rudiak's chem degree was from Lebanon Valley College. Rudiak did have an art degree from RISD as well, I believe. I'm perfectly happy to correct mistakes when they come up. No problem for me. That's the nature of friendly discourse.

    Also, Sandy, what do you think of Mathias' testing vis-a-vis my explanation of non-stoichiometric compounds? Do you see my point?

    Thanks again,
    Kevin Sullivan

  4. #24
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    Kevin, Your earlier post implied that I was included in a bunch of those that practice bad science. You seem to be working in the wrong trade, and now that Carl Rove is stepping down or over, maybe there is an opening for your brand of spinning.

    I don’t support Jeffrey’s web postings. There were flaws in some of his steps. I chose to let that stuff go, just like I let a lot of stuff go that is wrong that B&S post on your site; which had numerous misstatements about aspects of the platinum/palladium process.

    Why do I want to fight with you about your “science”? You are trying to say that SpGr has no place in testing and making of ferric oxalate? I won’t say that. Can Sp Gr give you an indication of the quality of your ferric? Yes, but not to the quantity of ferric in the solution or the purity thereof.

    Sp Gr in the production of liquid ferric can be a strong indicator as to its potency. And it is quite important to stress, CAN BE. It can also be that there is an inappropriate use of the tool and idea of SpGr while testing freshly made ferric.


    “I have no idea what the discussion was on the alt-photo-list back in 1994.” Well, Kevin since you are referring to it and putting words in my mouth, don’t you think you should know what was discussed?

    “Is this first hand information, second hand, third hand, etc.? Obviously you weren't there personally, so don't take offense.”

    Well, I was personally there, since the “there” that I refer was the dialog on the Alt Photo group, not being with either John or David.

    “Where did I accuse you of bad science”?

    “But I don't think it excuses Eric Neilsen from posting third-hand misinformation which slights B&S without telling the whole truth.”

    “But I'm not going to sit around and let a bunch of bad scientists with bad technique tell me that our fine product is 10% contaminated. These folks are either grossly uninformed or intentionally misleading people.”

    Kevin being one of a select few names in your rant, and having supported Dick Stevens’ work about making ferric, your innuendo about a bunch of people would seem to include me.

    And since you want to talk science, where did you publish the finding about the change in chemistry with the addition of oxalic acid? Was this run through a mass spectrometer? Green, yellow,….

    I believe that there is no one here that is putting in to doubt the dubious nature of “pure” ferric oxalate. If you have trouble with Jeffrey you should take them up with him. As for making ferric, I believe a more appropriate use of this space would be a discussion based upon question and answer/ answer and question. For those that haven’t made their own ferric oxalate and wish information on how to, that is the question. Not whether or not someone feels that it is a waste of time, or that a product exist that is “just as good so why bother”. These are people that make hand made prints, perhaps hand made is part of their quest. I support those people.

    If any of you care, I’d go look in and around Aug of 1994 in the alt photo archive for the making ferric discussion. It may have been a little later, but it will give you the a more complete understanding.


    mustering up all the respect I can,

    Eric Neilsen

  5. #25

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    Eric,

    I dunno what to say Eric. You seem to have decided to voluntarily include yourself in the category of bad scientists I was refering to. I meant mostly JM and anybody who buys into his fake research and defends it. If that includes you, then so be it.

    But you seem to indicate that you don't trust Jeffrey's science and don't believe his research, so fine. You are a good scientist because you can smell the BS when its piled up high. So no harm, no foul.

    I only mentioned your name in reference to the DMK/Rudiak situation, in which you indicated they attempted to "improve" our product through their own testing, and the implication that despite all their hard work B&S wouldn't listen. This simply isn't what happened.

    Yes, specific gravity can be a useful tool for measuring ferric oxalate, of course. But you seem to agree that it does not indicate purity.

    Sorry if you felt that made you bleed over into the scientist category. I consider the scientist to be the guy performing the research, in this case Mathias. In some cases I used the plural "scientists" to indicate a more generalized scenario ("people performing meaningless tests") as a larger category, not just this specific case.

    I really only have one issue here. I rarely jump into the fray and comment. But when it is called for I will. I don't chase Eric Neilsen around on the web just to bad mouth him. I don't care.

    If you are going to be pissed at me Eric, be pissed. Clearly I'm just talking science here, let's look at the methods and results. Yeah, I'm not too subtle about how I feel about bad numbers being reflected onto B&S. But that emotion is directed at the science and testers. Even on a personal level, as I stated earlier, I'm okay with Mathias. I'm totally okay with Sandy King. But if the science is lacking, and I won't bite my tongue for fear of waking people out of their dreamworld.

    I feel I've made my point.

    Cheers,
    Kevin Sullivan

  6. #26

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    Quote Originally Posted by Ole
    It's a safe bet that any chemical containing trivalent iron ("ferric") is non-stoichiometric. Even something as simple and common as rust varies wildly! Add oxalic acid to that, and you don't have to be a particularly bright scientist to guess that it's going to be diffcult to quantify "purity": The oxalic anion is a very strong chelating agent, and will cling to anything in just about any possible configuration.

    Which got me to thinking: Oxalic acid is used as a rust remover in several different applications. Could ferri oxalate solution be made by dissolving rust (or a "purer" FeO(OH)*nH2O in oxalic acid? A small addition of dilute hydrogen peroxide to assore the oxidation state of the iron might be a good idea, but at least it would avoid a whole lot of tricky process steps and explosive chemicals?
    Hi Ole,

    Interesting idea. It would be fun to make custom FO from famous sources of rust. Scrape some rust off the Brooklyn Bridge or the Eiffel Tower and and then photograph and print those objects with their own Iron. I don't think just adding oxalic acid will do it, might need some other procedure to free up the rust then convert it over, but I'll ask Dr Howard Efner when he comes by, he might have an idea.

    thanks for your input,

    Kevin

  7. #27
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    Quote Originally Posted by Kevin Sullivan
    Hi Ole,

    Interesting idea. It would be fun to make custom FO from famous sources of rust. Scrape some rust off the Brooklyn Bridge or the Eiffel Tower and and then photograph and print those objects with their own Iron. I don't think just adding oxalic acid will do it, might need some other procedure to free up the rust then convert it over, but I'll ask Dr Howard Efner when he comes by, he might have an idea.

    thanks for your input,

    Kevin
    Kevin, You might also talk to Te Rice or Bob Nugent. They used a formula that started with steel wool.

  8. #28
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    Should have read, Ted Rice

  9. #29

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    Sorry, thought I was done but this was too tempting...

    [/QUOTE]And since you want to talk science, where did you publish the finding about the change in chemistry with the addition of oxalic acid? Was this run through a mass spectrometer? Green, yellow,….
    [QUOTE]

    Uhhhm, where to start, Eric. This is basic chemistry. No need to publish it in a fancy journal. And a x-ray mass spectrometer will usually only tell the amounts of pure elements (how much oxygen, iron, hydrogen etc.) not necessarily how those elements are arranged. (FO or oxalic acid, h20, etc.) Also, gas spectrometers don't work because the FO breaks down before it reaches a gaseous state.

    I can fax you the chart Dr Howard Efner drew for me that explains it quite well, he seemed to think the whole thing was organic chem 101 level basics. I don't think the chem journals are that interested in this level of redundancy.

    Ole even mentions it, in a round about way, here:

    Add oxalic acid to that, and you don't have to be a particularly bright scientist to guess that it's going to be diffcult to quantify "purity": The oxalic anion is a very strong chelating agent, and will cling to anything in just about any possible configuration.
    The concept is that the wild tangled arms of the FO can be neutralized with the addition of oxalic acid. The oxalic grabs on to these loose arms and straightens them out, and they can no longer bond to each other as easily. This actually changes the non-stoichiometric FO into a stoichiometric compound, because the FO atoms are bound with oxalic, they can no longer randomly clump together. Now they have a more or less fixed structure. This is why adding oxalic acid to pure FO cause a color shift from muddy yellow brown to the bright emerald green. Its the shift from non-stoichiometric to stoichiometric with the addition of free oxalic acid that causes it to turn translucent green. This is well documented and understood, I'm suprised you aren't familiar with this idea.

    This is very easy to test visually if you have some pure FO, just keep adding oxalic acid and watch it turn green. I wouldn't say we are chemically changing the FO to something that is not FO, we are simply controlling its form with oxalic acid.

    I think that explains it. There's a little more info in the book The New Platinum Print which also includes Rudiak and DMKs prefered formula. (18g Oxalic Acid to 100ml FO#1, whew, way to much for my taste.)

    Cheers,
    Kevin Sullivan

  10. #30

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    Quotes all screwed up in above post, but you'll figure it out

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