Failed Experiments Starting With Dye Powders And Distilled Water

[FrMark]

I thought I should write about some of my recent adventures with trying to make my own inks from scratch, well, from dye powders and distilled water.

 

I happen to work in a university chemistry department and had a lot of time on my hands during the time the students and faculty were gone for winter break. We have a couple of shelves in a couple of rooms with interesting dye molecules. Most are intended to be used for staining cells for observation with an optical microscope.

 

I started at a couple milligrams/milliliter and in some cases went as high as 50mg/ml (green naphthol green).

 

pH values were on the lightly acidic side.

 

I thought I'd be clever and focus on a blue and a purple I liked in fairly strong concentrations that also happen to have had pharmaceutical uses (anti microbials). Methylene blue has been used as an anti-malarial, for instance, but it turns the urine green, then blue and eventually the whites of the patients' eyes turn blue. This made it hard to get people to keep taking their meds. Gentian Violet is still used as a topical anti fungal (thrush infections, primarily, I think) but at the cost of making the patient bright, strongly purple where it is applied. This stuff is a pretty serious purple at 1mg/ml. The starting powder is so purple it's green! Actually, methylene blue powder is nearly rust red until it gets wet.

 

But, the one I was using most, the methylene blue, at 5 mg/ml (the solvent is just distilled water) or thereabouts wants to dry out in the pen and clog the works. I thought at first the problem was the pen because I'd been using a pen with a somewhat damaged feed because it had an easy to clean plunger converter. But, when a pen with a sac converter that never gave me problems before started to choke on this mix, I realized the problem was my "ink" not my pens.

 

So, much pen cleaning ensued and the first pen is now back in service with some commercial ink (Sheaffer blue from a cartridge, it's all I had on hand, but I actually like it pretty well and have for years). The cartridge looks like it ought to fit a Parker 75 but doesn't and so I used a Sheaffer pen to poke the hole in the end of the cartridge an pipetted 1/2 the contents into the Parker 75's converter. I know crazy, an eyedropper fill in a modern pen!

 

Now it works for pages at a time with nary a choke. I'm glad for it. The 75 was a college graduation gift over a 1/4 century ago that's in nearly perfect condition because it had nib issues that all of y'all helped me solve very recently. Now I'm loving it.

 

I think the inks made in the lab will be used in the conquering of dip pen calligraphy so won't be wasted. But until I learn more about ink formulations, I'm not putting what the adult fans of legos call MOC's (my own creations) into my better pens!

 

As a side note, I tried to use paper chromatography to determine what the blue dye(s) are in the Sheaffer blue. I can give you a list of 6-8 things I'm pretty sure aren't in it, but I can't say what is. There's a number of much more sophisticated instruments in the various labs here that could get me the results, but the effort is not really worth it for a $10 bottle of ink.

 

If you are interested in this sort of thing, let me know. I could tell you about hot pink and fluorescent yellow, too. I can't imagine writing with them but some people might like it. Also, some molecules could be used to tell you if you are using cheap paper (as if the feathering won't give it away). I was surprised to see that with one of the two filter papers I used that Bromophenol blue immediately turned dull green to yellow. This means the pH of the paper is in the 3-4 range or possibly lower as that was what it arrived at after being dosed with dye. That's reasonably acidic (Vinegar is 2.5 roughly, neutral is 7, each number is a 10x change in acid concentration, or a logarithmic scale, like for earthquakes). This suggests a way of invisible writing if you picked your indicator dyes carefully. Pure FD&C Blue 1 is a nice turquoise at 5mg/ml.

 

Again, I'm not sure any of these simple mixes are good for fountain pens. Methylene blue at 5mg/ml is not in my hands. Methylene blue is not likely to grow mold, but who knows about the rest of these? I don't. Well, gentian violet probably won't. But it's your pen and your stained fingers if you don't wear gloves. I disclaim any responsibility.

[Corona688]

I'm definitely curious! I'm almost more interested in the messing around with inks than the writing.

 

Methylene Blue happens to react with iron, your first try was bad luck!

 

Using PH indicators as ink is interesting. Imagine an ink that warns you when used in poor archival conditions by turning a weird color...

[FrMark]

Bromophenol blue is blue until the pH drops below pH 4 then it turns greenish then if more acidic, weak yellow. One of the filter papers I used for some simple paper chromatography caused this material to immediately turn green! So, it would act as a warning you are working with pretty acidic paper.

 

Most of the materials I've been working with are histological stains or pH indicators or both or just dyes for various colors or fluorescence tracers.

 

I know methylene blue reacts with certain iron ions but I did not figure the concentration I was using in my stainless/plastic/gold etc fountain pens would cause any harm to the pens. I detect none.

 

The problem that I did see that is that at 10 mg/mL in plain distilled water tends to clog the pens, not flow well, etc. I may be near the limits of solubility and/or it might be the particulate content I can't see. The air here has been very dry some day recently was 11% humidity before running it through a heater and lowering it further. I may need some glycerine or something else as humectant and or some surfactant to increase flow but that tends to make the ink feather and for most I'd need some sort of antimicrobial (but probably not for gentian violet or methylene blue where are already anti microbial). I'm going to put this on hold 'til the next long school break at least. There's a lot still to try: First there are a bunch of molecules I've not tried, Second, paper chromatography is too blunt an instrument so far for reverse engineering a favorite ink, plus various formulation "improvements" including good filtration.

 

I was using these "inks" last night with some dip pen nibs and like the colors a lot, but after sitting a few days to weeks, it's obvious that there's particulates in virtually every one. I don't have filters that'd take out very fine fines, especially not for small volumes, or without diluting the dye to the point of unusability. I do have access to rotary evaporators but they aren't the best tools for concentrating water solutions. I suppose I could try freeze drying

 

Most of the materials I'm working from are very old, too, when it was not uncommon for dye molecules to be about 50% active ingredient and the rest contaminants. these look to be a little better than that for most of them.

[Corona688]

I was using these "inks" last night with some dip pen nibs and like the colors a lot, but after sitting a few days to weeks, it's obvious that there's particulates in virtually every one.

 

How are you dissolving them? The old hot-water trick may help.

[Corona688]

Got any Fluorescein? That could be an interesting one, either red or green depending on concentration.

[amberleadavis]

Hey, I'm enjoying reading about your experiments. Please keep sharing.

[FrMark]

I did make up some fluorescein. It's yellow/green to red/orange depending on concentration. It only fluoresces dry on paper at the paler yellow concentrations somewhere in the 2mg/ml range---notes are at home and I'm still at the church office where I have a internet connection. Phloxin is super hot pink even at 2 mg/mL.

 

Gentian violet or Crystal violet is pretty at 2-7 mg/mL.

 

Naphthol Green takes 50 mg/mL (ancient bottle!) to get to a green that I think has enough authority, but many people would probably find it o.k. at 10 mg/mL

 

Fuschine Red Basic 10 mg/mL is a lovely wine red heading toward brown/red.

 

Safranin Bluish 2mg/mL is a purple-y-er red wine color.

 

I was after a blue that looks like my Sheaffer blue. I don't have a budget to collect a lot of pens or commercial inks. I started down this path because the bottles were sort of singing to me during an academic break with little for me to do and I have in an academic lab all the glassware and lab gear to play a lot. That's sure changed with the start of the semester! Ink researches on hold 'til ?June?

[FrMark]

Also related is filtration.

 

There are filters for taking out tiny particulates. We don't have that tech readily available in teaching labs. I'm not ready to spring for it myself. Though someday I might.

 

Any kind of typical filter aid (ie diatomaceous earth) assumes much larger volumes of filtrate and a willingness to dilute and re-concentrate. I'm not looking to go that route, though I could.

 

I'm looking for syringes to take up the material and then squeeze it past some 0.5 micron (to pull a number out of the air) filters stuck onto the luer lok fittings on the syringes. These little filters have relatively small dead space (I used to use them 30 years ago in a Pharma lab with radioactive samples, I presume they are still in production). I've been working in 10-20 mL batches. It's not hard to weigh out 20 mg or 500 mg or whatever and its enough to see what the material's like.

 

As to using hot water to get things into solution, I do that with photography chemicals and sometimes once they are in solution they stay there. But with many things all you will do is super saturate and then hard to dissolve things like to find scratchy spots to make crystals again and that sounds too much like a pen feed getting clogged to me.

 

I'm glad to say that I've found a sonicator in the labs in the department so now I might be able to get the last of some yuck out of some pens.

 

But like I said in the last message, this is likely to be on hold for a few months. I may eventually post some pictures of the mixes but what I see on the paper doesn't match what my phone camera displays and after we transmogrify to your screen, I'm not sure there's much point. Agree/disagree?

[DrDebG]

Interesting experiments. After you make your concentrations, have you tried to centrifuge to separate the particles from the solute? Using a vial centrifuge in small quantities (i.e. less than 50 mL), then decanting the solute might reduce the particles in your pen. Just a thought. . .

[FrMark]

Centrifugation is a great idea, especially if the supernatant were taken off with a pipette so as not to stir up the pelleted material in the bottom of the tube. We definitely have centrifuges that would handle 10-20 mL at a time. I like solutions that don't require any further costs on my part!

[Corona688]

I may eventually post some pictures of the mixes but what I see on the paper doesn't match what my phone camera displays and after we transmogrify to your screen, I'm not sure there's much point. Agree/disagree?

 

If your bright colors don't photograph well, be assured, neither do ours. Microsoft and HP dumbed computer color fidelity down to match 1982 television fidelity, back in 1996, and this was adopted industry-wide, even in cameras. Color is now equal everywhere, for the most part, and equally bad everywhere, for the most part.

 

It's honestly a little disturbing. Several generations of digital artists may not have seen the important primary colors of art. I didn't realize how bad it was until my camera rendered a brilliant, but out-of-gamut blue as grey.

 

There's no reason to be ashamed of your photos, in short; please post them anyway.

Edited February 8, 2018 by Corona688

[Sholom]

You need at least a humectant (propylene glycol will be less smeary than glycerol when the ink dries, and less prone to bacterial/fungal growth as well). A wetting agent is a good idea, and with your cationic dyes, it needs to be cationic, nonionic, or amphoteric, but absolutely not an anionic (precipitation likely). Pluronic F127 adds some water resistance as when the ink is dry it gels when it gets a little water on it and F127 is a weak wetting agent you can use more of it. Surfynol 465 would be more typical for an ink but it is easy to add too much.

 

Don't mix cationic dyes, like the two you started with, with anionic dyes as almost all such combinations precipitate. Inks that are going to be stored for more than a few weeks need a preservative as well (again neutral or with charge to match the dye(s) you are using); for a few months storage around 1% isopropanol or methanol should work, but something stronger is needed for commercial shelf life. I can be more specific about materials if you get more involved with ink making. Yes I've made several types of ink, including fountain pen inks for my own amusement but I'm retired from lab work so no more lab access or ink making.

 

Top of the line cameras and monitors can do better than the sRGB colors that Corona688 is referring to, but digital color fidelity is a difficult and quite complicated subject. Take anything you see on a monitor with several grains of salt unless you know that both your computer system and the source material are fully and compatibly color calibrated, preferably recently for your monitor. That should NOT stop anyone from posting photos, but do remember that exact color accuracy is very unlikely (and in general we here know that).

[FrMark]

Sholom, Thanks!

 

What you say about additives makes sense, though I have very little experience with surfactants and formulation chemistry. My forte once was synthetic organic for the pharmaceutical world.

 

What are typical humectant concentrations? Somewhere around here I've seen some propylene glycol,. We have liters of of glycerol (and if I develop a bio-diesel teaching lab, I'm going to generate more!).

 

One relatively concentrated surfactant/wetting agent I do have is Kodak's Photo Flo. I was about to try introducing tiny quantities of that when I ran out of time for this project temporarily. I will have to look up the molecules you mention and do some compare and contrast. What would typical concentrations be?

 

Part of my interest in Methylene Blue and Gentian Violet is that they are both used, or have been, as anti-microbials. We have Thymol and Phenol which are somewhat preservatives. 1% iPrOH or MeOH ought not change the flow properties too much. What do you suggest that's more sophisticated/stronger and what would the usage rate be?

 

For starters, where color is concerned, I was hoping to be in a singe pigment per color. Ultimately, if this goes far enough, mixing colors becomes an issue and as many have noted chemical compatibility is an issue. Is there a chemical supply house that specializes in water soluble, non reactive dyes and is less costly than Aldrich (which is usually the most expensive supplier!).

[FrMark]

About color rendering:

I have a friend who is a professional photographer who started with film and works completely in digital now except for a little film scanning (one place we overlap, I use his scanner!). He and another one I asked about doing some custom printing a couple years ago labor mightily to have what's on the screen show up on the printer output and have those reflect what they intended when they took the pictures. I wish more people would print photos. What's the point of having more than about 2-4 Mpixels if you don't output to print? You'll never see the extra ones on a computer screen.

 

I sometimes paint in oils and I occasionally change the colors of things around to suit me, though I find it hard to do. My first conscious experience with limited color gamut was trying to make a pale pink rose with Cadmium Red Light. No can do. It goes grey. I needed something else as the starting point for the red/pink I wanted (I used a Quinacridone Magenta, Alizarin's fugitive). It's astonishing how wide a color space we have now with oil paints and what was done with more limited color intensity in the past. Frequently it's said and I'm coming to believe it's true that for most things, value relationships are more important to human perception of reality than color, hence B/W photos "work" even though the color is wrong and the values are compressed (sometimes expanded) rather considerably compared to real life. Unfortunately, my favorite pigments and knowledge about them in oils cannot be translated to fountain pens, though they could with dip pens and some really difficult photo printing technology (stacked layers of chromate sensitized gelatins)!

 

It's hard to beat single pigment high end oils (or water colors etc) for color. It's sad to think artists working in the digital space might have zero experience with them.

 

I've found the iPhone to be really good except when it's not: specifically red florals just don't render right (they tend to blow out) even on it's own screen where things would be most controlled. When I get home again where my lab notebook is I will take some pictures and post them.

 

I'm not set up at home to show the fluorescence of Florescein, however, sorry. I guess I could just bring the book back to work. Give me at least a few hours.

[Corona688]

About color rendering:

I've been geeking out on this subject and may talk your ear off, thanks for indulging me as far as you have, ignore me or tell me to shove off if I get tiresome

 

I wish more people would print photos. What's the point of having more than about 2-4 Mpixels if you don't output to print? You'll never see the extra ones on a computer screen.

Web quality covers a multitude of sins, if you viewed my average photo full-res you'd be disappointed And the poor quality of computer prints has led to the common perception that sRGB is somehow a better way to show things.

 

My first conscious experience with limited color gamut was trying to make a pale pink rose with Cadmium Red Light. No can do. It goes grey.

I approached the problem from the opposite direction - where to find a nice swatch of brown tones in RGB color space? It's not on the HSV wheel, red and yellow blend with no browning inbetween. I disappeared down a rabbit hole of data when I discovered the real color wheel and its exhaustive list of pigments, but the upshot is even "pure colors" mix differently as pigments than light and browns appear when you darken yellow. In RGB, browns are hidden in an extradimensional space of saturation and lightness so you'll never see more than one at a time on a color wheel.

 

Frequently it's said and I'm coming to believe it's true that for most things, value relationships are more important to human perception of reality than color

We'd notice how bad sRGB is every day if our eyes didn't adjust to it, but it's made the colors it can't show all the more poignant when we notice them. It happened almost the same time as flat screens became popular, causing a swift and clean changeover from the wild uncalibrated mess we had before to the uniform blah we have now. I thought at the time "well, they're a bit washed out but they'll get better" but they didn't, they're adhering to the standard of badness. That 1982 television fidelity became the foundation for the last 21 years of graphics, printing and photography was an amazing decision.

 

Unfortunately, my favorite pigments and knowledge about them in oils cannot be translated to fountain pens

There again you may find the RCW interesting as it's all about transparent colors.

Edited February 9, 2018 by Corona688

[FrMark]

There's a huge amount of information about color perception and real world pigments at handprint.com

 

It's aimed at watercolors but it helped me quite a bit.

 

Also search for Robert Gamblin's "Navigating Color Space" which is 2-3 'tube videos. Excellent for the oil painter, but an overall useful way to think about mixing pigments.

 

At least we have better definition/more pixels than in 1982. It's hard to watch old TV programs on a computer screen, I've been spoiled that way at least. I will look into the real color wheel.

 

Back to dyes, any practical advice on humectants, anti-microbials and wetting agents is gratefully accepted.

[FrMark]

I found a photo of some of the inks.

[FrMark]

And here is another:

[Corona688]

Thank you! Very unconventional colors, especially that orange. Unless that's just your camera, that is an unusually powerful orange. And that green has potential I think! That "bluish" I think isn't coming out correctly, if it's supposed to be bluish I suspect most of the blues aren't coming out right in the photos, but the gentian violet looks particularly dense.

 

Your observation on nib pens vs fountain pens is interesting. If you used some of the bigger tips or maybe a steel brush you might get results more like a fountain pen.

 

As for ink chemicals, without access to lab chemicals I've been making do with what I have: DOT3 brake fluid(polyethylene glycol plus colorant) and lemon dish soap(detergent, yellow colorant, foaming agent and yog knows what else). Mixed results: Better flow and better nib-wetting, but my pigment inks still settle overnight.

Edited February 11, 2018 by Corona688

[FrMark]

The Gentian Violet aka Crystal violet is v. dense, it's close to the limit of solubility at that concentration. It has a v. high tinting strength (high molar extinction coefficient), too, even for a dye.

 

Safranin Bluish is reddish, but maybe it is the closest to blue of the Safranin family? It surprised me too.

 

Most of the blues look purple until they dry out on the page, on my screen the colors are fairly accurate.

 

The orange is that orange, but it's fairly strong concentration and not something I'd put through a fountain pen w/o filtration or centrifugation.

 

I like the green, but it takes a lot of it to get to that color density.

 

I really wish I knew what dye molecules are typically used in commercial inks. I don't expect them to tell me! My choices were guided by some chemical intuition and by what was on the shelves. What's on the shelves was picked for use in staining microscope slides or needed for teaching labs, not for making ink.

 

You'd have to pay me a lot of money to put pigment inks in a fountain pen again. It can work, but it's a lot of trouble and not what FP's are designed for. That's dip pen territory. Unless the particles are exceedingly tiny and relatively low density, they will want to settle out.