Water Resistant Inks -- How Does Noodler's Do It?

[Miz Black Crow]

Noodler's amazes me. The color options, the shading, the water resistance (some-but-not-all inks). I have nothing but respect for Mr. Tardif. This thread is one of wonderment, amazement, and homage.

 

One thing that irritates me, however, is that he does not offer a true bulletproof CYMK set (with the obvious exception of Black.) This means that the inks I want to make for myself won't be bulletproof. And bulletproofness is a sticking point for me, or at least water resistance. (I don't write anything worth forging anyway, so for the time being let's throw out bleach/acetone/ammonia/..... resistance.)

 

So for the chemists in the room: how can one make a water-resistant, dye-based ink? The dye retailers I've called don't think it can be done. (They mostly retail to cloth dyers, so their lack of expertise in inks isn't surprising, but cellulose reactivity is cellulose reactivity; all cellulose-reactive dyes I've come across require activation with a base like soda ash or NaOH, and then are unstable in a bottle. )

 

The closest I've come to an explanation of Tardif's dyes on this forum is this:

 

  Quote

 

A little comment on Noodler's inks and reactive dyes....his water resistance isn't a result of his use of reactive dyes...an instant reacting dye that reacts with paper, will also react with water very quickly and will be useless in less than a day in water... Reactive dyes DO tend to give better bleach resistance and wash resistance....I leave you to ponder what he does with his inks to make them water proof.... (search inkjet patents, and consider that his inks smudge, but don't wash off with water, a reactive dye by itself wouldn't rub off if it is reacting with paper). This is by no means meant to put down Noodler's inks. I personally think they are great and as soon as I figure out exactly how he does it, believe me, I'll add "super-awesome-resistant-mega-inks" to my lineup.

 

Unfortunately I saved the quote but not the link in my notes. I believe Chemyst stepped in and countered that yes, they are reactive dyes.

 

We know that water resistant CYMK inks are possible, because De Atramantis makes them too. (Unfortunately they're very expensive here in the US.)

 

So. Who wants to take a stab? What makes Bulletproof Black so bulletproof? How can one make a water resistant ink from a dye base?

 

I'll offer some clues, or at least properties of Noodler's that I've noticed:

 

--He offers (at least partially) water resistant blacks, and purples, and browns. (Though usually the water resistant component is black...)

--He DOESN'T offer truly water resistant yellows or oranges. (Operation Overlord*)

--He USED TO offer essentially CYMK inks from I think Swishers (Goldfinch for yellow, which he was "permanently sold out of" at one point, Hellbender Red, Brittania's Blue Waves -- see the Noodler's CYMK thread). He no longer does so. Is this lack of interest, or a change in availability, or....?

--Noodler's likes to form bubbles in my bottles, indicating he uses A LOT of surfactant. This is also evidenced by the degree to which it nib creeps.

 

So far I've:

--Done patent searches related to inks (I still haven't found a single patent related to fountain pen inks; the ONE I was able to find seemed to talk about a "ball point fountain pen ink" which was odd.) There are lots of patents related to inkjets and ball points, but none specifically related to FPs. Most of the inkjet patents are pigment-related, but not all.

--Done MSDS searches for major ink makers. I've learned some about what other stuff goes in ink, but the only actual dye I've found was a direct dye used in Pilot's rollerball inks.

--Called Pro Chemical and Dye, DharmaTrading, and Keystone; the first 2 have no idea what I'm talking about (and think it's impossible); the last hasn't called me back yet.

--Done general dye research, especially at .

 

A list of threads worth reading if this topic encuriouses you too:

Fabric Dye as a Basis for Ink: https://www.fountainpennetwork.com/forum/topic/269610-fabric-dye-as-a-basis-for-ink/

Make Your Own Ink https://www.fountainpennetwork.com/forum/topic/2183-make-your-own-ink/

The Open Source Ink Project: https://www.fountainpennetwork.com/forum/topic/227894-open-source-ink-project/

Physics Articles Related to FPs: https://www.fountainpennetwork.com/forum/topic/288121-fountain-pen-ink-behaviour-fountain-pen-physics-journal-articlesreferences/

Mixing Glycerine In Ink: https://www.fountainpennetwork.com/forum/topic/257406-mixing-glycerine-in-ink/

Surfactants in Ink for Improved Flow: https://www.fountainpennetwork.com/forum/topic/229403-surfactants-in-ink-for-improved-flow/

 

So.... thoughts?

[SallyLyn]

Around 2007 ?? There was another thread on CYMK. At that time suggestions were Navaho, Shah's Rose, Yellow and Black. As you have mentioned only the Black was waterproof.

Whiteness of the Whale if still exists or someone has to sell, might give you some other options.

[dcwaites]

The comment in the quote is wrong.

 

Cellulose-Reactive dyes were developed for the textile industry, specifically T-Shirts, so that the prints on cotton (cellulose) T-shirts were more fade resistant.

 

When the dye (which is soluble in water) comes in contact with cellulose (t-shirt, paper, but not cats or fingers) it makes a chemical bond with the cellulose that is so robust, you have to destroy the cellulose to remove the dye.

 

The problem is that the range of dye colours available which are cellulose reactive is quite limited compared to ordinary dyes. That is why you can't get pure cyan, magenta, yellow dyes that are cellulose reactive. Nor pure blues, which is why Liberty's Elysium isn't bulletproof/cellulose reactive.

 

The reason some of the CR/Bulletproof dyes smudge is because of the CR reaction. The ink goes down on the paper (usually a hard, dense paper like Rhodia/Clairefontaine/Nu:Elite) and the first part hits the paper and reacts with it, and stops moving. This stops any further ink from penetrating into the paper, so it sits on top of the paper and just sort of semi-dries out, not reacted with anything. This is the part that smudges. If you use the ink on a more absorbent paper (ordinary copy paper) then you don't get the smudging.

 

I do believe that someone has made some blendable CMYK Pigment inks.

I hope someone who reads this can bring up the post.

[Miz Black Crow]

Dcwaites, my question is to which particular kind of dye he uses (, and how he stabilizes them so that they're fiber-reactive AND stable. All the dyes I've found require an alkali agent to activate them, and do not remain stable once activated for more than a couple of hours. Most also want to be used at high temperatures (>50^oC), though not all.

 

This brings up another question about Noodler's: how does he manage to have his dyes be cellulose-reactive *and* pH neutral?

 

The only thing I can think of is that the dyes he chooses don't need the high temperatures or the acidity, but I don't know how they operate.

 

One possible explanation, posited here:

 

  Quote

 

Noodler's inks use fiber reactive DYES; what makes them permanent is the inclusion of Na2CO3, sodium carbonate, (aka, soda ash or washing soda). Sodium carbonate is a salt, created from the distillation of carbonic acid. Aniline based fiber reactive dyes, when placed on a fibrous material such as cloth or paper, (wood pulp fiber), become permanent when sodium carbonate is added via a chemical reaction. That is what makes Noodlers inks permanent but still safe for fountain pens.

Best regards,

Sean

This explanation doesn't explain why the inks are pH-neutral, though. I'm not aware of any dyes that are stable after the addition of alkali, but that doesn't mean they don't exist.

 

(Procion MX dyes, or dichlorotriazine dyes, aren't even supposed to be stable in water for the long term, but other members have done it... by "pre-reacting" the dyes to make them stable. This also makes them non-waterproof. Remazol dyes, or vinyl sulphones, are at least water-stable without activating agents and are often sold in liquid forms, but I don't know what the shelf lives look like, and I doubt they'd be shelf-stable once activated.)

 

Another pigment/dye explanation, from the same thread (that started off as a comparison of blue inks, of all things; such a threadjacking there was on this poor thread....)

 

  Quote

 

With all due respects (really!) to all above in the pigment ink debate, I think we have a terminology problem here. "Normal" dyes are by definition completely soluble in the medium they are designed for (which may or may not be water) up to some concentration level. Their solubility limit often is a function of temperature, so if where you store your inks gets colder in the winter (my study can drop below 60F if the auxiliary heat is not on), some dyes may precipitate out to some extent. When the ink warms up and is shaken they will redissolve. They may also begin to come out of solution if enough water in the ink evaporates, especially if the inks are highly saturated (in the chemical concentration sense - saturation in the color sense is a different phenomenon).

Notice that I put normal in quotes above. Many, many dyes when present in sufficient concentration in water will undergo a process called aggregation. This can be at the molecular level, i.e. two dye molecules start traveling around together as a unit, or the units can get quite large. If these units are large enough, they can become colloids, solids that are so fine that random thermal energy is sufficient to overcome the force of gravity so that they do not settle (colloids that Michael Faraday made in the mid-19th century are extant and at least of them haven't settled yet). At this point, one COULD call these solids pigments, but they behave quite differently from most materials that are made to be sold as pigments. They don't settle and if the particles are small enough, they are completely transparent. If the average size of said particles is in the nanometer range, they would today be called nanoparticles (although they were known and partially understood long before the term nanoparticle was invented).

Where it gets complicated is that there is no sharp dividing line between these colloidal materials and "real" pigments. There is a smooth transition between the states, so that a particular dye in a particular mix of water, surfactants, and other stuff may form something that is just a little bit bigger than a colloid as defined above and show some settling, yet still be of a particle size to move smoothly through a fountain pen nib. These intermediate particles might start showing some opacity both in the bottle and on paper, but still not behave like ordinary paint pigments that are large enough to lodge in the channels of a fountain pen. I suspect (but do not know) that some of the more opaque Noodler's inks (and maybe others) have particle sizes that fall in this range. Such inks will be more prone to settling and be more sensitive to water evaporation and thermal shocks, but as long as their solids resuspend on shaking, they should be safe for the average fountain pen. They may separate a bit in the pen over time (as noted with some Noodler's inks) but the motion of the pen will generally be sufficient to remix the inks.

It is possible for these "large colloid" inks to undergo a particular type of failure that can develop over time. In any colloid, there is some force present that is opposing the further growth of the colloidal particles. This can be either electrostatic (the particles all have the same charge and like charges repel) or the result of materials adsorbed on their surfaces that create a repulsive force via solvation effects (too complicated to explain here - you'll need to trust me on this one or a spend a good bit of time with a colloid science textbook reading about steric stabilization - the name itself is a misnomer in my opinion). If the almost non-colloidal particles are not full stabilized (this can occur for quite a number of reasons), then the particles may continue to slowly grow in the ink until they get to a size that they separate out too rapidly and either collect in the ink reservoir or form a film on the reservoir or feed channels. I have a new bottle of Noodler's Golden Brown that arrived this way. I cannot get the black component to come through the nib (broad and medium italics) of my Osmiroid 65 unless I have shaken the pen and rinsed the nib with water immediately before writing. I believe others have noted that Golden Brown tends to settle more than some other "near-bulletproof" inks (several of which I use regularly), but I think my bottle is passed being usable, at least in Osmiroid nibs. Note that my nibs are not clogged - the orangy-yellow soluble dye in Golden Brown comes through nicely (except I don't like its color at all).

At some point, colored particles do get too big to flow cleanly through a fountain pen. Many (but not all) paint pigments fall into this category. These are the pigments that Sean is referring to and no they should not be in fountain pen inks, nor do I think anyone deliberately puts them there. To summarize, the lowest maintenance inks are the ones with fully soluble dyes at a concentration low enough that aggregates do not get as large as nanometer sizes. These are your classic Waterman's, Herbin's, etc. as well as some of the Noodler's and Private Reserve inks. Others of the latter two brands and some others (e.g. certain of the newer Diamine inks I suspect) have high enough dye concentrations that they are more sensitive to temperature changes and evaporation but are still not colloidal. Others of the Noodler's inks, as well as the Japanese nanoparticle inks, are colloidal in part or in whole. Properly formulated and maintained they are still quite safe for fountain pens, but all bets are off if you like to boil or freeze your inks or mix them with the wrong other inks. Colloidal inks may age faster than fully in solution inks, and if they seem to be clogging pens or separating too much in your pens, you should toss them or use them in dip pens. Again, there is no sharp line between these categories, so at least some of the debate between dyes and pigments in fountain pen inks is moot. If it flows in your pen, it is safe to use, and if not don't keep using it. I'm sure every ink manufacturer understands at least the practical aspects of what I've described if not the detailed chemistry.

Sorry for the long discourse, but this is a more complicated subject than it looks, and I've only scratched the surface here. My chem Ph.D. is over 30 years old and I knew none of this until 10 years later when I went to work for a photographic company. I've been doing pigments, dyes, and dispersions ever since so I'm not making this up. Hope it helps.

Sholom

 

So now I'm left to wonder how this works in practice, by what process this can be replicated. The more I find out, the more questions I have.

 

.....I'm gonna have to run an Inksy RCT, aren't I? Aw, carp...

Edited February 2, 2016 by Miz Black Crow

[chewytulip]

  On 2/2/2016 at 6:19 AM, Miz Black Crow said:

Most also want to be used at high temperatures (>50^oC), though not all.

 

This might be the only part of this question that I can sort-of answer. Although those dyes "want" a high temperature, they actually work just fine at room temperature. I regularly use fiber reactive dyes on cotton fabric, and it's always at room temperature. Just needs to sit a while longer, usually. But you're right about a mordant - I still need soda ash.

[Miz Black Crow]

  On 2/2/2016 at 7:40 AM, chewytulip said:

  On 2/2/2016 at 6:19 AM, Miz Black Crow said:

Most also want to be used at high temperatures (>50^oC), though not all.

 

This might be the only part of this question that I can sort-of answer. Although those dyes "want" a high temperature, they actually work just fine at room temperature. I regularly use fiber reactive dyes on cotton fabric, and it's always at room temperature. Just needs to sit a while longer, usually. But you're right about a mordant - I still need soda ash.

I'm also assuming that ink has a higher dye concentration than a vat of fabric dye, though this may be incorrect. I wonder if higher concentration of dye would mean better/quicker cellulose reactivity, since more molecules may be available (even if conditions are less ideal)....?

[dcwaites]

Ok, you've gone into this in far more detail that I could. You might want to address your questions to FPNer Chemyst, who is either closely associated with Nathan, or is Nathan. It would be interesting to see how much information you could get, though.

 

However, he isn't the only ink maker to go down that route, as the PR Invincible inks are also cellulose-reactive.

[Miz Black Crow]

  On 2/2/2016 at 8:56 AM, dcwaites said:

Ok, you've gone into this in far more detail that I could. You might want to address your questions to FPNer Chemyst, who is either closely associated with Nathan, or is Nathan. It would be interesting to see how much information you could get, though.

 

However, he isn't the only ink maker to go down that route, as the PR Invincible inks are also cellulose-reactive.

 

.....You know I completely forgot about the PR Invincible inks?

 

The list of people I'd love to see get involved in this thread are quite a few--Pharmacist, Cyber6 (who's attempted ink-making from reactive dyes), yourself, Chemyst, ElsaB, KWZI, anyone who was involved in the Open Ink project from back in the day....

 

I hardly think Mr. Noodle would give away the keys to the inky kingdom, though, and I don't know how he'd feel about someone trying to engineer a parallel ink (though bulletproofness is not my aim; waterproofness is.) I kind of wish you could tag particular users and have it ping them, but I'll probably send out some polite requests for comments later.

[Witsius]

Richard Binder reports that there is a particulate in Noodler's bulletproof inks that gives them their namesake qualities. (link below) My own anecdotal experience seems to back this up. When I've used those inks, I've noticed a residue left behind that won't flush out with water. It has to be wiped off. It doesn't stain or anything, and it wipes off very easily. I can only describe this substance as a very fine "soot." However, I'm perfectly willing to admit that apart from one article written by a well respected and surely knowledgeable pen expert, and my own limited experience, I cannot say with any certainty how Nathan makes his bulletproof inks.

 

I suggest that unless Nathan Tardiff reveals to the world how he makes his bulletproof inks, we'll all just be speculating.

 

 

http://www.richardspens.com/?page=ref/pendoctor/4.htm

[amberleadavis]

Miz, if I may suggest ....

 

Year of the Golden Pig is waterproof and Fade Proof. BUT keep in mind that a lot of the waterproof inks are chalky.

As DCWaites explained right now, we don't have a perfect waterproof Cyan (the De Atramentis Turquoise is nice, but not perfect. I have not yet tried the R&K or Octopus).

 

The question I have for you, is HOW WATERPROOF does it need to be? You can mix almost any of the CYMK colors using Linda's charts and then add Ghost Blue to make it water resistant.

[Miz Black Crow]

  On 2/2/2016 at 5:08 PM, amberleadavis said:

Miz, if I may suggest ....

 

Year of the Golden Pig is waterproof and Fade Proof. BUT keep in mind that a lot of the waterproof inks are chalky.

As DCWaites explained right now, we don't have a perfect waterproof Cyan (the De Atramentis Turquoise is nice, but not perfect. I have not yet tried the R&K or Octopus).

 

The question I have for you, is HOW WATERPROOF does it need to be? You can mix almost any of the CYMK colors using Linda's charts and then add Ghost Blue to make it water resistant.

 

My understanding is that the highlighter inks don't play well with others in a mix, but I'm ordering some samples from Goulet soon (including Blue Ghost and YOTGP and several others), and we'll see how it goes. Right now I'm curious as to the chemistry, and the curiosity is almost as driving at this point as the desire for waterproof inks. (It would also be nice to be able to make my own blends and not rely on Big Ink, but that's a secondary concern.)

 

My waterproofness requirements for my inks are to leave legible text after an hour's soaking in tap water. Nothing unreasonable; I don't demand complete lack of ink movement or chemical resistance. Just insurance against spills or dropping a journal in a puddle

[amberleadavis]

I look forward to seeing your results.

[Miz Black Crow]

Well, since this thread hasn't seemed to turn up any answers yet, I'm going to have to get cracking on an Inksperiment. I intend to try the following, and would welcome any and all input on this experimental design. If you have any thoughts as to how to proceed, or any changes you would make to this design, PLEASE feel free to tell me! I won’t be insulted. I’m no chemist, and I may have some of the chemistry wrong. (My work is parascientific but is in the area of medicine, not fluid dynamics or hydrochemistry.)

 

If anyone knows of a good chemical way to bond dyes to paper that isn’t triethanolamine or sodium carbonate, PLEASE let me know. I’ve heard of using 2-picolene (2-methylpyridine), but I don’t have access to it.

 

Objective: To produce a dye-based, pen-safe, viable fountain pen ink, which boasts water resistance to the point of legibility after drip testing and soak testing. Resistance to other solvents (bleach, ammonia, .....) are bonuses but not required for this series of tests to be considered successful. The ink must remain stable in solution and remain waterproof over a period of no less than 6 months (with 6 months being considered "indefinitely").

 

Background: We know that there are multiple inks on the market that are cellulose-reactive (water-resistant), dye-based inks. We know that these inks are produced by chemistry, rather than the dark, dark magic which immediately comes to mind. We know that these inks are advertised as pH-neutral, however, pH neutrality is not a required aspect of the neoformulation.

 

Given a patent search, it becomes evident that many early dye-based permanent inks are the result of adding strong alkali solutions and/or strong salts to traditional dyes (Direct or Acid dyes). However, neither of these ingredients are particularly desirable in fountain pen ink in the modern era, due to the possibility of corrosion of stainless steel nibs. Likewise, volatile organic solvents are not desirable, especially due to the risks to manufacturers of working with VOCs.

 

Current, commonly-available fiber-reactive dyes include Procion MX dyes, which are not known to remain stable in aqueous solution for prolonged periods, Cibacron F dyes, which are of unknown longevity, and Remazon dyes. This last category of dye is particularly of interest to the inksperimentrix, since they are of a class of dyes (vinyl sulfone) known as bifunctional dyes; namely, they are reactive on two sites of the dye molecule (as opposed to monofunctional dyes, which are only active at one site). Remazol dyes are also known to be shelf-stable in aqueous solution and are in fact commonly sold in stock solutions.

 

These stock solutions are of particular interest to the inksperimentrix, accomplishing two very important goals. Firstly, they alleviate one inconsistency in inksperimentation: solution concentration. Secondly, the inksperimentrix absorbs less health-hazard risk when using stock solutions, since dyes are only health-hazardous when inhaled in powder form (and if she inhales a liquid, she has problems worse than whatever irritation inhaled dyes may cause).

 

Thus, a Remazol vinyl sulfone bifunctional dye solution shall be chosen as the dye upon which to base the initial ink formulation. A relatively visible color shall be used, such as red, to help with identification of issues such as SITB (S—t in the Bottle), precipitates falling out of solution, or other potential changes to the ink. (A waterproof red would also, selfishly, fill a hole in the inksperimentrix's current collection.)

 

However, questions remain as to how one may stabilize the ink, increase its reactivity to cellulose (if required beyond direct application with a pen), and how to cause whatever mixtures produced to be shelf-stable for multiple years.

 

Vinyl sulfone dyes are activated by the use of alkali agents (soda ash, or sodium carbonate, is a common activating agent; so is pot ash (a vague term for potassium-based salts such as potassium carbonate or potassium chloride). Soda ash seems less caustic, is more readily available at better prices, and shall be used in this experiment. Additionally, other binding agents such as triethanolamine have been suggested and used in other inks; triethanolamine shall be tested both in parallel and combined with sodium carbonate.

 

Glycerine shall be added as a flow modifier and humectant. For a surfactant (to reduce surface tension) a 1:100 (1%) dilution of Purpose hand soap shall be used. This will be added toward the end for FP testing to modify flow. Note: Triethanolamine acts as a surfactant and may reduce surface tension in a satisfactory manner on its own.

 

Experimental Design

 

Stock Solution Preparation

1. A “stock solution” shall be made involving 500mL of Sterile Water and a Remazol dye solution. The ink that has been purchased is Jacquard's Green Label Scarlet in a 2oz bottle. This procedure is written assuming ~50mL of dye solution will be used, for a total volume of 550mL.
2. Add Glycerine 5mL per 100mL of solution (per Pharmacist’s recommendation). Total volume 25 mL for 500mL; 27.5mL for 550mL.
3. Thymol shall be added at 2gtt:100mL (11gtt per ~550mL). This is an antimicrobial/antifungal. Hopefully it smells pretty.
4. Ink mixture shall be gently agitated to produce a uniform solution.

 

Preparation of Ink Samples for Controlled Trials

1. Ink shall be divided into 30mL containers (or 60mL containers with 30mL of solution) as follows:
   • Vial A: 30mL Stock solution without changes (CONTROL SAMPLE)
   • Vial B: 30mL Stock solution + Sodium Carbonate (0.5g – 1.5% w/vol)
   • Vial C: 30mL Stock solution + Triethanolamine (1g – 3% w/vol)
   • Vial D: 30mL Stock solution + Sodium Carbonate (0.5g) + Triethanolamine (1g)

 

Methodology for Testing of Ink Samples

 

Inks shall be tested at the following times:

• 1 hour
• 24 hours
• 72 hours
• 14 days
• 30 days
• 90 days
• 180 days

The methodology for examining and testing each vial shall be as follows:

1. Physically inspect each ink for problems: precipitates, SITB, etc. Note: Any SITB is to be treated with an additional 1-2 gtts of Thymol and monitored for additional S.
2. Prepare a color swab in the Inksperimentation Notebook using a Q-tip.
3. Prepare a writing sample (not for submersion) using a dip pen. Thoroughly clean and dry the dip pen between samples.
4. Prepare a water-swab-type writing sample using a dip pen. Thoroughly clean and dry the dip pen between samples.
5. On a separate piece of Rhodia paper, prepare six spaces, lettered by a know water-resistant ink (eg Old Manhattan Blackest Black). Label areas A - F.
6. In the spaces below the lettering, write a sample for each mixture: “60 minutes 60 minutes 60 minutes”
7. 50 minutes later, in the spaces below the above text, write a sample for each mixture: “10 minutes 10 minutes 10 minutes” .
8. 10 minutes after completion of the last writing sample, submerge the water resistance sheet face-down in a shallow dish of water. Leave submerged for 1 hour. Dry face-up on a paper towel.
9. During soak test, perform water-droplet tests on prepared samples. Allow ink to sit for 30s, then swab with a Q-tip to dry.
10. Record notable findings in the Inksperiment Journal: changes in color relative to baseline and/or control; water resistance (and changes therein) over time; etc. General properties such as bleed/feather, dry times, etc. can be tweaked later and are secondary to primary functionality (color & resistance to soak/drip).
11. Post above findings with associated photographs to this thread on the Fountain Pen Network forums.

 

Criteria for Discontinuation

 

When one or more of the following criteria are met, the ink formulation shall be discontinued for use, with the exception of the Control group (sample A):

1. Heavy precipitation of solutes leading to nonfunctionality of the ink.
2. Complete and utter loss of, or drastic change in, color relative to control. This is especially important in changes over time.
3. Absolute and total failure to resist water. Note: ALL THAT IS REQUIRED IS LEGIBILITY following exposures; total waterfastness is not mandatory.
4. Development of SITB which fails to respond to additional Thymol.

 

Any sample which fails in testing shall be emptied, its bottle cleaned and used to produce a new formulation or variant of a better-behaving formulation.

 

Areas to Consider Should Above Options Fail

 

• Dye-based inks tend to like salts. While high-salt solutions are not considered desirable for fountain pen use, small quantities of salts such as table salt (sodium chloride) may be considered. Sodium chloride solutions are commonly available at isotonic solutions of 0.9% (saline), or 90mg NaCl per mL of water; this may be halved or even quartered easily. In fact a 0.3% (1/3NS) solution would be easy to make by using 10mL of NS + 20mL sterile water. This solution would have to be tested for corrosive capability on steel nibs; a “sacrificial lamb” nib would have to be inserted and remain in a bottle for an extended period to prove lack of corrosiveness.
• Basic compounds could be used (for example, increasing the concentration of ink solutions) to raise pH, perhaps further activating vinyl sulphone dyes. Pot ash (potassium chloride) is one such compound. Sodium bicarbonate, or household baking soda, is a weaker base but could work as a substitute for sodium carbonate, IF the latter is a successful approach to inkmaking.
• Other fixatives, such as ProChem’s PRO Fix, are an option, but the simpler and wider-available the components, the more successful the ink will be (and the easier it will be for other inksters worldwide to acquire the components).
• Alternatives to Thymol include phenol itself (harder to acquire and a known carcinogen), Dowicil (harder to acquire in reasonable end-user quantities), salicylic acid (uncertain how this would play with alkaline dye activators), Germall Plus.

 

This inksperimental design is open to public comment, especially while I wait for Amazon-acquired components to arrive. Please please please leave any feedback or suggestions here.

Edited February 5, 2016 by Miz Black Crow

[dcwaites]

Is the Jacquard's dye a pure dye in solution? It's not already made up for textiles?

Otherwise, sounds good so far.

[amberleadavis]

As I recall, the Toucan inks used a dye which was pretty water resistant.

[Miz Black Crow]

  On 2/5/2016 at 9:58 PM, dcwaites said:

Is the Jacquard's dye a pure dye in solution? It's not already made up for textiles?

Otherwise, sounds good so far.

GREAT catch. A look at its MSDS reveals it involves dye, water and "Acedic acid" (sic?) 1.5%. It is unknown if the higher concentration of the dyes (not available on Amazon and therefore not purchased for this inksperiment), as may be more useful if larger batches are to be made, also contain acid, as the MSDS is more cryptic.

 

The vinegar may be used as a fungicidal agent, not to manipulate the dyes. Then again, they ARE pH sensitive, but activated by alkali, not acids. So who knows.

 

Inksperiment continues.

[Sasha Royale]

Noodler's makes a very fine product. In their place, I would be very shy about giving up a recipé.

[Miz Black Crow]

Update

Dyes have arrived, though not the activating agents (soda ash, triethanolamine). I’ve begun some simple experimentation and will have to adjust my plan due to dilution testing. (The original plan predicted 50mL:500mL water; this would not produce a viable ink. 1:1 or 3:2 may produce viability. Owning two bottles of dye, this brings total volume of ink available up to 4oz = 120mL + 180mL H2O = 300 mL total diluted ink.)

 

The dye in question is Jacquard Silk Dye (green label), Scarlet #712. This is a vinyl sulfone dye that comes in pre-mixed solution, along with acetic acid (presumably as a preservative).

 

So far I’ve done the following inksperiments:

• Dye at full concentration. This actually produced a quite viable and pleasant ink. It goes on a bright red and dries to a saturated scarlet. It’s an incredibly saturated red with reasonable flow out of the bottle. However, it offers minimal water resistance after 10 or 60 minutes on the page (test performed by running tap water for 1m on dried sample). A 24-hour test is underway but not expected to be successful. Dry time on Rhodia is in the 30-45 second range with a medium nib. It offers no shading to speak of. No feathering on Rhodia.
• Dye 1:1 Water (2mL:2mL). This offers similar color saturation with slightly more shading but absolutely no water resistance at all. Dry times – not tested. Feathering -- None observed. Bleedthrough -- none on Rhodia.
• Dye 1:1 Water (2mL:2mL) + ~1/12^th to 16^th tsp baking soda (1/3 to ¼ of 1/4tsp). Remember how earlier we said this dye is preserved with acetic acid, AKA vinegar? Yeah, this produced bubbles that caused a lot of volcano-style red ink coming out of the sample vial (~1mL lost). There was no change in water resistance (still barely legible after 1m of running tap water).
• Dye 10:1 isopropanol (70% rubbing alcohol). This paradoxically increases dry times. It would be expected that isopropanol would increase paper penetration and decrease dry times. This offers no change with water resistance.
• (Dye 10:1 70% isopropanol,)~ 1:1 with water. This dilution was done in the converter and didn’t change much. Diluted again 1:1 (now dye+isopropanol 1:2 water) produces a faint red line. This shades well but is too pale for my tastes. Dry time is ~15s on Leuchtturm, which is comparable to Rhodia.

Conclusions:

1. Vinyl sulfone dye alone is not sufficiently water resistant.
2. Isopropanol does not affect water resistance of the solution, and causes an odor.
3. Sodium bicarbonate (baking soda) does not induce dye fixation or increased reaction with cellulose.
4. Honestly, if you want a lovely red ink.... buy a bottle of this dye. You’ll get 60mL of beauty for $3.50 at your local craftsy store. If you want shading, dilute (and potentially mix); can generate >100mL ink if diluted. If you want water resistance.... I don’t have the answer for that yet.

Next round of testing

• Will attempt (Water 3:2 Dye)10:1 isopropanol : 1 glycerine (by vol) to modify flow & test for viability of ink (ignoring water resistance). The purpose of the dilution is to improve shading; the glycerine and isopropanol to modify flow and dry times. In a 5mL sample vial this will break down to: 3mL H2O, 2mL dye solution, 0.5mL isopropanol, 0.5mL glycerine. Shall be modified for flow during testing.
• Upon arrival of dye fixatives (ethanolamine, soda ash) later this week, will inksperiment with adding these to ink in small quantities before proceeding to larger-volume testing. Since water resistance is the primary aim, this will be to the point of saturation in solution for initial testing.

Inksperiment continues. (Photos to come.)

[dcwaites]

What mordant is supposed to be used by the dye when used on textiles? soda ash, triethanolamine ??

 

Acetic acid would be more of a biocide, ascorbic tends to be used as a preservative at least in food dyes. Which is understandable, as you really don't want vinegar-flavoured cup-cakes.

[Miz Black Crow]

  On 2/10/2016 at 1:00 AM, dcwaites said:

What mordant is supposed to be used by the dye when used on textiles? soda ash, triethanolamine ??

 

Acetic acid would be more of a biocide, ascorbic tends to be used as a preservative at least in food dyes. Which is understandable, as you really don't want vinegar-flavoured cup-cakes.

Jacquard recommends soda ash, which is a strong base; baking soda is a weak base, so it may not act in the same way on the dye compound. Triethanolamine was suggested in another thread but may not work; we'll see what happens when it arrives. Hopefully it doesn't take my eyebrows off.

 

As for the vinegar, I meant "biocide" and typed "preservative", so I think we're on the same page, but I hadn't considered when they might use acetic vs ascorbic!

 

I'm very curious as to what happens when sodium carbonate (soda ash) is added, whether it will bubble and froth too (like the sodium bicarbonate did). I hope not :-/