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

[Miz Black Crow]

Deleted duplicate post, because mobile view is irksome.

Edited February 10, 2016 by Miz Black Crow

[dcwaites]

Deleted duplicate post, because mobile view is irksome soul-destroying.

 

There, fixed that for you.

[Miz Black Crow]

 

Deleted duplicate post, because mobile view is irksome soul-destroying.

There, fixed that for you.

 

:lticaptd: :lticaptd:

 

...I had to open my laptop to include these smilies in my reply, because when I tried to go from "fast reply" to something that would include smilies on my phone, my phone tried to recreate the desktop experience of FPN... excluding smilies. And now I can't get it to go back to Mobile view.

 

The things we do for love...

 

By the way, I made a mix last night of 3mL water : 2mL dye : 0.5mL glycerin : 0.2mL isopropyl : 1 drop Thymol. HOLY COW does Thymol have a strong scent at this concentration! I wrote in my journal last night before bed and the page still smells pleasantly of thyme (working with the bottle actually gave me a touch of headache and my hands smelled like thyme all night). The ink is a very vibrant red, not much shading. No water resistance to speak of, but we knew that going in. Inksperiment continues.

[Miz Black Crow]

UPDATE

The soda ash (sodium carbonate) I was awaiting arrived today right before I left for work. I wound up mixing up a 5mL vial of the following components in the parking lot outside of work: Soda ash ~1.5mL to Remazol stock solution ~3.5mL. The idea was to include more sodium carbonate than would be stable in solution, to produce a solution saturated with the carbonate (ie unable to dissolve any more soda ash). This was observed by the fact that a solid portion of the carbonate remains in the bottom of the vial. (Adding dye solution, which contains acetic acid, to the salt did produce some bubbling but nowhere near as much as was expected or was observed with the sodium bicarbonate [baking soda]).

 

The resultant ink was then loaded into a fountain pen, with the following results:

• Color: While the ink continues to lay down on the page as a beautiful scarlet red, when dark, the color is now a red-black, almost a dead ringer for Noodler’s Red-Black, in fact (with less shading).
  
• Behavior: No significant change from pure Remazol other than color variation (as above).
  
• Waterfastness: At 10-60m after mixing, the ink exhibits no significant change in water resistance from pure Remazol dye alone. Despite some very apparent ongoing chemistry once upon the page (as evidenced by color change), the ink still fails a 60s running water test (10m dry time) and a drip test at 20m dry time. 60m tests are impractical at this time, as I’m currently in class renewing one of my work certifications.

The next components to arrive will be Glauber salts and triethanolamine; I intend to try 4 parallel inks: (dye + salt); (dye + triethanolamine), (dye + soda ash + Glauber salt), (dye + triethanolamine + salt). If all of these fail to provide significant water resistance, I intend to try a 5th formulation: (dye + soda ash + triethanolamine +salt). I believe that the salt may be an important component involved in binding the dye to the cellulose. It is also a pH neutral salt, which, if it is successful on its own, may be what allows Noodler’s to be pH neutral.

 

For those concerned about corrosion, note that Glauber’s salt is Sodium Sulfate, which is used in the dyeing process to assist binding and is used in order to prevent corrosion of metals; it appears that most of the corrosion involved when metal contacts table salts is from the chloride component, not the sodium component. However, to be safe, if becomes apparent that sodium sulfate is necessary to the waterfastness of the ink, I will leave a nib partially submerged in an ink solution containing significant quantities of sodium sulfate to ensure it does not corrode nibs.

 

Inksperiment Continues.

[dcwaites]

If you want to sacrifice nibs to science, you can get batches of 5 or 10 chinese #6 nibs on eBay.

[Miz Black Crow]

Forgot to post this after I wrote it Here's an update from +- a week ago....

 

Update

 

Glauber’s salt arrived yesterday. I built a quick mix using dye stock solution and Glauber’s salt beyond maximum concentration (eg with precipitate).

 

Not only does this mix fail to resist water after 10 minutes dry time, the precipitate formed a crystal which attached to the bottom of the vial and was extremely difficult to remove (water, isopropyl soaks were ineffective; it required the equivalent force to icebreaking with a chopstick to remove ). Even when combined with soda ash it was ineffective at resisting water.

 

Glauber’s salt may be necessary in some formulations for whatever reason but it is not to aid Remazol dyes with water resistance.

 

The next arriving component will be triethanolamine. If this fails to produce water resistance, I may have to either do more research on activating agents or else attempt inksperiment with a different class of dye component.

 

Inksperiment continues.

[Miz Black Crow]

Update

 

TL;DR: This mix is the first success I’ve had with water resistance, but it comes at the cost of feather and bleed. The question is whether I can accomplish the former and also mitigate/eliminate the latter.

 

Triethanolamine arrived last night. I would have had time for more serious testing if I had realized this before 11pm. As it is, I’ve had time only to formulate one preliminary batch of ink.

 

Triethanolamine (TEA) is a carbon-based surfactant and penetrant, consisting of a carbon atom with three ethanol groups (triethanol-) and an amino group (-amine). The idea behind it, as I understand it, is that the ink bonds with the TEA, which also binds to paper on a separate binding site, though I don’t know which aspect allows it to bind to which reagent. It's also a weak base with a pH of 10-11, though having used stronger bases (soda ash), I'm pretty sure this has nothing to do with functionality.

 

It's a common ingredient in cosmetics-making, and comes in a liquid formulation, which apparently can and does freeze at low temperatures and required rewarming. Once warm and fluid it becomes a thick, viscous liquid. I added ~0.5mL of this liquid to ~3mL of Remazol dye solution and began testing. I then loaded this into a pen and began testing.

 

Last night I only had time to do a water resistance test, which was very promising compared to control samples. This is the first bit of success I’ve had with inducing water resistance.

 

The sample was written on Rhodia dot paper, allowed to dry for 10 minutes, then placed in a kitchen sink and placed under a running faucet for 60 seconds in a manner similar to previous control trials. The mix held up fairly well to this torture testing, remaining distinctly legible, although faded, where control samples had washed away almost entirely.

 

The trade-off to using triethanolamine appears to be that it induces feathering, even with a medium nib, on Leuchtturm. It also bleeds through on occasion, and when it does it usually goes into the following page. In addition, the mixture produces some ink leak into the cap in the Levenger L-Tech I’ve been testing the ink with. (Those familiar with the L-Tech will note that the cap finial is screw-off, which permits ink leak out of the pen....)

 

I’ll have to attempt to balance penetration and surface tension with water resistance. Tonight I intend to balance the triethanolamine with some glycerin to see if that can reduce flow while retaining penetration / water resistance.

 

I also intend to test triethanolamine + soda ash to see if there is any form of multiplicative effect on water resistance. (Remembering the darkening effect soda ash has on the dye component, I may use only a small amount, and I honestly don't think it will change anything but it's worth a shot.)

 

Inksperiment continues with head high and a glimmer of hope in the eye.

[onotopen]

Hi

 

I don't normally visit this area of the the Forum, so please forgive me if this is all old hat...

 

Goulet Pens did an interview with Dante Visconzi in which he discusses ink, although the main thrust of the talk was about Vacuum Fillers.

 

(Davyk put me onto it in relation to Vac Fillers.)

 

In it he mentions the four main ingredients including Gum Arabic which is used as a thickener (it may be that because it's water-soluble this may not be very good for 'waterproofness') I throw it into the pot for what it's worth...please feel free to throw it out again !

[Miz Black Crow]

Hi

 

I don't normally visit this area of the the Forum, so please forgive me if this is all old hat...

 

Goulet Pens did an interview with Dante Visconzi in which he discusses ink, although the main thrust of the talk was about Vacuum Fillers.

 

(Davyk put me onto it in relation to Vac Fillers.)

 

In it he mentions the four main ingredients including Gum Arabic which is used as a thickener (it may be that because it's water-soluble this may not be very good for 'waterproofness') I throw it into the pot for what it's worth...please feel free to throw it out again !

 

Thanks for the video! It's a really cool vid! As for the gum arabic, it and glycerine seem to have basically the same function, to thicken the ink and prevent spread. (The problem I'm working on now is actually related to this; triethanolamine increases water resistance but also induces spread, feather etc.)

 

He does make me wonder whether an acidic mix would work better than a basic mix, though. Hmmmm....

[Tayanna]

Miz Black Crow,

 

How is the inksperiment going? I've loved reading up on what you are doing and hoping to here more results and thoughts from you.

 

I think I want to join in on the inksperiment to see if we can't collaborate to the end goal. Cheers!

[Miz Black Crow]

Miz Black Crow,

 

How is the inksperiment going? I've loved reading up on what you are doing and hoping to here more results and thoughts from you.

 

I think I want to join in on the inksperiment to see if we can't collaborate to the end goal. Cheers!

 

Sorry for the lack of new data!

 

I discovered after posting my last update that the feathering and bleedthrough induced by triethanolamine (admittedly at 10% concentration by volume, which is rather high) was wholly unacceptable. Other than trying adding Jacquard's own Dye-Set Concentrate to the dye (which ended in predictable disaster and crazy clumpiness), I haven't tried anything new. I can't even get Procion dye to bond to cellulose within 10 minutes enough to withstand 60s of running tap water, so I'm pretty much all out of ideas at this point. The only other thing I can think of is finding some other kind of penetrant to push the ink deeper into the paper (replacing triethanolamine), but honestly, I don't have the dosh right now to buy ANOTHER component that might not help. This patent ( https://www.google.com/patents/US5141556 ) suggests using some substances, which turn out to be relatively expensive, and my chemistry mojo isn't strong enough to work out whether any of it is safe to bring into my house.

 

That being said, I've moved laterally, into making the prettiest inks that I can with the items on hand. I've been inksperimenting with various mica powders and colors/dilutions (I bought a couple more bottles of Remazol dyes, and I've had some good results with colors!) When I have something solid I'll show it off in the Inky Recipes section.

 

I suppose I could try a solution using less triethanolamine and see if I can get penetration without feather/bleed.... Hmmm. Also I could try adding other surfactants (dish soap >> Purpose hand soap, btw, which also induces feathering on its own, and does not improve waterfastness).

 

Do YOU have any ideas how to go forward? Since none of my additives have worked with Remazol or Procion dye to achieve waterfastness (other than triethanolamine, which broke the ink), I'm left to marvel at Noodlers' dark, dark magic and be in even more awe than I was when I started.

[thorn]

I experiemented with textile dyes without luck a few years ago. The textile dyes break down quickly from what I remember. I wonder if the water proof ink is pigment based? Think Platinum Carbon Ink.

Edited March 6, 2016 by thorn

[Miz Black Crow]

I experiemented with textile dyes without luck a few years ago. The textile dyes break down quickly from what I remember. I wonder if the water proof ink is pigment based? Think Platinum Carbon Ink.

 

Pigment inks work, but the risk with them is pigment size and aggregation, and the sensitive channels in FP feeds. Then again, the Document inks from DA are pigment inks. Worth considering. I've also been toying around with pigment in a dye, which is a REALLY interesting setup (think of the Shimmertastic line, or the 1670 series of inks). But Noodler's is confirmed to be dye-based, not pigmented, so it's definitely possible to achieve water resistance with dyes. The questions that remain are, which dyes, and how?

[thorn]

 

Pigment inks work, but the risk with them is pigment size and aggregation, and the sensitive channels in FP feeds. Then again, the Document inks from DA are pigment inks. Worth considering. I've also been toying around with pigment in a dye, which is a REALLY interesting setup (think of the Shimmertastic line, or the 1670 series of inks). But Noodler's is confirmed to be dye-based, not pigmented, so it's definitely possible to achieve water resistance with dyes. The questions that remain are, which dyes, and how?

 

I wonder where one would get pigments that are really small?

 

Where is the info on Noodler's being dye based? I have read on the forum people talking about cellulose dyes, but nothing on Noodler's site. At least what I have seen in the past.

[Tayanna]

Miz Black Crow,

 

Hmn, I am wondering if a weaker surfactant would be better. Maybe it would allow the ink to bond with the paper better and should feather less because it would have a slightly higher surface tension.

I'll run some ideas by my O-Chem professor and see if we can't come up with a few ideas.

[dcwaites]

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.

 

...

 

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. )

 

 

...

 

I just thought I would go back to basics, and did a Google Search on "chemistry of cellulose reactive dyes"

 

Are any of the links that come up helpful?

Edited March 7, 2016 by dcwaites

[WirsPlm]

I suppose I could try a solution using less triethanolamine and see if I can get penetration without feather/bleed.... Hmmm. Also I could try adding other surfactants (dish soap >> Purpose hand soap, btw, which also induces feathering on its own, and does not improve waterfastness).

 

Don't use dish soap, it will mess up your results, it's not a pure surfactant and has things to penetrate and remove stains/grease. I use Kodak PhotoFlo, which I found for a reasonable price on eBay.