Is Noodlers Black pigmented or dye-based?

[BrassRatt]

On microscopy -- 

Of the inks that are "pigment fountain-pen" inks, sometimes called "nanoparticle" inks, what is the usual range of particle sizes?  Do we have any reference for that?

 

Even a very general range would inform us whether we should expect to see the particles at 100x or 400x magnification, or not. 

 

[BrassRatt]

Does anyone around here have (access to) a lab centrifuge?  (I don't.). It seems that pigment particles are likely denser than water, and thus likely to settle when centrifuged. 

 

Centrifuging some  known pigment inks and the controversial Noodler's Black, for comparison of behavior, might give us useful information. 

 

Or has someone tried this and I just didn't find it? 

 

[OCArt]

1 hour ago, BrassRatt said:

Does anyone around here have (access to) a lab centrifuge?

I've got a salad spinner!

[dipper]

24 minutes ago, OCArt said:

I've got a salad spinner!

Since reading the hilarious topic about pens in salad spinners (elsewhere in these forums) I now often use my spinner to remove water from pens after rinsing.  I calculate a maximum centrifugal acceleration of 200"g" can be achieved.

..... But only for a few seconds, then my motor arm goes numb and falls off.

 

I think electically driven centrifuge machines in laboratories, used to separate suspended solids from a liquid, are generally left running for longer than that.

[arcfide]

Another bit of reading for the research pile:

 

Substantive dye - Wikipedia

 

Something else has been commented on or claimed: it has been remarked by Nathan at some point, IIRC, that the saturation of the dyes is so great that at times the dyes can no longer remain in solution and will precipitate out. 

 

So, I guess, one thing that might be tried is a dilution of Noodler's Black and a thorough shaking, to see whether the dyes are different then versus in their highly concentrated state. 

 

Another situation at play here, is that if Noodler's is getting a particular product that is called a dye, and if Nathan is basing his own information on the information of the chemical supplier (very possible), then it is possible that even Nathan may not be fully aware of the exact properties of the ink. 

 

 

[TSherbs]

I appreciate the contributions here. I have been learning some things! 

[arcfide]

I feel like this is a touch off topic, but I can't hold my fingers back. 😉 

 

When it comes to functional claims made by Noodler's, I've found them to be generally accurate but for one main issue. That is my experience with their water solubility. Nathan has said before that various Noodler's inks should wash off with water even if they dry up on plastics, and that they should only really permanently affix themselves to cellulose fibers. 

 

Even allowing for "normal staining" of some Noodler's inks which can be considered, I just don't find this to be true for most of Noodler's bulletproof inks that I have tried. For example, Nathan has said, even giving a demonstration, that "Noodler's Black will wash off of fingers and smooth surfaces with just water." Well, it certainly doesn't wash off of fingers in any degree that I would consider as actually washed off (maybe I'm misremembering that claim). And my experience of these inks in plastics is that it just doesn't hold up there, either. Others have said that things wash of well enough, but to me, washing off implies that the ink should wash off of plastics without mechanical means being necessary to dissolve or remove the components, and that means all the components, and that includes, IMO, water pressure. That means you should have to rub or rinse with any force in order to get the ink off the plastic. But in my experience, Noodler's inks often leave a film behind which doesn't wash off, and very often leave parts of the dye around which doesn't wash off, even though it can be rubbed off gently. 

 

Neither of these cases counts as actually cleanly rinsing from a pen. Indeed, I would consider many of the dye-based Noodler's inks no more, and sometimes less, low maintenance than pigmented inks, because they tend to cling in the same way. I would not have confidence that Noodler's bulletproof inks would rinse out of my Lamy, Platinum, Sailor, or Pilot feeds if the ink dried up in those pens, and that to me is the whole point of a water soluble, "rinses clean" claim. I don't even get that when the ink hasn't dried on the pen. 

 

This is probably the claim made by Noodler's that annoys me the most and that, to me, undermines the trust of the Noodler's information sheets. In everything else, I haven't been able to show inconsistent behavior to the claims made. This makes me inclined to at least believe Nathan when he says that they are dye-based, but I think it also warrants a deeper investigation if someone wanted to take that one, because it's also not completely obvious that there couldn't be something here going on that would potentially invalidate that claim with respect to what we think of when we think of dye-based inks. 

[yazeh]

On 3/14/2023 at 9:19 AM, LizEF said:

IMO, this is really good evidence both for "not pigment" and "is cellulose-reactive".

I doubt it. Unless the pants are polyester! Btw those images are fantastic

I have used Noodler's cellulose reactive inks to patch up bleach splotches on a couple of shirts  but they have to be cotton

 

On 3/14/2023 at 2:08 AM, Mangrove Jack said:

I dropped an open bottle of Noodler's Black Bulletproof ink and significant quantities of ink splashed onto my white trouser and white wall. 

 

Using a sponge, soap and water I got all the ink off the wall and no stain remains. Also, after a good overnight soaking in laundry detergent and a machine wash my trouser has only the mildest of stains and can still be well used for official functions.

 

My guess is that if the ink had pigments in it to make it permanent it would not have washed off a white wall and white cloth this easily/well. 

 

 

You're lucky. I have traces of Noodler's cellulose reactive inks, on one of my cotton Tshirts, and even there's a splash somewhere on the bedcover, that no matter of washing has made a dent into it. Were your pants 100% cotton? Or a mix?

[LizEF]

57 minutes ago, yazeh said:

I doubt it. Unless the pants are polyester!

Pigment should have stained both - though we don't know how quickly it was removed.  That it slightly stained the pants, suggests it may be cellulose-reactive but was gotten to in time to prevent most of the reaction.  (At least, this was my thinking.)

 

58 minutes ago, yazeh said:

Btw those images are fantastic

Thanks!

 

59 minutes ago, yazeh said:

I have used Noodler's cellulose reactive inks to patch up bleach splotches on a couple of shirts  but they have to be cotton

Clever!  Now I want to try this on a grey shirt I have...

[LizEF]

11 hours ago, arcfide said:

So, I guess, one thing that might be tried is a dilution of Noodler's Black and a thorough shaking, to see whether the dyes are different then versus in their highly concentrated state. 

Hmm.  When I'm done with the current slide, I'll find a bottle (I have no empty sample vials at the moment), put in a drop of Noodler's Black, then several drops of distilled water, mix thoroughly, and then put a drop of that on a slide to see if the "grains" are still there or have disappeared.

[inkstainedruth]

11 minutes ago, LizEF said:

Pigment should have stained both - though we don't know how quickly it was removed.  That it slightly stained the pants, suggests it may be cellulose-reactive but was gotten to in time to prevent most of the reaction.  (At least, this was my thinking.)

 

Thanks!

 

Clever!  Now I want to try this on a grey shirt I have...

Yeah.  I have a purple shirt that has a fleck of bleached out color on it -- probably from using hydrogen peroxide in the laundry from after my husband's abdominal surgery (almost 3 years ago at this point... 🤬 -- we should have sued the surgeon into oblivion at the time...).  

Anyone have any idea of what Noodler's purple inks are cellulosive reactive? 

Ruth Morrisson aka inkstainedruth

[TSherbs]

2 hours ago, arcfide said:

I feel like this is a touch off topic, but I can't hold my fingers back. 😉 

 

When it comes to functional claims made by Noodler's, I've found them to be generally accurate but for one main issue. That is my experience with their water solubility. Nathan has said before that various Noodler's inks should wash off with water even if they dry up on plastics, and that they should only really permanently affix themselves to cellulose fibers. 

 

Even allowing for "normal staining" of some Noodler's inks which can be considered, I just don't find this to be true for most of Noodler's bulletproof inks that I have tried. For example, Nathan has said, even giving a demonstration, that "Noodler's Black will wash off of fingers and smooth surfaces with just water." Well, it certainly doesn't wash off of fingers in any degree that I would consider as actually washed off (maybe I'm misremembering that claim). And my experience of these inks in plastics is that it just doesn't hold up there, either. Others have said that things wash of well enough, but to me, washing off implies that the ink should wash off of plastics without mechanical means being necessary to dissolve or remove the components, and that means all the components, and that includes, IMO, water pressure. That means you should have to rub or rinse with any force in order to get the ink off the plastic. But in my experience, Noodler's inks often leave a film behind which doesn't wash off, and very often leave parts of the dye around which doesn't wash off, even though it can be rubbed off gently. 

 

Neither of these cases counts as actually cleanly rinsing from a pen. Indeed, I would consider many of the dye-based Noodler's inks no more, and sometimes less, low maintenance than pigmented inks, because they tend to cling in the same way. I would not have confidence that Noodler's bulletproof inks would rinse out of my Lamy, Platinum, Sailor, or Pilot feeds if the ink dried up in those pens, and that to me is the whole point of a water soluble, "rinses clean" claim. I don't even get that when the ink hasn't dried on the pen. 

 

This is probably the claim made by Noodler's that annoys me the most and that, to me, undermines the trust of the Noodler's information sheets. In everything else, I haven't been able to show inconsistent behavior to the claims made. This makes me inclined to at least believe Nathan when he says that they are dye-based, but I think it also warrants a deeper investigation if someone wanted to take that one, because it's also not completely obvious that there couldn't be something here going on that would potentially invalidate that claim with respect to what we think of when we think of dye-based inks. 

 

I have a different definition of "washes off" when it comes to fountain pen inks, especially when having dried or put in a narrow tube like a pen barrel or a converter: I think that expecting one to agitate the cleaning solution or to apply pressure with a cloth or Qtip is reasonable. Noodler's Black clearly does not simply "rinse clean" from a converter (rinsing is hardly even possible, except with a syringe) and many, many even non-permanent inks do NOT "rinse clean" from hands, clothing, other fabrics and surfaces, etc. 

[yazeh]

2 hours ago, inkstainedruth said:

Yeah.  I have a purple shirt that has a fleck of bleached out color on it -- probably from using hydrogen peroxide in the laundry from after my husband's abdominal surgery (almost 3 years ago at this point... 🤬 -- we should have sued the surgeon into oblivion at the time...).  

Anyone have any idea of what Noodler's purple inks are cellulosive reactive? 

Ruth Morrisson aka inkstainedruth

Polar Purple 

Tchaikovsky (though it's fluorescent) . 

I have a sample of Polar Purple, if you want I can sent it to you

[inkstainedruth]

I suspect that (from what I've seen of it) Polar Purple isn't going to be dark enough a purple.  But thanks for the offer....

Ruth Morrisson aka inkstainedruth

[dipper]

22 hours ago, BrassRatt said:

On microscopy -- 

Of the inks that are "pigment fountain-pen" inks, sometimes called "nanoparticle" inks, what is the usual range of particle sizes?  Do we have any reference for that?

 

Even a very general range would inform us whether we should expect to see the particles at 100x or 400x magnification, or not. 

 

As one reference point, below are some images of a pigment ink that has larger particles than fountain-pen "nano" inks. This is Winsor&Newton Calligraphy Black. The particles are clearly visible at 100x magnification.

My size estimate (detailed below) is a mix of all sizes from 0.7 micron to 7 micron.

 

 

THE EXPERIMENT

 

Glass cover-slip placed with one edge resting in contact with a microscope slide and the opposite edge raised up by the thickness of a piece of 90gsm copier paper. Ink name written on the paper in 4B pencil.

Ink then pipetted onto edge of cover-slip until the wedge-shaped space under the slip was filled with ink.

 

 

All images below are with the microscope at 100x magnification. Phone camera was supported above the eyepiece by resting onto an old 35mm camera microscope adaptor. Illumination is from below = "transmitted" light.

 

In the first image little dark patches are clearly seen. That's not pigment particles though. This is the plain white paper seen in transmitted light...

 

And here is one of the 4B pencil lines of the text written on the paper...

 

Here is the ink! Dark line at right of image is the edge of the cover slip that is resting on the microscope slide...

 

Moving slightly across the cover-slip to an area where the ink layer is deeper...

 

And at about 1/3 of the way across the ink layer is so thick that the dim image is nearly impossible to capture. The white spot is an air bubble I think...

 

After a distance of blackness we reach the edge of the cover slip that is resting on the paper slip. That edge is a fine vertical line in the image below. I interpret the crisp black edge as a layer of ink between the cover slip and the paper, and the fuzzy patch as ink below the paper. The halo of dark speckles is not ink. That is the white paper seen in transmitted light.

 

What size are the black pigment particles seen above?

We need a reference particle of know size.....?

.... ouch! ... Draw a drop of dipper blood and place on a second slide with cover-slip and paper - as done with the ink.

 

From Wikipedia..

A typical human red blood cell has a disk diameter of approximately 6.2-8.2 µm and a thickness at the thickest point of 2-2.5 µm and a minimum thickness in the centre of 0.8-1 µm, being much smaller than most other human cells.

Those red blood cells look about the same size as the very largest of the ink pigment particles. The ink has many smaller particles, down to the smallest sizes visible at 100x. I estimate those smallest visible ink pigment particles are about 1/10 the size of the bigger chunks. (The range of sizes and presence of the larger chunks makes this ink decidedly NON-nano.)

Using the Wikipedia size for red blood cells, and my estimates of relative sizes, the calculated result is that W&N Calligraphy Black contains pigment particles at all sizes from 0.7 micron to 7 micron. Sizes smaller than 0.7 micron may be present - but not visible in this test.

[TSherbs]

Dipper, that is very cool! I really appreciate your interest and time and effort and thoughtfulness about the topic here. 

[dipper]

Thanks @TSherbs. I hope to have time to do the same tests with Sailor Kiwaguro soon - a "nano" ink.

 

Started with non-nano to be sure of observing something more than grey mist!

[LizEF]

1 hour ago, dipper said:

Thanks @TSherbs. I hope to have time to do the same tests with Sailor Kiwaguro soon - a "nano" ink.

 

Started with non-nano to be sure of observing something more than grey mist!

Should be interesting.  My images of Kiwaguro didn't show individual particles, though at the time, I was just looking for interesting images and didn't try going to 400x or 1000x to see if I could find particles.

[LizEF]

And, FWIW, here's Noodler's Black again, at 400x (this means a 40x objective with a 10x eyepiece) with scale added in.  The grid is 100µm x 100µm, and the scale is 100µm divided into 11 segments (I usually do 330µm divided into 11 segments of 30µm each and forgot to change the segment count, so we get a weird number).  As you can see, I'd have to get out the oil and view it at 1000x (100x objective) to come close to estimating particle size.

 

 

And as far as I can tell, the ink hasn't changed appearance on the slide since day 1 - once it set it place, it hasn't moved or morphed.

[TSherbs]

Awesome, thanks Liz.