Chemistry Of P51 And Superchrome Ink

[Albus]

P51 and superchrome ink is infamous for dissolving celluloid, causing corrosion and clogging.

 

I believe the following link is the receipe for P51 ink.

http://www.fountainpen.it/images/f/f7/Patent-US-1972395.pdf

 

Listed are the ingredients

Ammonium vanadate

Thymol

Phenol

Ethylene glycol

Water

 

Ammonium vanadate is soluble in water at 4.8g per 100mL, which is not really very soluble

It is even more soluble in alkaline solutions ie higher pH. Hence, this accounts for the fact that both inks above have pH = 12.

 

Ethylene glycol is used to keep the pen moist but I believe celluloid is soluble in it. There is mention of isopropyl alcohol, they both do the same in keeping the pen moist but it has the additional benefit of making the ink dry faster ie it is more volatile.

 

Ammonium vanadate is an interesting compound. It is oxidative and the product of its reduction can be insoluble. (vanadate is reduced when it oxidise another substance). And the primary purpose of using ammonium vanadate is because it will be reduced by oxygen in air to form a insoluble salt and deposited permanently on paper.

 

Most interestingly is that ammonium vanadate being a oxidising agent, particulary in alkaline solution, can oxidise silver to silver ions and these silver ions by react in such a way (i think) to form insoluble salts. So it will corrode silver. For gold, i am not too sure but i think it will take a lot longer.

 

So the corrosive property of the ink is threefold,

1. ammonium vanadate = oxidation of silver, forming insoluble salts that clog

2. ammonium vanadate = forms insoluble salts inside of pen

3. Ethylene glycol / ispropyl alc. = dissolves celluloid.

 

 

Very interestin chemistry

 

The patent also mentions the use of potassium ferrocyanide, which interesting is more soluble than ammonium vanadate at 28.9g per 100mL. But it is less effective permanent and requires the use of about 10 times more by weight than ammonium vanadate.

 

I hope to see someone use both ammonium vanadate and potassium ferrocyanide to recreate the inks. Possibly with and w/o the use of isopropyl alc.

Edited October 7, 2013 by Albus

[amberleadavis]

Thank you for the information.

[inkstainedruth]

Interesting. I didn't download the .pdf link (not yet, anyway -- but I might), but if I understand what you're saying (and my high school chemistry is both really rusty and -- as I recall -- not *nearly* as interesting), it sounds as if Superchrome is/was very alkaline *and* possibly having some iron gall component -- which is weird because *that* would make it acidic....

If this stuff was as corrosive to celluloid as it sounds, it's no wonder Parker started making pens out of Lucite.

Ruth Morrisson aka inkstainedruth

[OcalaFlGuy]

Ruth,

 

More specifically, they made the Lucite pens to be able to handle that ink. (The ink beget the pen.)

 

The major marketing push of those 2 inks was that they dried much faster than all the other inks. Parker knew celluloid would not work with those inks.

 

I think it may be David Nishimura's site that has some pics of sterling silver P-51 breather tubes eaten up by Superchrome and it's pretty gruesome. While some would argue to the contrary, I suspect it even eats some of the plating off the P-51 fillers.

 

Both are Exactly Why I say not to worry about putting any modern ink in a 51.

 

Bruce in Ocala, Fl

[FarmBoy]

Old patents sure are interesting. They often leave one thinking "now what are they really doing".

 

Any working proposals the formulations used to get the different colors?

[Dan Solomon]

Very interesting! Thanks for sharing !

[Wheatflower]

  On 10/9/2013 at 1:32 PM, FarmBoy said:

Old patents sure are interesting. They often leave one thinking "now what are they really doing".

 

Any working proposals the formulations used to get the different colors?

 

Someone needs to 'obtain' the patent info for Parker Penman Sapphire ink; then the interested people on this forum could sponsor a clandestine lab to manufacture it and distribute it on the black market.

 

They can call the project..... Inking Bad.

[Albus]

  On 10/9/2013 at 5:12 PM, Wheatflower said:

 

Someone needs to 'obtain' the patent info for Parker Penman Sapphire ink; then the interested people on this forum could sponsor a clandestine lab to manufacture it and distribute it on the black market.

 

They can call the project..... Inking Bad.

 

Well, if you can get the patents or the recipe someone can recreate it.

 

As pharmacist had done with the iron gall ink.

[psfred]

I don't believe those are the inks that became Superchrome, as most Superchrome or P51 inks are NOT water resistant and do not change color like iron gall inks. That is what the Ammonium Vanadate was for in the inks, to act like ferrous tannate and precipitate into insoluble compounds on paper.

 

P51 and Superchrome inks contain around 20% isopropyl alcohol in order to make them dry quickly -- dry writing with wet ink! -- and the alcohol is what eats celluloid. The high pH was to make the metallic dyes soluble, as these were "supersaturated" inks like Noodler's are today.

 

I don't think there is any ink on the market currently that damages pens like Superchrome does -- indeed, in 1956 Parker took Superchrome off the market due to the damage it did to even Parker "51"s, notably corroded breathers in the Aerometrics and serious clogging issues. Great inks, but troublesome in actual use form many.

 

Peter

[Albus]

  On 10/20/2013 at 9:35 PM, psfred said:

I don't believe those are the inks that became Superchrome, as most Superchrome or P51 inks are NOT water resistant and do not change color like iron gall inks. That is what the Ammonium Vanadate was for in the inks, to act like ferrous tannate and precipitate into insoluble compounds on paper.

 

P51 and Superchrome inks contain around 20% isopropyl alcohol in order to make them dry quickly -- dry writing with wet ink! -- and the alcohol is what eats celluloid. The high pH was to make the metallic dyes soluble, as these were "supersaturated" inks like Noodler's are today.

 

I don't think there is any ink on the market currently that damages pens like Superchrome does -- indeed, in 1956 Parker took Superchrome off the market due to the damage it did to even Parker "51"s, notably corroded breathers in the Aerometrics and serious clogging issues. Great inks, but troublesome in actual use form many.

 

Peter

 

This should be the more complete receipe

 

http://www.google.com/patents/US1932248

[raging.dragon]

If the pH really is 12, I'd expect that to eat celluloid and many other plastics.

[MarkTrain]

These patents are from 1931 at time when Parker was developing Quink. It is not clear if and what these have to do specifically with formulas for Quink or Superchrome ink. My guess is that the formulas were/are proprietary and it is anybody's guess what really went in.

Edited October 25, 2013 by MarkTrain

[Albus]

  On 10/25/2013 at 3:59 AM, MarkTrain said:

These patents are from 1931 at time when Parker was developing Quink. It is not clear if and what these have to do specifically with formulas for Quink or Superchrome ink. My guess is that the formulas were/are proprietary and it is anybody's guess what really went in.

 

 

Yup. This is some speculation. But the only ink we know that is alkaline, contains ingredient that melts celluloid is the P51 and superchrome.

[Tweel]

  On 10/25/2013 at 2:41 AM, Albus said:

This should be the more complete receipe

 

http://www.google.com/patents/US1932248

 

That recipe is quite a mud pie -- they were putting clay (Bentonite) in fountain pen ink!

[ps4ever]

_{Fascinating post. If you have ever seen this ink, you know it was a toxic swamp. Having the components broken down makes it even scarier. That's why this was Parker's greatest mistake that ended up producing their greatest pen.}