Celluloid Piston Filler Affecting Ink In The Barrel

[Gasquolet]

I have a Tibaldi Bononia that has a weird effect on the ink I fill into it: Over about 48 hours it changes the ink's colour, to be pretty much unrecognisable.

 

Initially I thought it was a problem with the ink so I started a thread here but I now realise it is the pen causing this, not the ink.

 

I have had two inks in the pen; Akkerman Blauw Van Vermeer and Rohrer & Klingner Alt Goldgrün, both have changed significantly in 48 hours in the pen, see the lower two writing samples in this photo to illustrate the affected blue ink and the colour it should be. Please ignore the upper samples, this was a coincidental red herring; not a similar effect at all.

 

 

The Alt Goldgrün (not pictured though I will upload a photo for reference) has lost almost all it's green content, going a rather pleasant gold colour like a faded KWZ Honey. I flushed the pen well before the first fill and between inks.

 

I have noticed a stronger than 'normal' camphor spell in the cap since this pen has been inked.

 

My questions: Is the celluloid breaking down and acidifying the ink or is something else happening? Is this a known phenomenon? Can I stop/ prevent it or at least reduce the effect significantly?

 

Any helpful advice gratefully received, this pen is far too nice a writer not to use.

Edited April 20, 2018 by Gasquolet

[OMASsimo]

I'm not aware that celluloid affects inks. But I know that certain nib materials or nib platings do. Does the colour change really happen in the barrel? The two lines you wrote did not consume much ink. Does the effect persist when you write one or two pages?

[praxim]

I am unfamiliar with the Tibaldi Bononia, its age or construction, so the following may be wholly inapplicable.

 

Recently, I filled a very old, well-cleaned, Onoto 3500 with Robert Oster Fire Engine Red, a bright red. It emerged a darker red. A quick check of the original ink did not show change in its colour, so it had to be the pen, which is hard rubber in barrel and feed.

 

My assumption is that, like ageing wine an oak barrel, the Onoto is imparting to the new ink flavours it absorbed from blue and black inks over years of use. Under the circumstances I think it neither desirable nor necessarily possible to clean out my pen entirely. If I want original colour, I will put it in a new cartridge converter, otherwise, each older pen will impart its own distinctive flavour.

 

Whether this bears any relationship to your Tibaldi's behaviour I do not know. See the opening caveat.

[Gasquolet]

I like the wine analogy. I have had a couple of pens with long dried up ink residue that has dissolved to give interesting effects, in fact I'd pay well for a bottle of the one off colour I once got out of a well flushed vintage piston filler I decided to fill with Iro Kon Peki. It took a day or so to develop but the resulting blue with shading tinges was superb but I've never been able to repeat it.

 

In the case of the Tibaldi; it is a late 90's celluloid (cellulose nitrate) piston fill pen where I believe the piston moves directly within the barrel, not a liner of another plastic. The Bononia is a rather rare bird in that it was an LE of 500, in production at the time of the demise of that iteration of the Tibaldi company, I'm not sure how many are in use these days.

 

My pen had allegedly not been inked but, like a lot of Tibaldis of that era has some indications that not all is well; some corrosion to the metal trim and more than usual tarnishing of the 18k nib.

 

I have read some more and found this post/ article which, while it doesn't explain the phenomenon I'm seeing directly, does suggest I perhaps have a pen that is slowly killing itself.

 

Here's an over-lit photo of the current ink in it's progression over the last few days, and the pen. The only signs of deterioration on the pen are some old corrosion spots on the trim plating and the nib's tarnishing which if I'm honest, I think has become more pronounced in the last few days.

 

 

If this is a case of 'celluloid disease' I suppose I'm hoping for some advice on how to help the pen live as long as possible.

[mauckcg]

Interesting. Porous material maybe or an absorbent material that pulls part of the ink out?

[Gasquolet]

I'm not aware that celluloid affects inks. But I know that certain nib materials or nib platings do. Does the colour change really happen in the barrel? The two lines you wrote did not consume much ink. Does the effect persist when you write one or two pages?

 

Sorry, should have said; in the photo above, at least half a page, often a lot more is written between each test line. It's quite a wet medium nib so I'm fairly confident the change is happening in the pen, not specifically in the feed/ at the nib.

 

I just did an experiment and unloaded a couple of drops onto a paper towel. The colour was uniform and it writes much the same after that experiment as before. Am going to try to resuscitate my pH meter to see if I can do a pH comparison between fresh out of the bottle ink and the stuff in this pen.

 

Reading the above linked article, I may actually be better using an IG ink in the pen as typically more alkaline inks like Iroshizuku or Sailor (not sure about R&K) may be more aggravating to unstable celluloid.

[CS388]

It's an interesting situation. I still find myself wondering if it is not a build up of old ink residue/stain in the pen which is discolouring the new inks. Have you tried putting the pen parts in for a long soak (days)? Or using a penflush to make sure the barrel and other parts are completely ink free?

 

I realise that you've probably already tried this, but felt it was worth mentioning.

 

Good luck.

[pen2paper]

 

cool.conservation-us.org/jaic/articles/jaic30-02-003. by JA REILLY - ‎1991

edit to avoid a hot-link but credit author

Edited April 22, 2018 by pen2paper

[siamackz]

It's an interesting situation. I still find myself wondering if it is not a build up of old ink residue/stain in the pen which is discolouring the new inks. Have you tried putting the pen parts in for a long soak (days)? Or using a penflush to make sure the barrel and other parts are completely ink free?

 

I realise that you've probably already tried this, but felt it was worth mentioning.

 

Good luck.

I have expericed the same situation as the OP and it was because of stubborn remnants of ink in the feed/section inside.

 

Were you the first owner or did you buy it used? If you know which ink was used in it first then check to see if the new colour you are betting is a mix of the old and current ink.

 

Otherwise, I would just put it through a serious cleaning program - remove nib and feed if you can, otherwise use raipido eze and then keep filling the pen with ink and placing it tip down on a bunch of tissues allowing the water to pass through the nib slowly. Do this as many times as needed till the tissue shows almost no colour.

[Gasquolet]

Thanks for these pointers. I am genuinely interested in the complexity of this material, even if I am barking up the wrong tree with this pen.

 

I am not the first owner, in all likelihood not the second either so the assertion that the pen was un-inked was just that. I did pull the feed and nib as the collar they are in is absolutely not for moving. The nib and feed came out clean but that doesn't mean much about the inside of the pen. I'll be honest and admit that when I flushed it with water and didn't notice any colour I went straight onto ink. I have not soaked it with water.

 

I'll do that next. If I don't think about being a bit worried about the pen I'm quite enjoying the 'alt gold' ink as it appears to now be.

[kazoolaw]

Can't help with your problem except to guess that maybe ink is getting past the piston into the barrel.

 

The real reason for my comment is to urge you to post in the review section about your Bononia. It was the one Tibaldi of that era which eluded me, and which I've never seen listed for sale.

 

gary

[Gasquolet]

Gary, I've never posted a review. I have been along time reader of this forum and very occasional contributor. I have never thought myself worthy of reviewing a pen when others do it so well.

 

I will take you up on this though. It'll take a bit of preparation to get the photography right; I am not great at that aspect but would like to do it justice. As I have all but one of the pens produced by Tibaldi in that era of the name's history I can hopefully add a little objectivity to a review of the pen, given that it's almost 20 years out of production.

[OMASsimo]

This case is quite puzzling indeed. I'm not really familiar with Tibalidi but kid of recall they were a top notch Italian pen maker before WWII. I doubt they used any poor quality materials. I love celluloid and have a fair number of celluloid pens from the 1930 through current. As I already mentioned, I've never seen anything alike what you experience. So, I would be very surprised if it was due to the celluloid.

 

Anyway, lets analyse a bit more systematically. You say there is fading of the ink colour and you also show a drastic colour change. Colour change could be explained to some degree by mixing with a colour of a contamination by old ink. But what I see is rather the opposite. You show a sample of a warmish green turning into an orange-brownish colour. Of course, mixing green and red would yield brown. But it doesn't look like this here because in this case I would expect the hue to get darker. I'd rather think that the ink is composed of at least two tints one blue and one yellow-orange (maybe the "gold" in the name of the ink?). If the blue is depleted by some chemical reaction, this would result in a yellow-brown ink eventually. You might try to find out by thin-layer or paper chromatography what the ink is composed of and if this would be a valid explanation of your observation.

 

The second test you suggested yourself already. Fill the pen with clear water after a thorough flushing and let it sit for a few days. Then check if it picked up any colour and, if you have a chance, measure its pH. If the water comes out colourless, you can reject the hypothesis if a contamination. Some dyes change colour due to different pH (this is how you measure pH with an indicator strip). You could put a drop of your ink into the water from the pen and check if this changes its colour. Or you could check if your ink reacts on pH by adding a bit of acetic acid or e.g. baking soda solution. If you see an effect, you know that it changes colour either in the acidic or alkaline medium.

 

My first suspicion was a catalytic effect of the nib. I have an Ancora pen with an 18k gold nib which is plated with some white metal but I don't know which. The typical would be rhodium, but it also could be platinum or palladium or any kind of alloy containing some of those or similar metals. This pen has the strange habit to deplete certain ink colours over time, obviously by a catalytic process. But if I write a few lines, the ink colour is back to normal. So, this doesn't seem to be your case either. I really puzzled.

[CS388]

...snip...

 

The second test you suggested yourself already. Fill the pen with clear water after a thorough flushing and let it sit for a few days. Then check if it picked up any colour and, if you have a chance, measure its pH. If the water comes out colourless, you can reject the hypothesis if a contamination.

 

Excellent idea.

[ele]

The color it is turning is the color of one of the components in Alt-Goldgrun; I know this because I've run out that ink on a chromatography strip once...

[Gasquolet]

Little techy update on this pen. The colour of the ink hasn't changed much since the last of the writing samples in the photo above, perhaps it's a bit lighter but essentially all the green components have gone.

 

I have got my pH meter up and running and recalibrated it just before using it (2 point calibration at 7.01 and 4.01 with the manufacturer's solutions.) This was left to stabilise for a few hours before as I hadn't had it in use for a couple of months and they don't like to be left out of storage solution/ allowed to dry out.

 

With the ink that remained in the Bononia, I 'painted' the sensor with the nib as I expelled the ink slowly. There wasn't enough ink to do the normal procedure which is to immerse the sensor. This gave a reading that didn't fully stabilise but got as low as between 1.56 and 1.61 before running out which, needless to say is extremely acidic for an ink.

 

I then flushed the instrument and repeated the experiment by 'painting' fresh from the bottle Alt Goldgrün onto the sensor with an ink syringe until it stabilised at 5.23.

 

I flushed the pen out at length after this until I got clear water back out. It's now soaking in clean water.

 

 

The color it is turning is the color of one of the components in Alt-Goldgrun; I know this because I've run out that ink on a chromatography strip once...

 

I would agree, my suspicion is that the gold/ caramel colour is a pigment that isn't affected by the change to the ink pH. I have a drop of ink in 5ml of acetic acid in a shot glass on my desk at the moment so see what happens. After an hour, not much.

 

Not sure how to disassemble this pen and don't want to break it so at the moment am waiting to see what comes out of the pen with the soaking water.

[OMASsimo]

I think we're getting close. Just one question, how old is the pen?

[Gasquolet]

I think we're getting close. Just one question, how old is the pen?

The pen was made in 1999, in celebration of the status bestowed upon Bologna (historically called Bononia) for the year 2000; one of the European cities of culture that year and the only one in Italy.

 

I understand most of the Tibaldi pens of that era were made by Etruria Srl though I think the material of the Bononia was unique to that pen model and Tibaldi, not appearing on other Etruria made pens at the time or since.

 

I am going to leave the pen filled with water for the next couple of days while I travel for work, will see what we find when I return to it later this week.

[OMASsimo]

Thank you for the response. I only knew about the original Tibalidi manufacturer before WWII, so yours is made by a new company. I couldn't imagine the old celluloid to cause such an effect. But with recent material I wouldn't be so sure.

 

Anyway, I was shocked to read that you measured a pH of about 1.6! This is extremely acidic and certainly can explain the degradation of a blue dye. Now, a pH of 1.6 could correspond to 0.025 molar nitric acid or sulfuric. A mixture of both is used to make the nitrocellulose of celluloid. If the product isn't washed properly, some acid could remain in the material and then wash out into your ink. If this is the case it would mean that they used very poor quality nitrocellulose for the production of the celluloid. You would have to wash out or neutralize the residual acid somehow.

[Gasquolet]

Long delay to this update, thought it might be useful and interesting should anyone have any suggestions:

 

As per above, I flushed and filled the pen with water on the 24th April.

On 1st May, the water was drawn out of the pen with an ink syringe and tested: pH 2.56 The pen was again flushed several times and refiled with water.

On 2nd May the water drawn form the pen was pH 3.55

On the 3rd pH was 3.49

On the 4th pH was 3.27

Then long gap until today, 11th when the water was drawn out and tested at pH 3.32.

 

On each of the last 4 tests the soaking water came out colourless, no trace of old ink. It always has a notable acrid smell though, a little acetic/ camphor smelling.

 

So it seems to me that my pen is emitting an acid rather than being a residue I'd not flushed out before. Another noticeable thing is that when I had the nib in the pen, the gold surface is getting a cloudy, almost chalky tarnish. A little of this appeard to deposit on the outside of the cap too in the area of the cap threads but I only noticed this once when the pen sat un-handled for several days.

 

Not really sure what to do next. I am distraught at the potential loss of this otherwise very nice pen.

 

Any ideas if there's value in soaking the pen in something neutralise the acids? The last thing I want to do is cook the pen internally, also, if the acids are being 'produced' by the material, then I need to stop their formation, not simply neutralise them.

 

All suggestions gratefully received.

 

Makes me appreciate the robust urushi over ebonite pen I was using today even more!