Does Ethylhexylglycerin Change Ink Flow Characteristics? I Think Not, Based On Surface Tension

[piojo]

Note: if Inky Recipes is a more appropriate forum, perhaps a moderator could move this post?

 

I'm experimenting with ink flow improvement, as my BSB is very hard starting, and dries nearly solid in the feeds/nibs of my pens. I gather the first thing to do is add a preservative, because whatever else I add to the ink may increase its susceptibility to contamination.

 

I thought phenol, quaternion-15, or phenoxyethanol would be a good choice. Phenoxyethanol, though relatively untested, was the only preservative I could buy locally (after ruling out the common food preservatives, which are no good in alkaline liquids). (Chloroxylenol is very easy to get, and I wonder whether it would work.)

 

The phenoxyethanol I bought was combined with ethylhexylglycerin, which is a surfactant. I need to increase the ink flow, but not by adding a huge amount of surfactant! (I'll be adding 0.5% preservative, but I'll start with only 0.0001% nonionic surfactant. Obviously I don't want to add too much!) I couldn't find any online references to ethylhexylglycerin in ink, so I set out to find out whether it significantly changes surface tension.

 

I measured about a drop of preservative as 15 mg, then diluted it with water to around 3.2 g total, to get 0.5% preservative. I mixed and used a pipette to drop six drops of water, then six drops of mixture onto a clean plastic surface. I examined the contact angle with a magnifying glass, and could not tell the difference between the two groups. As an additional control, I mixed half a percent of dish soap into water and examined six drops. They spread, and looked nothing like the other two groups. (In this photo, the soap is nearest the camera. The batch with the disinfectant is in the middle.)

 

My conclusion: despite being a surfactant, a modest amount of ethylhexylglycerin does not noticeably change the surface tension of water when used at normal rates as a preservative. It is thus not likely to have a large effect on ink flow. (Flow is not directly caused by surface tension, but there is some relationship. To see the difference, read about how "super spreaders" do not have the lowest surface tension.)

Edited August 11, 2018 by piojo

[Mech-for-i]

interesting observation, I wonder what would be a good lubricant for tricky ink

[piojo]

  On 8/11/2018 at 2:46 PM, Mech-for-i said:

interesting observation, I wonder what would be a good lubricant for tricky ink

I'm gonna try Triton X-100 and one of more of glycerin, PG, and lube (you heard me), but I'm afraid Baystate Blue has deeper problems. When I took a pen apart, it wouldn't get clean with ammonia and dish soap. With rubbing alcohol, tons more ink was washed away. So if the ink is actually drying hard (and insoluble) inside the feed or nib, a more drastic measure may be needed. And it's possible the problem is insoluble. By the way, if you want some BSB/chemicals to try, I'm in your area.

Edited August 11, 2018 by piojo

[Corona688]

It does not have surfactant properties, no.

 

If they still sell it around where you are, you could try medical iodine, like you'd use on cuts. Yes, it's colored, but you only need teensy amounts.

 

As for surfactants, many people swear by Triton X-100 for their private formulations. In commercial products, triethanolamine is very common.

 

You are correct to guess really, really low for amounts. Check this Pilot MSDS for the closest thing we have to an example formulation. 0.4% dye, 0.1 - 1.5% flow agent, 0.4% preservative.

Edited August 11, 2018 by Corona688

[PJohnP]

We've had some discussions on this topic here in FPN over the years, so a search will benefit you towards some suggested solutions for flow improvements. However, telling someone tartly just to run searches is a trifle rude, so I'll point to a thread that I started about six years back :

 

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

 

I'll make apologies in advance for some of my posts in that thread - they tended to get a bit more technical than many people might find advantageous. Shrug. Years of experimentation in my work have led me to a more technical style in discussing some types of topics. Although it might be a bit vain, I can continue to attest for my comments in that thread, and so referenced it.

 

I still use Photoflo for flow improvements in ink, most recently on an IG ink about a fortnight back. It's entirely possible that there are "better" additives, but Photoflo is still (relatively) available, and the quantities needed for flow improvements in fountain pen ink are such that it does not significantly affect other colligative properties of the fluid. Triton X-100, if the Sigma-Aldrich spec page is correct, should provide a similar effect. However, I simply popped into an old-school camera store when I wanted a surfactant, and the Photoflo bottle that I obtained has met my needs for years past, and likely for years to come. No fuss, no muss purchasing, eh ?

 

Glycerine, dish soaps, dishwasher surfactants have all been discussed fairly well here in FPN, and there are varying degrees of success and contentment with their functions in fountain pen ink. People generously offered some other tested alternatives in the thread noted above. Again, an FPN search on the topic will likely yield some other, perhaps better explained, commonly available materials for improvement in ink flow characteristics, and I believe that there may well have been concatenation of discussions on the topic in more recent times by one of the able moderators here at FPN.

 

In my case, I've found that even the most recalcitrant ink has responded well to Photoflo, and I've been carefully restrained on additions in achieving those findings. As an engineer and a scientist, I've long been aware of the maxim, "The perfect is the enemy of the good."

 

YMMV, or 100km/L, if you're located where that measurement of performance is the typical discussion point...

 

 

 

John P.

[piojo]

  On 8/11/2018 at 3:49 PM, PJohnP said:

We've had some discussions on this topic here in FPN over the years, so a search will benefit you towards some suggested solutions for flow improvements. However, telling someone tartly just to run searches is a trifle rude, so I'll point to a thread that I started about six years back :

 

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

 

I'll make apologies in advance for some of my posts in that thread - they tended to get a bit more technical than many people might find advantageous. Shrug. Years of experimentation in my work have led me to a more technical style in discussing some types of topics. Although it might be a bit vain, I can continue to attest for my comments in that thread, and so referenced it.

 

I still use Photoflo for flow improvements in ink, most recently on an IG ink about a fortnight back. It's entirely possible that there are "better" additives, but Photoflo is still (relatively) available, and the quantities needed for flow improvements in fountain pen ink are such that it does not significantly affect other colligative properties of the fluid. Triton X-100, if the Sigma-Aldrich spec page is correct, should provide a similar effect. However, I simply popped into an old-school camera store when I wanted a surfactant, and the Photoflo bottle that I obtained has met my needs for years past, and likely for years to come. No fuss, no muss purchasing, eh ?

 

Glycerine, dish soaps, dishwasher surfactants have all been discussed fairly well here in FPN, and there are varying degrees of success and contentment with their functions in fountain pen ink...

Thanks, John. I'm going to really enjoy reading that. You don't heed to apologize to me for being technical--my post is a bloody lab report!

 

I read somewhere on this forum that Photoflo is just dilute Triton X-100 and propylene glycol.

 

I'm mostly concerned with how to keep the BSB from drying hard. I think a waterproof ink may have different problems/solutions than a regular ink. For example, wetting the nib doesn't fix the problem after a clog. (Nothing does, in my experience. The pen only writes well for 2-3 days. Then it needs to be cleaned. Similar problems with other pens.)

 

But I'm not going do get deep into researching solutions until the surfactant I ordered arrives in the middle of the week. It'll be my first stab at a solution, since people seem really impressed by it.

Edited August 11, 2018 by piojo

[PJohnP]

  On 8/11/2018 at 4:07 PM, piojo said:

Thanks, John. I'm going to really enjoy reading that. You don't heed to apologize to me for being technical--my post is a bloody lab report!

 

Not to worry - I report results in that thread, if perhaps not to the level of a lab report... I can hardly toss stones at someone who is quite methodical in their assessments ! <chuckle>

 

The specific surfactant chemicals that you mention are similar if not identical in most of the photographic print surfactant materials. I personally have found that the concentrations in products like Photoflo are far more than necessary for providing improved flow in fountain pen inks. Dilution or scrupulous care in droplet size are needed with Photoflo for successful results. The use of even more concentrated surfactants would simply (?!?) mean further dilution in order to use them with inks. That will mean a two- or three-step set of dilutions for the concentrated surfactant over the photographic surfactant, a trivial exercise for a chemist *, but sometimes more daunting for the casual user.

 

The combinations of ink, paper, and specific pen nib assembly create a plethora of variables to control for the ink-modifier. In addition, there are other variables such as the ambient pressure and humidity that play strongly into the discussions. I live at about 2,220m with lower humidity, so many inks that are considered "slow-drying" pose less of a problem for me. OTOH, when I travel to sea level in high temperature and high humidity conditions, matters obviously change a lot. I'm simply not about to try and make a multi-dimensional matrix for all of the effects observed, perhaps because I would then feel (slightly) compelled to run the sets of experiments to populate the matrix fully. I do have several other parts of my life that this would unpleasantly displace. <arched eyebrow>

 

Being that I'm an engineer (as well as a scientist), I look for the simplest solution - pun intended - for a problem like ink flow, and therefore went into the photographic surfactants. It's also arguable that I'm essentially lazy, but that circulates around again to the good/perfect maxim... <chuckle again>

 

BSB is a (very) long debated ink at FPN; debated in some cases to levels of antagonism where the moderators had to freeze threads, alas. However, few of the discussions around the ink related to making changes in ink flow characteristics. I've tried the ink, but the writing characteristics for me were such that I did not find it a compelling choice, and so left it behind me. As well, the pen cleaning aspects of the ink, while manageable with some care, were also such that I didn't find the ink to my writing tastes. This is truly one of those areas where researching the topic inside FPN could turn up a vast number of discussions on how to "tame" the ink to, perhaps, your satisfaction. Having noted that, I would also comment that some threads on BSB went into non-technical discussions that may not assist you...

 

I'll be interested to read how you are able to address that specific ink, and look forward to your posts on the topic. <warm smile>

 

 

John P.

 

 

* For those readers in the UK or in some Commonwealth countries, the use of the term "chemist" could be either a pharmacist who compounds medicines or the person working in the scientific field of chemistry. One may pick the definition that best fits their needs...

[Corona688]

  On 8/11/2018 at 5:30 PM, PJohnP said:

Being that I'm an engineer (as well as a scientist), I look for the simplest solution - pun intended - for a problem like ink flow, and therefore went into the photographic surfactants. It's also arguable that I'm essentially lazy, but that circulates around again to the good/perfect maxim... <chuckle again>

I've wished for a while we had some sort of industrial process chemist here to tell us the ins and outs of flow. I suspect there's a sweet spot of density, viscosity, and surface tension we're supposed to aim for. Every time I dig into it I come to the conclusion "wow this is complicated" and go back to trial-and-error.

[PJohnP]

  On 8/11/2018 at 5:45 PM, Corona688 said:

I've wished for a while we had some sort of industrial process chemist here to tell us the ins and outs of flow. I suspect there's a sweet spot of density, viscosity, and surface tension we're supposed to aim for. Every time I dig into it I come to the conclusion "wow this is complicated" and go back to trial-and-error.

 

<deep chuckle>

 

I'd be more than willing to take on that research if I could be funded to a level that would allow me to continue to meet my monthly and yearly costs of living !

 

Without any sarcasm, the number of variables involved would make such an effort several or more years of full time research with experiments. That's not including individual preferences for what that "sweet spot" would be, I might add, which would further elongate the process. As a humorous aside, so long as new inks would be introduced, I'd continue to be employed in that research venture. Now, if only I could find some entity to fund such a project !

 

You will find some systematic discussions on dilution and the use of adulterants in many threads, such as this one :

 

https://www.fountainpennetwork.com/forum/topic/199472-in-praise-of-dish-soap/?p=2032116

 

but I have not seen an overall systematic assessment of a substantial number of inks in the type that you are asking for within FPN. Yet.

 

However, if you look at Post 8 in that thread from Sandy1, you'll see a very well laid out approach for dilution and addition, especially within the section "Tuning the Ink". That approach is a solid scientific manner in which to research effects on inks from adulterants. Anyone undertaking these approaches will need to invest in some basic chemistry lab measurement equipment in order to perform a series of experiments. It's important to note that some locations have legal restrictions on getting chemistry lab equipment. While graduated titration burets aren't on those lists, obtaining them is not always as easy as one might think. Without having some fairly specific equipment, performing the experiments in a systematic manner is not simply not possible.

 

All of that written, if I've made comments on FPN over time on my vision of adulterating inks for flow and other characteristics, I've stood on the shoulders of people like Sandy1 to elevate my view.

 

 

John P.

[Corona688]

  On 8/11/2018 at 6:11 PM, PJohnP said:

Without any sarcasm, the number of variables involved would make such an effort several or more years of full time research with experiments.

I came to the same conclusion. Some things are easy to measure, some aren't. But I also have the niggling feeling that if I ever find an expert, he'd slap me upside the head for going to so much trouble and hand me a chart. 99% water shouldn't be this hard.

 

  Quote

You will find some systematic discussions on dilution and the use of adulterants in many threads.

It's all qualitative. We know X-100 works way better than dish soap, but I couldn't tell you why.

 

That ink tuning procedure looks very helpful.

Edited August 11, 2018 by Corona688

[Corona688]

  On 8/11/2018 at 7:35 PM, Corona688 said:

I have the niggling feeling that if I ever find an expert, he'd slap me upside the head for going to so much trouble and hand me a chart.

Well well. That got me thinking. They might hand me these charts:

 

http://burningsmell.org/images/i/triton-x100-tab2.jpg http://burningsmell.org/images/i/triethanolamine-tension.png

(They're both the same units, by the way, despite the different symbols)

 

Which tells me a few things.

1. Triton X-100 is a potent surfactant -- one part in ten-thousand cuts surface tension more than in half.
2. The Pilot formulation I linked earlier, with 1.5% triethanolamine, has a surface tension near water.

Meaning, surface tension could be a lot less important than I thought.

Edited August 11, 2018 by Corona688

[PJohnP]

  On 8/11/2018 at 8:14 PM, Corona688 said:

It's all qualitative. We know X-100 works way better than dish soap, but I couldn't tell you why.

 

That ink tuning procedure looks very helpful.

 

...

 

Triton X-100 is a potent surfactant -- one part in ten-thousand cuts surface tension more than in half.

 

...

 

Meaning, surface tension could be a lot less important than I thought.

 

 

Heh. As you now have found, it's indeed quantitative.

 

On the Triton X-100 front, this is precisely why I used photographic surfactants. Given that I needed to dilute Photoflo already, using a far more concentrated surfactant wasn't to my personal advantage. Everyone's different, of course, and I would be intellectually interested in the specific degrees of dilution for the Triton X-100, but given that I have a bottle of Photoflo in a desk drawer (next to inks, naturally), I very much doubt that that I will get past the level of intellectual curiosity.

 

Writing further on the quantitative front...

 

My findings, in parallel with others, have been that dilution and adulteration are necessary for the best results. Rather than trial and error, randomly tweaking one variable or another, I'd go about this systematically for an ink that I liked but found intractable for daily use.

 

I usually try dilution first with a smallish sample of a desirable but poorly flowing ink, and I follow a roughly similar process to the one Sandy1 provides for the use of a surfactant.

 

Depending on the ink anywhere from a 5:1 through 3:2 (ink:water) ratio of dilution have been needed. It's extremely ink-specific, and has not been at all predictable by brand or water-resistance or colour. Essentially, the experimental approach has been to make a series of notes with each progressive dilution of that small sample that comment on the flow characteristics (and other things as needed), and then to carefully assess the colour/readability of each sample. In a few cases, nothing more than progressive dilution to a certain point has been adequate to make the ink useful in my personal estimation.

 

In other cases, dilution has continued beyond the personally acceptable colour/readability level without success in flow characteristics.

 

If that's the case, I would select the dilution level that I found most acceptable, and then to roughly follow Sandy1 "ink tuning" approach, again, keeping notes as I go.

 

One could assemble a matrix from this to bring it to a repeatable experimental science level, but the couple of times that I did that, I found it an extremely tedious exercise. I eventually went to simply noting the dilution and Photoflo quantity on a ink vial or bottle. After all, I was "tuning" the dilution and surfactant levels to my own personal taste, or, as you termed it "sweet spot". The entire process, using some defined ink, distilled water, and Photoflo quantities could be knocked out in something like a quarter to a half hour, if I was so inclined. Once I was done, I went back to other tasks.

 

After some time, I settled on one or two inks that I liked as EDC items (e.g., Noodler's Zhivago as noted in the referenced thread), and I haven't been playing beyond those in the last few years. As fun as it was to "tame" Noodler's Manjiro Nakahama Whaleman's Sepia, that simply wasn't an ink that I wanted to use every day, and, as I found out, many of the most recalcitrant and stubborn inks were not inks I wanted to use day-to-day. So I stopped experimenting. I might start again some day, but perhaps not today.

 

I think that I mentioned above in the thread that I was looking for the simplest solution... <warm smile>

 

 

 

John P.

Edited August 11, 2018 by PJohnP

[piojo]

  On 8/11/2018 at 6:11 PM, PJohnP said:

 

Anyone undertaking these approaches will need to invest in some basic chemistry lab measurement equipment in order to perform a series of experiments. It's important to note that some locations have legal restrictions on getting chemistry lab equipment. While graduated titration burets aren't on those lists...

Home chemistry is illegal in Texas? That's horrifying! I would have expected education to be as much a right as personal protection. But that's a handy list. It's too bad vacuum filtration/distillation/drying is so much more expensive than the rest. I imagine I could get all the rest for a hundred bucks or two, given that I'm a stone's throw from China.

 

I don't imagine you need all that for inks, but a distillation setup would be very handy for getting phenol, which I wasn't able to buy locally—SamCapote recommended phenol as a preservative after carefully considering several factors. His analysis considers something that ElaineB's nice (if general) thread didn't consider: phenol is traditional and known, so it may need be a safer bet without testing separately in each ink. But phenoxyethanol is used in almost everything these days, and it tolerates a wide range of pH, so it is another safe bet. Any craft store that caters to soap/cosmetics compounding probably has phenoxyethanol.

[minddance]

Finally some useful scientific discussion here on this forum and not some brainless advertisements. Thumbs up!

[PJohnP]

  On 8/12/2018 at 3:28 AM, piojo said:

Home chemistry is illegal in Texas? ...

 

...phenol is traditional and known, so it may need be a safer bet without testing separately in each ink. But phenoxyethanol is used in almost everything these days, and it tolerates a wide range of pH, so it is another safe bet. Any craft store that caters to soap/cosmetics compounding probably has phenoxyethanol.

 

 

Let's just say that the drug trade has made for some rather interesting laws here in the US.

 

There are some art material preservative solutions containing phenol that are available. Following Sam Capote's posts on the topic, I obtained some and used them with some vintage inks that I acquired to maintain their situation. Phenol fell into disrepute due to some toxicity hazards, but, as any practising professional in the health and safety field would mention, it's the dose that determines the effects. The dosages necessary to treat ink are not within such a range for hazards.

 

All of that mentioned, for some readers of threads like this one (or the referenced ones), diluting and adulterating inks for personal satisfaction is an excessive effort. With so many wonderful inks available now - I've ventured the hypothesis several times here at FPN that we have more individual ink choices now than in the history of fountain pens - one can simply move on from an ink that is not enjoyable. For some of us, "tinkering" with the ink product is a fun exercise, and as we've seen with a number of people, that sometimes becomes a new avocation and brand of ink.

 

Isn't that a wonderful byproduct of the love of pens and inks ?

 

 

 

John P.

Edited August 12, 2018 by PJohnP

[Maurizio]

My post is nothing more than my unscientific, subjective observations, but I offer it here as another bit of observational data. I have had succes with glycerin and a commercial product, designed to dilute paint, Liquitex Flow Aide. I don’t know if it contains the same substance being referred to here or not.

 

https://www.fountainpennetwork.com/forum/topic/321641-shocking-ink-adulteration/

[PJohnP]

  On 8/12/2018 at 11:41 PM, Maurizio said:

My post is nothing more than my unscientific, subjective observations, but I offer it here as another bit of observational data....

 

That's some nice work, including a decently long list of inks that were tested !

 

Even more to the point, it addresses the OP's question about BSB.

 

Neatly done, and thanks for adding to the discussion.

 

 

 

John P.

Edited August 13, 2018 by PJohnP

[Corona688]

Just to note, Liquitex Flow Aid seems very similar to X-100/Photoflo, at least some of the same important ingredients.

Edited August 13, 2018 by Corona688

[PJohnP]

  On 8/13/2018 at 12:56 AM, Corona688 said:

Just to note, Liquitex Flow Aid seems very similar to X-100/Photoflo, at least some of the same important ingredients.

 

Indeed. The set of commercially available surfactants is a pretty straightforward one.

 

The real trick is carefully reading the SDS and fact sheet to ensure that concentration is well understood. As you've so correctly shown with your data, this becomes important for adulteration of inks.

 

I mentioned in another thread that to apply adulteration to an ink like PR Tanzanite, an ink well-known for very easy flow, could have some pretty deleterious effects in a shirt pocket. High concentration surfactant added with a liberal hand could have the same effect on some other inks...

 

 

 

John P.

[Honeybadgers]

  On 8/11/2018 at 3:11 PM, piojo said:

I'm gonna try Triton X-100 and one of more of glycerin, PG, and lube (you heard me), but I'm afraid Baystate Blue has deeper problems. When I took a pen apart, it wouldn't get clean with ammonia and dish soap. With rubbing alcohol, tons more ink was washed away. So if the ink is actually drying hard (and insoluble) inside the feed or nib, a more drastic measure may be needed. And it's possible the problem is insoluble. By the way, if you want some BSB/chemicals to try, I'm in your area.

 

Per Nathan, BSB is designed to be destroyed with bleach.