(Note: None of this is a paid endorsement or advertising. Just my own humble opinions. Remember my advice... Listen to everything a bubbler has to say, but test it for yourself! So much of what makes a recipe "good" seems to be in the eye of the beholder.)
8/05
I was ordering Cricket Hill Powder today and had a brief conversation
with Bill Mailloux (owner/chemist), finally. What a nice and
knowledgeable fellow. He's a man whose job it is to provide all sorts
of products for people who need to make bubbles and foam. From their
Giant Bubbling Powder to fire fighter foam and foam for special
application uses in the agriculture industry. He's even a lurker
here (on SoapBubblefanciers group). He says he does enjoy all of our more solution oriented bubble
talk and at some point when his time frees up a bit, would like to
join in the discussions. I really hope he does.
In our conversation he had the following tips based on what he's read
here and has allowed me to share them with everyone. I should say,
these seemed like ideas just off of the top of his head! What a big
deal it would be for us if he joined and we might be able to pick in
his brain a little deeper. And perhaps we would tickle him too with
our collective observations concerning bubbles, foam and all. Anyhow,
I was furiously scribbling notes in my car (parked) on a bad cell
phone connection so I hope what I have to write here is true to his
revelations. Here we go...
1. Concerning the white percipitate (junk) that forms sometimes in
mixed solutions. This is likely biodegration (biodegradation?) and
happens when the mix starts to biodegrade. When the mix starts to
degrade the ph goes down. As a result of the ph going down the
precipitate forms, which further causes the ph to go down faster. To
counter this, he suggests adding a very small amount of Baking Soda,
he suggests 1/8 of a teaspoon per 2 liters. This ph raising remedy
should revive the bubbling action and halt the biodegration. (Here I
look at my notes and hope I got the "up" and "down" parts right, it's
what I have on paper so I go with it. Tom, how's your science on this?)
2. How should we know what our ph is? Use a pool test kit. Our
mixes, he believes should be around 7 or 7.2 ph for best
effectiveness. His solution is ph balanced and therefore stings eyes
less. And he was not surprised by the fact that my CHP mix does not
age well. After a week it goes "bad". He says that's the bidegration
at work and to toss in some baking soda to improve it. He intended
his mix to be eco-friendly as well and is intended to be used right
away for the most part.
3. Speaking of his powder, it took 2 years to get the formula right.
It's meant to make big outdoor bubbles. The powder itself, when
stored needs to be protected from moisture and heat.
4. Speaking again of his powder, and this I think will knock some of
our socks off, it contains the same ingredient included in the "old
Dawn"! Yes, he's familiar with the "old Dawn" and that secret
ingredient... he's keeping a secret. I haven't tried bribes yet but
he seemed pretty firm in his stand, and who can blame him?
5. 1 pound of his CHP is to be mixed with 1.5 gals of water.
6. He's got the best price (I'm pretty sure-certainly better than I
could find elsewhere) for glycerin. No it's not listed on his site
but does sell it. He thought it was 2 or 3 dollars a pint (I got a
gallon and will let you know for sure). There are many different
grades of glycerine and I was happy to learn he uses the same grade
(USP~about as pure as you get~food grade) as I've been using and
championing.
7. He was very interested in our talk of foam and it seems to be a
topic dear to his heart. He's a maker of Industrial Foaming Agents
and produces a foam for farmers to use when fertilizing to mark the
edges of their long rows so they don't over spray. Regular globs of
(colored?) foam drop from the tips of the large tractor booms as they
motor along.
8. He wants us to think about warm air as a lifting agent for
bubbles, as it's cheaper than helium. Especially warm moist air.
He's not exactly sure how to make it happen but just wanted to throw
that into the discussion.
After another conversation with Bill, here's what I wrote to the Yahoo group...
He was so taken with our group's discussions of polyvinyl
alcohol (the Japan posts) that he decided to do some experimenting.
For another product he produces, he has a supply of PVA that comes in
a water & glycerin mix so it's already water soluble. It seems PVA
usually comes in a pelletized form or powder, to which you have to
heat to a temp of 150 degrees or so to get it to combine with water.
So, this water-soluble PVA he added to his CHP solution and found it
to be a good additive to strengthen and add lifetime (those benefits
are my best recollection, which gets worse every week I'm sorry to
report). But, and here's the thing, the PVA raised the normally PH
balanced solution to above 8. And the solution would not bubble at
all. After PH testing, he added about 1/8 teaspoon citric acid
(per 1/2 gal solution) which brought the PH back down to 7 or so
and it then bubbled brilliantly. He's still working on it
but thinks as a bubble booster PVA holds promise.
It's his opinion that one of the most important factors when
experimenting with solution alterations is to monitor the PH,
because the PH really needs to be stable and at around that 7 (7.2)
mark to work well in many cases, surfactantly speaking. When I asked
him about the coloring of our solutions throwing off readings on PH
test strips, he said; 1. The liquid pool tester kits are more accurate
than strips (at the pool store today the Mgr. debated this). With the
liquid test, you put solution into a vial, add a couple of drops of
the testing liquid and watch the color change and compare it to a
chart to read the PH level. 2. It's fine to dilute our soap
solutions with (and I need to double check this) 25% more water.
The dilution will not affect the results but it will thin out the
color of our detergents enough to make the results read accurately.
I bought both test strips and a liquid test kit to see what
happens. After the wee bit of chemistry I've been trying to
digest, his concern over PH makes sense and I intend to find a way
to fit it into my bubbling work.
Alcohol, long story made short: alcohol is bad for the bigger
bubbles like we make because it evaporates so quickly and leads to
the top thinning out even faster. Upon evaporation the M- effect
does not come into play to "pull liquid" up from the bottom where
the bubble is thicker. However - alcohol is good for foams. It
strengthens the tiny bubble structures, which is why we sometimes
find websites about making soaps and shampoos etc. promoting the
use of some alcohol.
Beer? The alcohol is bad but the other stuff in beer might very
well be good, such as the sugars and glycerine type substances.
The trouble with talking about alcohol (and PVA for that matter) is
there are so many variations of it to say "for certain" anything
unless you specify which kind of alcohol and what it has to react to
(other ingredients). I think this is what he would like us to
understand, there are so many variables in the brews we put together
that it's nearly impossible to say anything is for certain beyond
the basics such as altering how much water or glycerine or dish soap
or what kind of dish soap. As a matter of fact he said, "I'm not sure
there's any real science behind bubbles." He went on to explain the
difficulties in taking/evaluating every possible reaction between
ingredients or solutions into account to hyper "fine-tune" a mix,
because it all goes out the window as soon as the temperature of the
solution changes, or impurities from dirty
wands/buckets/hands/deterioration get introduced, or the humidity
changes or even barometric pressure. Not to mention how hard you
blow air into the bubbles on a given day or how sunny it is or
isn't. I noticed as well that even with all of these factors
against him and his CHP, he was still able to produce the best
solution he personally could be happy with for what he wanted it to
do - most of the time. (He's building from scratch though.) Even
that much success makes him happy. But still gives him the feeling
there's something else he could be doing to improve the mix so he
experiments. Because really, it's not a science, and because of that
fact you can't ever really feel you've done all you could.
Now, in general, the more concentrated the dish detergent is you're
using, the more likely it is to contain greater percentages of
alcohol. Because alcohol helps concentrated surfactants to function.
It's his opinion that "aging overnight with the lid off" is indeed
ridding the solution of the alcohol (and a bit of water, but the
alcohol goes first).
It's now 10/05 and Bill's introduced New Bubble Additives which I'm pretty excited about. What follows are bits of e-mail exchange that you might find interesting.
From Bill:
The PVA solution that I sent you is produced for use in other applications. The solution is applied to a surface in as a concentrate and dried to form a thin film or coating that can be peeled off in a thin sheet. I believe that this is similar to what you are seeing with the bubbles except when it is added to the bubble solution and diluted many times with water in combination with the surfactants the evaporation of the water from the bubble wall forms an extremely thin plastic like surface that increases the tenacity toward other bubbles. This is only what I believe happens. (This was a reply to my commenting that the PVA solution seems to make smaller bubbles cling together with more tenacity.)
The other solution I sent to you contains some glycerin and thickeners which makes it easier to disperse into the bubble solution. The thickeners are not hydroxyethylcellulose and doesn't form the "residue".
Both of the sample additives I sent to you are available for purchase. I need to investigate the actual cost but I believe it will be in the $20 a gallon range and should be available with 1-2 weeks notice.
What is the pH of the Mr.bubble and Dawn solution? If this pH is around 8 then the additive will not change the pH, while if the pH of the bubble solution is near the 7.0 - 7.2 then the additives will raise the pH to near the 8.0 range.
My first thoughts on the poly ethylene oxide is that it is not much different then the PVA material. Both are high molecular weight polymers that are not all that much different chemical structures.
Later from Bill:
I now have the PVA and other material, same as the samples I sent to you, and we plan to ship it to you tomorrow. After getting the information on pricing it looks like the PVA material will sell for $22.00 per gallon and the other material (thickener, glycerin mixture) will sell for $21.00 per gallon plus shipping costs.
I have decided to call the PVA material "Bubble Max P" and the Glycerin mixture "Bubble Max G" and will be labeled as a "soap bubble performance additive." If you have any grand ideas that you want to share with us as to what we should call or label them don't hesitate to let us know.
..............
From KMJ to Bill
Did I tell you that I like that your thickener does not "settle out" in a mix like the cellulose? I'm also experimenting with my winter blends now that it's cold again and the indoor humidity tends to hover somewhere around 20% ~ ugh! I think your glycerin is thicker than the kinds I've been buying from health food & soap making web-sites. The extra viscosity takes some getting used to, especially with the the humidity down so low. I add in a lot of glycerine to my winter brews, and when I make big bubbles 24" + and get them to live for a long time, by the time much of the water has evaporated out and the bubble pops, a huge white residue that I call a beard (or ghost, depending on the size) falls to the floor. It's all part of long lived bubbles in winter I guess, however it's disconcerting to have what looks like bird-doo fall on my shoulder. I can counter it by popping the bubble a bit early, which is fine. The other half of my brain thinks I should go for the biggest white ghost I can get and call it a "special effect" solution.
Adding a touch of the PVA is allowing for different possibilities in the arena of big indoor bubbles too, not just in the smaller bubble sculptures. It doesn't take much, maybe a tablespoon in a gallon of solution, to make a difference. (I'm currently adding more.)
I tried hot air as a lifting agent outdoors this week and really had some fun. I posted to the group it was your suggestion that I give it a try. You do remember suggesting it, yes? They were smaller bubbles (around 1 footers or so in >40 degree temps), just to test the idea, and it works well. It's certainly something to keep in mind as the colder weather approaches. It might bring a whole new flavor to outdoor bubbling in the winter.
I look forward to receiving your Bubble Max(s) P & G, and will intensify my exploration of them now that I can count on them as a renewable resource.
Is their availability something I can mention to the group? I'd need to be able to tell them, to the best of my knowledge, what they're made of. That is, the PVA is a mix of water, polyvinyl alcohol and glycerine. Your thickener is not hydroxyethylcellulose based, is water soluble and also contains glycerin. In evaporation tests, the thickener doesn't reduce to a gummy residue ~ so if it's not guar-gum or something like that, I'll share my speculation that yours is a yet unmentioned thickener. I'd also likely go on to speculate what I think they have to offer the world of bubble juice home-brewers.
I do want to double check with you that neither mixture is harmful to health or destructive to property. True? The PVA mixture does leave more of a "ring" behind when the bubbles pop on a hard surface, but even after drying, can be wiped away with warm water only. That's my experience to date, anyhow. Also the PVA tends to crust up my hands a bit more, but once again is easily washable. I've not tried hand-blown-bubbling with it yet, like Sterling does. I wonder if I'll end up with plastic coated hands? All of this, of course, depends on how much of it I incorporate into my recipes. Have you tried making bubble recipes with them yet, to set a sort of suggested amount to start out with?
As for names? It would be nice if you could tie them into the effects your ingredients have on the bubble skin. (Thickener is good for now, but how best to describe the PVA? To date, my experience has been that the PVA improves Bubble Sculpture blends ~ making the bond connecting the bubbles stronger, with out increasing the bubble's weight.) That's something that's been discussed with the group, and behind the scenes. We've been trying to bet a better handle on how additional ingredients act molecularly with-in the membrane that is the bubble skin. The traditional 3 layer sandwich model (soap - water - soap) must be improved with the addition of glycerin and other things, but we're (I'm) wondering why?
I asked an engineer/chemist/Prof. in Sweden (Göran Rämme) who has studied and written about the workings of bubbles for many years, and this was his reply...
...................................
"With regard to your question about the effect of additives
such as glycerol I assume that it is dissolved in the liquid phase
(also containing micelles of surfactants) in between the surfactant
layers on the surfaces of the film. Water and glycerol have
similarities in their structure e g OH-groups.This gives an increased
viscosity and prevent among other things evaporation of water from
the film. It is also related to the s k Marangoni effect (linked to
the Gibbs elasticity) acting in a stretching process of the film.
Micelles move to the surface dissolving and releasing surfactants to
fill out the space created between the surfactants upon stretching
the film...."
....................................
What's your take on this? Micelles have been described to me as "reservoirs" or pockets of additional surfactant like molecules (floating around in the center watery layer) that may be rushing to the surface of the bubble skin and delaying pre-mature bubble death by feeding the outside layer as it dries. Does that make sense to you? Some additives seem to adversely effect the skin's elasticity (making them "tight and glassy") so bubbles pop with a "snap" into a fine mist. Other additives, thickeners mostly, make the bubble skin "stretchier" (looser?) and pop with a splash and fuzz. I'd dearly love to explore bubble skins in dermitological terms, knowing why some additives cause the effects they do.
To answer your question about bubbles-in-bubbles: When most of the folks on the group, like Tom Noddy, talk about bubbles in bubbles, they are talking about blowing bubbles into the smaller bubbles used to make their on-wand sculptures. Or Sterling's bigger hand blown bubbles. Your powder does allow bubble-in-bubbling, but in my experience, the powder based solution (even when prepared correctly) is a bit too "heavy" for indoor wand work ~ as in building long chains of smaller bubbles. So, the answer to your question is, yes your solution does definitely allow for bubble-in-bubbling effects.
When folks like KellyO (and I) write about bubbles that will tear themselves apart into smaller bubbles (rather than simply bursting) when torn by strong outdoor breezes ~ your powder is good for that too. That's why folks have taken up the exploration of personal lubricants because of their hydroxyethylcellulose. (Something I continue to champion.) Near as I can tell, I was the one who first floated the idea that HEC makes the bubble skin more supple and "self-healing". I hope to discover your thickener does the same thing, but haven't tested it outdoors yet.
From Bill to KMJ
I see from your last e-mail that you had tried warm air for lifting the bubbles (and yes I do remember suggesting it) and looks like it may have some potential. I too had planned to try some bubbles with warm air but have not found the time. We have some heat guns for shrink wrapping at the Cricket Hill shop they are like super size hair dryers, may be too hot, but thought I could mix it with a stream of cooler air to get warm air without breaking the bubbles.
I think you could do this in warmer weather as well as in the colder temperatures. However you get more lift in the cold.
To answer your concerns about the availability of the Bubble Max P and G. Both are available in 1-gallon, 5-gallon, or 55-gallon containers and can be shipped within 3-days to 10-days of notice. I have no problems with you mentioning them to the group. As for the ingredients, the P-material contains water, PVA, some corn syrup, and a small amount of a nonionic surfactant. The G-material contains water, glycerin, thickeners, and an anionic surfactant. I cannot go more into detail then that.
As far as I know neither one is harmful to health or the environment. The residue that you are finding on hard surfaces I believe to be small amounts of the PVA left after the liquid evaporates. The PVA is a plastic like material but is soluble in warm water and can be easily washed away. I did try adding some of the of the P and G material to some of the Cricket Hill solution. I did only a quick test to see if I could see any differences. They both seemed to improve the bubbles and I noticed that the P material seemed to make the bubbles more durable the bubbles wanted to bounce before breaking when hitting the concrete floor. I used only a small amount and would think that 1-3 percent in the bubble solution should be about right but you may want to determine that for yourself as different solutions may require different amounts.
As for your question regarding the micelles, surfactant molecules, additives and how they relate to the bubble surface, I would guess there are many theories and thoughts as to how they all play a part in the bubble surface. Think of a surfactant molecule as a long chain one end is water soluble while the other end is oil soluble. In a water solution like a bubble solution the surfactant molecule will pull the oil like material into the water solution. At the surface of a surfactant/water solution the surfactant molecules line up in a microscopic layer with the heads (oil soluble end) on the surface and the tails (water soluble end) in the water phase. The oil soluble end will dissolve in oily material and will pull the oil molecule into the water this is how a detergent works to clean and remove grease and dirt. If you put a few drops of cooking oil on the surface of a glass of water it will just sit there in little droplets however if you add a little detergent like Joy or Dawn to the water first and then add the drops of cooking oil to it the oil drops will disperse into the water.
Water molecules have a very high surface tension and adhere to each other strongly while oil molecules have much lower surface tension. That is why water will bead on a wax surface while oil will flow out in a thin layer. In a bubble solution the oil soluble ends of the surfactant are on the surface and reduces the surface tension. This allows the bubble film to form and to stretch as the oil ends thin from stretching other surfactant molecules move to the surface to fill the voids as the surface gets larger and larger while the bubble expands. If a bubble is a sandwich of two surfactant layers with a water layer between them as you suggest, then we would have two microscopic surfaces with the surfactant molecules lined up with the oil ends at the surface on the inner and outer surfactant layers. In larger bubbles as the surfaces expand more and more surfactant molecules move to fill the void at the surface reducing the concentration of surfactant in the water layer between the two surfactant layers. Additives like glycerin are water soluble but are also somewhat oil soluble and there molecules are smaller then the surfactant molecules. I don't know but think possibly the glycerin molecules like the surfactant molecules migrate to the surface and can fill in the small voids between the larger surfactant molecules. Another idea is that the glycerin molecules are more fluid and may partially dissolve in the oil end of the surfactant molecule and improve there ability to flow while the bubble film expands.
Thickeners I believe work in more than one way. One way is that they increase the viscosity of the bubble solution this allows for more solution to adhere to the bubble wand allowing for larger or more bubbles to be made from a single dipping. The thickeners also seem to improve the stretching properties of the surface film of larger bubbles. Thickeners are all made of very high molecular weight material or very large molecules and have limited solubility in water forming thick, elastic, sticky solutions at low concentrations. Just how they work to improve the bubble surface would only be a guess. Any way I hope this hasn't been to boring for you.
I too have seen the some bubble solutions that make bubbles that break with a snap and leave very fine water droplets, while others break leaving the white residue. I have found that the snapping bubbles can be related to the concentration of the solution as well a the type of surfactant. The residue I use to call slime bubbles I have found to be related to the type of surfactants and additives in the solution. Weather conditions could exaggerate the forming of the residue.
If you've read this whole posting, you're likely the kind of bubbler who would be interested in my Solution Project. You can read more about that here.