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Re: Celluloid outgassing question...
Posted: Fri Nov 10, 2017 9:53 pm
by americanedgetech
If you combine the OKCA article with this article that I posted in another thread...
http://cool.conservation-us.org/jaic/ar ... 2-003.html
You have about an hour of reading, and combined they explain everything that a layman could ever need to know about celluloid decomposition.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 2:38 am
by John Carter
americanedgetech wrote:If you combine the OKCA article with this article that I posted in another thread...
http://cool.conservation-us.org/jaic/ar ... 2-003.html
You have about an hour of reading, and combined they explain everything that a layman could ever need to know about celluloid decomposition.
If conservators are to be prepared to face the treatment, housing, and exhibition needs of plastics, they must begin research and experimentation now. For many celluloid objects it is already too late.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 2:42 am
by John Carter
americanedgetech wrote:If you combine the OKCA article with this article that I posted in another thread...
http://cool.conservation-us.org/jaic/ar ... 2-003.html
You have about an hour of reading, and combined they explain everything that a layman could ever need to know about celluloid decomposition.
It could be months worth of reading...
https://www.abebooks.com/book-search/ti ... -plastics/
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 3:55 am
by americanedgetech
I think you missed the word "layman" JC.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 5:42 pm
by John Carter
americanedgetech wrote:
I think you missed the word "layman" JC.
lol... it looks like a rabbit hole.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 7:06 pm
by americanedgetech
I am also a member of a chemistry forum where we have discussed this to death. The closest topic to this one is "Which oil is best?"
So yeah... Rabbit hole is a very good analogy.
The one thing that everyone agrees on is there are too many variables to reach a consensus.
Another good analogy here is... Build two engines in the same facility, at the same time. Install these engines on a dyno and run them at the exact same rpm/power output, and they should last the exact same amount of time before failure. As we all know they never fail at or near the same time. After testing thousands of engines you will develop a range of failure rates but there will always be anomalies. Some will fail on the first start up, and others may out live the testing process.
Why is this? Variables in everything from the materials in the component parts to the air they take in.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 8:43 pm
by knife7knut
Read this post with interest and the comments and suggestions that ensued. I have posted several times in the past on this subject and for those who haven't read them I offer the following:
One of the biggest factors(in my opinion)in celluloid degradation has to be temperature. I base this on my experience with a similar material that has a tendency to degrade:vinyl and specifically vinyl used in automotive applications.I first noticed this when I bought a new Mustang GT in 1982. I had stopped smoking the year before and I began to notice that a film would appear on the inside of the windshield about every two to three weeks during the summertime. It would clean off reasonably easy only to re-appear in a few weeks.As the car was black(interior was red)and the windows usually up the temperature inside the vehicle was considerable.
I finally deduced that the vinyl covering on the dashboard was out-gassing and causing the film on the windshield. Attempting to arrest it through the use of various chemical preservatives was to no avail. Eventually the outgassing slows and stops but by that time the vinyl has dried to the point that it becomes extremely brittle and cracking commences.
Another factor in the degradation of celluloid I believe is the introduction of petroleum based products on the surfaces.On picture handled knives this is a death knell for any pictures on the undersides.The petroleum causes the image to gradually turn black and then disappear completely.
One of the strangest scenarios with celluloid handled knives is where one side completely disintegrates but the other side is completely unaffected.I have had several knives on which this has occurred and I cannot explain why.One was an Aerial coke bottle folder;another was a Novelty Cutlery Co.letter opener knife(both were picture handles);another was a Robeson swing guard and another a Camillus trapper(yellow cel)while still another was a KA-BAR folding hunter and a Buck Creek swing guard(cracked ice).
The Buck Creek was particularly insidious as the blade was corroding but the handles weren't showing any outward signs of deterioration. One day after cleaning it I pushed down on the lock and the entire back of the knife broke off! The out-gassing had completely eaten through the brass liners causing them to fail. The handles STILL showed no signs of deterioration.
Another one I bought just because it was so deteriorated was a small STA-SHARP pen that had completely broken in half(backspring included)but the stainless blades showed absolutely no signs of damage.
I wish I had an answer to the mystery of their deterioration and how to combat it;I would likely be a very rich man. Here are some pics of the ones I have.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 8:47 pm
by knife7knut
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Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 8:49 pm
by knife7knut
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Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 9:17 pm
by americanedgetech
I always love your posts Knife7.
The theory behind the Cell staying intact, and the steel deteriorating is simple. Wicking!
Once oxidation (rusting) begins (be it from a drop of water/humidity) the oxidized steel accelerates the wicking of the acid(s) from the celluloid. You will find the celluloid in contact with the oxidized steel has a micro dimpled texture created by localized shrinkage. This entire process that breaks a steel knife may be the wicking the acid(s) thru a thread sized channel that you may not even see with the naked eye or it may be the entire length of the material. Magnified examination will reveal the area(s) causing this action.
Another factor you mentioned is heat. That is 100% correct in that most chemical reactions are accelerated with heat, and completely arrested in the lack of heat. That is one of the laws of physics. Molecules move faster with increasing temperature. In fact that is what heat is. Accelerated molecules.
I believe that everyone has seen a steel component mounted to an un-sealed concrete floor rusting from the bottom up. Same action, wicking. The active oxidation accelerates the process.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 9:50 pm
by knife7knut
Wicking may explain the deterioration experienced behind the handles but a different situation exists with blades corroding on the exposed surfaces and not on the hidden ones. There is no surface contact and yet the deterioration commences quite rapidly. This would tend to support an airborne migration of vapors given off by the degradation. And there is still the mystery of one side of a knife handle completely deteriorating while the other remains virtually unaffected(see the pictures of the Aerial coke bottle).
I wish I had taken pictures of the Robeson when it started out-gassing.The yellow handle on one side was perfect and the other side completely crystallized.I only have a pic of the good side.
The United Boker Christmas tree handled knife I thought I had checked the deterioration by cleaning and coating the undersides of the handles with a prismatic vinyl tape I had left over from a lettering job on a boat but after several weeks the deterioration had returned.I have since replaced the handles with some blue plexiglass.I still have the handles sitting next to my computer and they are still exuding something slippery.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 11:13 pm
by tongueriver
One of the common scenes of cell degradation is a line of dark patina (or worse) along the spine of the blade, while the cell handles look pretty good. This is obviously air-borne oxidation of the knife steel, not wicking. I assume it is nitric acid fumes. I have also seen this in fixed blades wherein the oxidation was clearly air-borne.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 11:31 pm
by tongueriver
The three categories of cell which I now (mostly) avoid are: cracked ice, yellow, and German. One of my favorites is absolutely (so far) stable and is 100 years old. Otherwise I have maybe 100 cell knives that I am not afraid of.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 11:35 pm
by americanedgetech
You are both absolutely correct that airborne vapors are another yet completely different action. In those cases the vapor can not attack the steel it is actually touching so it is escaping, and attracted to the exposed steel.
That's what I mean by too many variables.
Perhaps Ted on the assembly line ate a slice of Vinny's famous olive pizza for lunch, and the oil(s) on his hands insulated the steel from the celluloid... Who knows?
If there were a direct answer, there would be no discussion, and without discussion a solution may never be found.
I have a pet experiment that I would like to attempt one day.
Immersing these handles in different bases such as sodium hydroxide, calcium carbonate, sodium carbonate, sodium bi-carb. ect, and to expedite the process of neutralizing the integral acids in the handles... running the experiment under vacuum.
It might take months to completely vacate the acids from the celluloid or it may take minutes. I do not know but I feel it is worth an attempt because such a process of stabilization could be quite lucrative.
On the other hand, vacating or neutralizing the acids just may degrade the material into something else like dust or goo.
When I have my shop finished, and all my knife stuff out there I will have my lab back so I can try some ideas out then.
I'm no genius but sometimes it is the outside the box guy, thinking differently that finds the answer.
Yellow cell ehhh TR?
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 11:38 pm
by knife7knut
What amazes me is the knife I posted above(easy open marked Elmer G Roberts Portsmouth N.H.)is close to a hundred years old and as nice as when it left the factory.
Re: Celluloid outgassing question...
Posted: Sat Nov 11, 2017 11:49 pm
by tjmurphy
Knifers are not the only ones that have/had to deal with the deterioration of celluloid. It is/was not uncommon to pull great-grampa's old Gibson, or other maker's, guitars out of the closet or from under the bed where they had been stored for years in their cases and find that the binding around the guitar or mandolin had been destroyed, along with the finish. The tuner buttons were not exempt from deterioration either. Martin Guitar used to make their pickguards out of celluloid and after attachment to the guitar, the tops were finished with, I think, nitrocellulose. The pickguards would shrink to the point that it would lift and pull and cause what is referred to as the "B string crack". It is very uncommon to find a pre-1980 Martin without the crack. Just my 2-cents on the subject.
Re: Celluloid outgassing question...
Posted: Sun Nov 12, 2017 12:21 am
by tongueriver
tjmurphy wrote:Knifers are not the only ones that have/had to deal with the deterioration of celluloid. It is/was not uncommon to pull great-grampa's old Gibson, or other maker's, guitars out of the closet or from under the bed where they had been stored for years in their cases and find that the binding around the guitar or mandolin had been destroyed, along with the finish. The tuner buttons were not exempt from deterioration either. Martin Guitar used to make their pickguards out of celluloid and after attachment to the guitar, the tops were finished with, I think, nitrocellulose. The pickguards would shrink to the point that it would lift and pull and cause what is referred to as the "B string crack". It is very uncommon to find a pre-1980 Martin without the crack. Just my 2-cents on the subject.
Some interesting comments there. I reckon there are still a coupla Martin boxes out there that will still bring a smile to my face. 'specially from this old boy.
https://www.youtube.com/watch?v=p_YB9SC7AV4
https://www.youtube.com/watch?v=UEkVkJax2Co
Re: Celluloid outgassing question...
Posted: Sun Nov 12, 2017 12:44 am
by KnifeSlinger#81
I saw a box at the tulsa show today full of outgassing knives, they were all in very rough shape. Practically a pile of rust.
Re: Celluloid outgassing question...
Posted: Thu Nov 16, 2017 3:39 pm
by wizrd
On outgassing - does WHERE & HOW you store your knives make a big difference? My Case Classic - 98 pattern in waterfall celluloid, this knife was OK for 24 years, stored most of the time in a flat, folding case with about 3 doz. other knives. Six months ago, I took it out to take some pictures of it, - and put it back in it's original box, -- pristine condition, & forgot it, -- 5 months later, opened box to find the knife covered with rust, - exposed blade areas mainly, solid with rust, - only one small rust area on unexposed blade , - and the back spring was thick with a black looking coating. which did not extend past the bolsters. Major shrinkage of scales, gaps between the scales and bolsters on both ends, and some curling, lifting of scales away from the liners on the ends. What was once a beautiful knife has now been buffed out to clean up the rust, and relegated to 'vehicle utility blade' to be left in the truck. Some other celluloids that are stored in a small wooden cabinet with plenty of air circulation have never shown anything like this. Regret I didn't ake any pictures of the rust.
Re: Celluloid outgassing question...
Posted: Thu Nov 16, 2017 10:57 pm
by americanedgetech
No one knows the answer to the question that you asked!
Perhaps the day you last saw the knife as "stable" there was a particularly acidic atmosphere? Maybe you cooked fish?
Just so that you all know that I am not trolling or pretending to be interested... here is my home lab.
I would seriously like to find an easy stabilization method. EASY is the key word... I'm not as smart as the chemists that can't figure it out but I have an imagination that is not restricted by education.
EDIT: Sorry they posted sideways but just click on them, and they are straight.
Re: Celluloid outgassing question...
Posted: Thu Nov 16, 2017 11:50 pm
by bladebuddy
Hey Ken ,nice looking lab setup. Do you need samples of celluloid that is outgassing? I have an Ulster fish knife with the yellow handles that are shrinking fast. Luckily the blades are stainless so no rusting going on. I need to have the knife rehandled. Is that something you can do? I thought I read that you were trying setup a workshop. Thanks Steve ( Bladebuddy).
Re: Celluloid outgassing question...
Posted: Fri Nov 17, 2017 1:15 am
by americanedgetech
Steve, I am trying my best to be a productive member of the "Knife Society.
I have been pointed out (not here) as a guy that posts too much but doesn't read enough. Give it what it is.
I have a lab that can make ANYTHING!
,and I like to make things.
Sooooo once I reach the point that I CAN provide something constructive to the knife community, I will take you up on your more than generous offer.
Until then I am just a new collector/poster that wants to help (like yourself sir). Perhaps WE could wind up as the next Dupont/Corning? Who knows... Maybe the "Cure" to Cell will be aspirin... Willow trees fix a lot of ills, and I have POUNDS of willow bark.(google search it). Just a hypothesis but does Hawkins REALLY know?
I'd give us a 60% chance of success! Nothing sucks seeds like a Canary that likes to suck seed!
I'm with you Sir! 100%
K
Re: Celluloid outgassing question...
Posted: Sun Nov 19, 2017 4:19 pm
by John Carter
americanedgetech wrote:No one knows the answer to the question that you asked!
Perhaps the day you last saw the knife as "stable" there was a particularly acidic atmosphere? Maybe you cooked fish? nu
Just so that you all know that I am not trolling or pretending to be interested... here is my home lab.
I would seriously like to find an easy stabilization method. EASY is the key word... I'm not as smart as the chemists that can't figure it out but I have an imagination that is not restricted by education.
That's really impressive. Are you a hobbyist with regards to chemistry or did your knife material interest drive you to develop the home lab? Wow, I have s million questions.
EDIT: Sorry they posted sideways but just click on them, and they are straight.
Re: Celluloid outgassing question...
Posted: Sun Nov 19, 2017 4:22 pm
by John Carter
John Carter wrote:americanedgetech wrote:No one knows the answer to the question that you asked!
Perhaps the day you last saw the knife as "stable" there was a particularly acidic atmosphere? Maybe you cooked fish? nu
Just so that you all know that I am not trolling or pretending to be interested... here is my home lab.
I would seriously like to find an easy stabilization method. EASY is the key word... I'm not as smart as the chemists that can't figure it out but I have an imagination that is not restricted by
EDIT: Sorry they posted sideways but just click on them, and they are straight.
That's really impressive. Are you a hobbyist with regards to chemistry or did your knife material interest drive you to develop the home lab? Wow, I have a million questions.
Re: Celluloid outgassing question...
Posted: Sun Nov 19, 2017 7:29 pm
by americanedgetech
LOL... I saw Breaking Bad, and figured THAT looked like fun.
Not!
I am actually working on developing a Graphine based epoxy for use with carbon fiber. I have a hydrofoil sport boat design (similar to the International Moth series of boats) that I am developing, and my main focus is to reduce the amount of carbon fiber cloth/epoxy used, and increase the strength while reducing weight, and cost.
I mess around with that, and I make my own dietary supplements like Ginko extract, green tea extract, my own aspirin from Willow bark, Lots of things...
Sort of like "Juicing" but to the billionth degree
Here's a 3-d rendering of one of the hulls... The idea is similar to a wind surfer on foils.