I’m not sure how to direct this post to Sphere/Duane but I suspect he might have some good ideas on this.
I used some cyanoacrylate glue to glue a granite seam and cured it with a dimethyl para toluidine accelerator. Four weeks later the stone turned blueish green where the accelerator came in contact with it.
I did a bit of research and found a wikipedia page with some information indicating that toluidine is used to make a blue dye.
http://en.wikipedia.org/wiki/Toluidine
I also found this random website that talks about removing toluidine blue dye with isopropyl alcohol.
http://www.histosearch.com/histonet/Apr06A/Re.Histonettoluidineblues.html
All I am trying to determine is if isopropyl alcohol is the appropriate solvent to mix into a poultice for removing the stain.
The chemistry is way over my head but it would seem the accelerator reacted with some alkalinity in the stone and turned into a blue dye. The second link I pasted in above seems to indicate that isopropyl alcohol will remove toluidine dye on some surfaces so it sounds like a good solvent.
Does anyone have a chemistry background that might help on this?
Thanks,
Karl
Replies
know anything about this?
Oh man..yeah, I've had "zip Kicker" do that where I didn't want it.
All I can come up with is mix Acetone and Denatured Alcohol. It very well may weaken the CA joint tho'.
How you can slow the evaporation while it "works" is a problem, maybe a layer of saran wrap over the area. I can't think of a "bleach" that is solvent based, that isn't so caustic as to etch the granite. Very possible that lye may work, drain cleaner-oven cleaner..carefully suspended in alcohol. (edit)..I see it's soluble in H2O if the solution is ACIDIC , so scratch the LYE, maybe go with Muriatic Acid and water. Lemon Juice, Vinegar..along those lines..Isoprop is denatured WITH water added, so that is diluted already..rememeber add acid SLOWLY to water.
All I can say is try everything ya got...and for sure, get back to me..I know a great chemist/paint tech guy, but he's in Wa. and is 3 hours behind me time wise. He'll know I'd bet.
Spheramid Enterprises Architectural Woodworks
Repairs, Remodeling, Restorations
They kill Prophets, for Profits.
Edited 2/6/2009 7:32 am ET by Sphere
Sphere, I would be very grateful for any information you could uncover. I put an acetone poultice on a small part of it as an experiment yesterday and should know if it helped at all by tonight.A geologist suggested using vinegar and letting it soak for an extended period. Reading about dye removal on a variety of sources led me to also consider hydrogen peroxide.I am still eager to hear any suggestions anyone might have.Thanks again,
Karl
The hydrogen peroxide might work, and chlorine bleach might work.
To keep alcohol from evaporating as quickly, I sometimes put a little mineral spirits, in shellac finishes to slow down the evaporation.
I would be really hesitant to get acetone next to the glued joint, because most of the ca glues are formulated to dissolve in acetone as a safety feature. When super glue first came on the market, it wasn't soluble in any of the common solvents that didn't burn skin, so it caused a lot of problems in the Emergency Rooms, when folks started showing up with their fingers glued to things.
Yeah, well, I'd not hold my breath. The quartz in the granite is the big problem I'm afraid. That will show even the teenyist bit of off color and magnify it under light. Hey, try some blue lights in the room!
Wait I might be on to something else with that wisecrack..focus a UV light on it and see what gives, UV is good at degrading and fading color. If the quartz is photoscopic enough it should maybe penetrate.
Can you post a pic? I'd like to SEE the affected joint, because maybe you could saw it through and reglue if it didn't seep too far, the project will be a kerf narrower and if its a counter top, maybe not a big deal?
In the future I guess 2 part epoxy or corian seam fill might be a better choice, or CA without accelerator. BTW, plain water or spit will speed up CA set rate.
I'll see if I can rattle Michael's chain today and see what he has to say.Spheramid Enterprises Architectural Woodworks
Repairs, Remodeling, Restorations
They kill Prophets, for Profits.
Here is my GURU of all things chemical.
http://www.michaeldresdner.com/
I emailed him and can call later in the day if I don't hear back..I'll keep checking my email as I work today.Spheramid Enterprises Architectural Woodworks
Repairs, Remodeling, Restorations
They kill Prophets, for Profits.
I am not sure if I know how to attach this photo but here goes.I am not too worried about the solvent attacking the glue as it has polyurethane behind the stone that is fully cured.The first photo is a much smaller stain and if the seam comes unglued the piece is still supported from underneath.The real problem area is photo called greenspot3 but it has either gotten worse or it just doesn't show up in the photo. Currently it looks like someone took a dark blue paper folder like title companies use for their documents, got it saturated with water and left it on the countertop overnight. There is a smaller green spot on the 4" backsplash seam that is undeniably mine so I can only assume I am responsible for the big spot.
It is so big 6 by 8" that I can't imagine what we did during the install. I used the CA to stabilize the 4" long backsplash seam while the primary adhesive set up. The actual stain is on the horizontal surface below the backsplash, as if I or my helper gave the entire area a HUGE blast of kicker. I don't recall either of us spraying it wildly but it was back before xmas when we did it.The stain adjacent to my actual seam is green in color but the BIG stain on the horizontal surface is more blue in color. Even though the color is different, I doubt the homeowner had anything to do with it.The other interesting thing is it took 4 weeks or more for it to show up???The reading I did on Toluidine dye gave me the impression that the more alkaline the surface is the darker it gets and it can be lightened by washing it with a lower ph solution or isopropyl alcohol. I always assumed granite was ph neutral but really don't have much awareness of the chemistry involved. Maybe the kicker ran down the backsplash joint, got sucked into the countertop underneath it and it didn't react and turn blue until an alkaline kitchen product absorbed into the stone many weeks later.This is a very porous stone (kashmir exotica) that has multiple coats of a good quality sealer on it and that may slow down the removal of the stain with a poultice.Thanks for the continuing input.Karl
I just enlarged the pics w/irfan view and kinda see the blue in the second one.
But , something is amiss. You say it took 4 weeks? Every kicker stain I saw happen ( and I have used gallons glueing bindings and frets in guitar work) happened rightaway as soon as it catalysed the CA.
And 6x8 can't possibly be caused by the spritz , what kinda kicker did you use? I have a 2 oz bottle of "Insta-set" that is a small pump and maybe has a fan of 2" or so at a foot away..something just don't sound right.
I see a green glob in the inside corner of pic one, is that it?
View Image
I see the line where it gets blue..is THAT it? Either way, I think its something else going on.
Spheramid Enterprises Architectural Woodworks
Repairs, Remodeling, Restorations
They kill Prophets, for Profits.
Edited 2/6/2009 12:30 pm ET by Sphere
The photo you pasted into your post with the "Green glob" is a minor issue. The big deal is the other photo where you cant really see the stain. It is the one that is 6" by 8" and when you are in the room looking at it, it is a distinct bluish green blotchy spot.The four week thing has me baffled as well. I had a few issues in the past and they appeared immediately. All I can speculate is that the Para Toluidine kicker was later activated as a dye when something altered the ph of the stone to a more alkaline level.I am hoping your chemical guru might have some thoughts. The other odd thing is that the stains I have seen occur before were always green but the big problematic one in this case is more bluish.The kicker comes in a giant aerosol can with a medium viscosity CA glue at my local lumberyard.
If my memory is correct it is dimethyl p-toluidine.Karl
Read all the posts and was wondering, do you have samples of the original stone to practice any stain removal technique on? As you stated, the stone is porous and that alone could be a big problem for you and any stain removal attempt. These aromatic amine form compounds called "AZO" dyes and, as you have found out, can be very troubling in applications such as counter tops. Finding a method to remove the stain may take time and at the very least, some trial and error to find, if at all. If you have some samples of the stone, apply some of the accelerator to the stone and let it sit undisturbed for a week or so to see if you can duplicate the stain. Then attempt various methods removal on the samples.In the mean time, see if the stain is just on the surface of the stone or below it, within the pours of the stone itself. In a small area, with a q-tip, apply some methylene chloride to the stain and rub gently to see if it's removed. Don't do this over a large area because it will dissolve the cyanoacrylate too and avoid getting it on your skin.
Good Idea! I do have leftover scraps and will hit one with accelerator to try and duplicate the stain. It will be much better to experiment on the stain at the shop rather than the clients home.The challenge is that the stain didn't appear for close to a month. Any ideas on how to accelerate the accelerator induced stain?Thanks for the suggestion,
Karl
A number of the substances mentioned, especially vinegar, are quite harmful to granite. Do not use any sort of acid.
Acetone should be safe.
Jeff
Are you thinking of limestone and marble in your cautions against vinegar. Granite has become a catchall term for just about any stone that can be cut into a slab and can take a polish.I have used full strength muriatic acid on some rust stained slabs to oxidize and remove the iron deposits without any lasting damage.On the other hand I have used distilled vinegar to remove the shine from limestone and marble slabs and it attacks the stone immediately.I have only successfully damaged granite with heat, abrasives, impact and as of now, Stains.I suppose there are a few acids that can etch glass and I wouldn't want them near a finished granite surface.Thanks for the input though as I am learning the dangers of thinking I know it all.Karl
Are you thinking of limestone and marble in your cautions against vinegar.
No! Do not use ANY acids of any kind on granite, including lemon juice, etc. - ever (they will etch the stone). Sealer does not prevent damage.
Jeff
I have a granite sinnk cut out we use for a pizza stone. After reading your post I poured a puddle of lemon juice, and apple cider vinegar on it last night. About an hour ago (8 hrs) I wiped it, and zero effect.Spheramid Enterprises Architectural Woodworks
Repairs, Remodeling, Restorations
They kill Prophets, for Profits.
Since this didn't show up for a month, are you sure it's from the glue and accelerator?http://www.tvwsolar.com
I went down to the lobby
To make a small call out.
A pretty dancing girl was there,
And she began to shout,
"Go on back to see the gypsy.
He can move you from the rear,
Drive you from your fear,
Bring you through the mirror.
He did it in Las Vegas,
And he can do it here."
Snort, Good question. I once before had a problem using CA glue and this particular chemical as an accelerator. The green color was much less intense and showed up immediately.On this job I used CA to glue a 2" strip of granite behind the sink to the countertop on either side while the primary adhesive set up underneath the stone. There is a small green patch near one of those 2" seams that I feel there is a very strong probability I am responsible for.The other seam with CA glue and accelerator was a joint between 4" backsplash and 18" full splash. There is a small green patch on that seam Again I would say there is a high probability I am responsible for that.The biggest stain is the one that is the real problem and I can't imagine how I could have caused it. It is on a clear horizontal surface beside the sink. The only reason I am feeling a strong responsibility to address it's removal is that it is only a few inches away from the 4" backsplash seam I used the glue on.The questionable stain is more of a blue color and the CA accelerator has always created a green stain so that adds to the uncertainty.If I hadn't used the CA glue anywhere I would think the homeowner or their kids had put a piece of blue paper or a blue cardboard folder on the countertop and let it sit with water under it overnight. Even thought the granite was sealed, the sealer only slows the penetration of foreign liquids.The homeowner is being very agreeable and not pointing any fingers nor am I but it is a mystery to me. Ultimately I just want to help them get it cleaned up to their satisfaction and add them to my list of 100% satisfied clients who will refer me to their friends.Karl
Was in a house with granite tops protected by red rosin paper... bad choice. I was thinking yours might have been blueberry popsicled?http://www.tvwsolar.com
I went down to the lobby
To make a small call out.
A pretty dancing girl was there,
And she began to shout,
"Go on back to see the gypsy.
He can move you from the rear,
Drive you from your fear,
Bring you through the mirror.
He did it in Las Vegas,
And he can do it here."
You are welcome to do whatever you like, and granites do vary widely in how they are affected by materials, however the ROT is:- NO ammonia (including Windex, etc.)
- NO acids (neutral PH cleaner only), no lemon juice, vinegar, soft drinks, wine etc.
- NO bleach (unless absolutely necessary in a poultice to remove a stubborn stain
- NO abrasive cleaners (especially if polished stone)
- NO silver polish (found out about this one the hard way)
For typical countertop 'stains' I would ramp up from:
- soap and water
- commercial neutral PH granite cleaner
- acetone
I have also safely used Gel Gloss
Isopropyl alcohol shouldn't be a problem either.
Jeff
Edited 2/7/2009 11:48 am ET by Jeff_Clarke
After reading your post I'm left wondering why anyone would put in granite? BruceT
Oh puhlease ...
Look it's one of the most durable, attractive countertops you can install. I have over 110 SF of Cambrian black antique and love it.
The list of 'don'ts' is very short compared to anything else. You can put hot pans anywhere on it without any concerns and the darker granites are incredibly hard - you're not going to scratch it short of diamond or carborundum.
I love our granite tops and wouldn't change them for anything else.
But I still don't put acids on them ...
And, my comments are supported by many sources ...
http://www.ehow.com/video_18200_clean-granite-countertop.html
http://www.doityourself.com/stry/granite
http://housekeeping.about.com/od/surfacecountertop/p/granitecounters.htm
http://www.countertopspecialty.com/granite-counter-top-care.html
Jeff
Edited 2/8/2009 9:26 pm ET by Jeff_Clarke
Just keep the sample at room temp to duplicate the conditions for the stained counter top. You need to find out if the toluidine accelerator is just on the surface or if it's absorbed into the top layer of the stone. If it's on the top layer then you might be able to polish it out, that's a better idea then using some solvent which my thin the toluidine and carry it further into the stone. Using white vinegar might also work, since that will make the toluidine more water soluble, but then the vinegar may color the stone too. I think that staining sample pieces is a much safer way to investigate the solution. It might take awhile to figure it out but what's a little time compared to a quick all out replacement of the whole counter top? Just keep the homeowners informed about your efforts and what your doing to fix the problem for the long haul.
Edited 2/6/2009 6:29 pm by woodway
Ok, Michael got back to me. It appears the fix ( if you call it that) is to use nitromethane ( funnycar fuel) and REMOVE the CA, It is also sold as 'Debonder' ( I have not searched out a source).
Then reglue, and skip the kicker.
Thats all I gots.
Spheramid Enterprises Architectural Woodworks
Repairs, Remodeling, Restorations
They kill Prophets, for Profits.
Sphere, that helps! I have a few bottles of debonder. I will give it a try when I go back to check it out on tuesday.Thanks,
Karl
Did you try contacting the manufacturer of the accelerator? Seems like they should know more about it than anyone else.
I've looked up dimethyl para-toluidine and toluidine blue dye. They are different compounds. The only connection is that methyl toluidine is used as a feedstock for synthesis of toluidine blue dye.
Dimethyl para-toluidine is a white crystaline solid at or below 43° C and is soluble in acids. It has one benzene ring with a methyl group and an amino group on opposite ends.
http://www.chemicalland21.com/specialtychem/finechem/n,n-DIMETHYL-p-TOLUIDINE.htm
Toluidine blue is made by reacting toluidine with other chemicals to form a sort of triple benzene ring molecule with sulfur, nitrogen,amide and amino groups.
http://stainsfile.info/StainsFile/dyes/52040.htm
I got an email from the client to let me know that the acetone poultice is working. It sounds like it may take four or more poultices to adequately diminish the color but as long as it works I am content.
This is the large bluish stain that I can't imagine how I created it using this glue/accelerator. It wouldn't surprise me if one or more of the family members may actually know more than they are letting on about something blue being left on a wet countertop for several hours.
I will call the mfg of the glue/accelerator kit in the am and ask them for more info on the greenish stain their product creates.
Karl
I called Fastcap who sells the adhesive and accelerator (they call it 2P-10). I think they knew less than me about the chemistry of the accelerator. I got the impression they just market the glue and it is made by someone else.They were nice enough to offer to send me a free glue kit with a different accelerator (heptane) and three different viscosities of glue for free so I could try out the other accelerator and see if it caused problems.I checked out the poultices progress this morning. The stain is coming out nicely with a poultice made of isopropyl alcohol and water. I am strongly thinking that the big stain by the sink was caused by something one of the homeowners family members left sitting in a puddle of water by the sink.I am glad to see it all get better I just wish I knew if I was the cause of the biggest stain.
Thanks to all of you for your input.
Karl