These slabs from Heritage look funky...

RockMyAmadeus · June 17, 2015

I have a Next Men #21 that has adhered to the inner well. It has been sitting in my house since the day it was received back from CGC, circa 2009. The inner well stuck to...and removed...ink from the front cover. The bottom right corner of the slab is busted, but the other three posts are intact.

It has NOT been subjected to any extremes of any kind, not heat, not water, nothing. It has been sitting in a box, in a house, surrounded by other slabs, inside my house, out of sunlight, moisture, anything that would adversely affect it. It was a 9.8. It is obviously not a 9.8 any more.

I have been extremely hesitant to bring it up under current conditions, as I am afraid that I will be told "too bad, there's nothing we will do about it."

The only circumstance was that it sat in a couple layers of bubble wrap for a few months. Is it possible that bubble wrap interacted with the inner well, on the inside of it....?

Possible, but rather unlikely and bizarre.

We shall see.

joeypost · June 17, 2015

Well done Heritage.

InvstmntComcSuply · June 17, 2015

Just to be clear, when you received it from CGC, the book was not stuck to the inner well?

Does the well appear melted similar to the other books in the thread?

Bomber-Bob · June 17, 2015

(thumbs u

RockMyAmadeus · June 17, 2015

No. I broke the corner myself, but the book was fine when it came back from CGC, and the well doesn't have any odd appearance.

Unca Ben · June 17, 2015

Topics like this would make me nervous if I had a really high dollar book in a slab.

I mean, can you imagine if, despite climate controlled storage, a book like ...

well, you know what I mean.

Tens, or hundreds of thousands of dollars (or more) stuck to an inner well. :eek:

InvstmntComcSuply · June 17, 2015

If it does not appear melted, then the other option is moisture causing the cover to stick to the Barex, then at some time later detaching and leaving ink behind. Elevated moisture content would not have had to occur on your watch.

It also seems unlikely that plastic that has laminated itself to the cover would come loose enough to remove ink from the cover. Although, I imagine there are degrees of bonding that occur at borderline temperatures.

Mark 1 · June 17, 2015

Would be nice to hear from CGC on this issue...

manetteska · June 17, 2015

Pic(s)?

RockMyAmadeus · June 17, 2015

Sure, when I can.

I promise, it's not bound, and doesn't contain Jack Kirby's long-lost comics.

jimbo_707 · June 18, 2015

I really wish CGC would address this issue. I have a number of old-label slabs that are could stand to be re-holdered in order to replace the (now 15-year-old) microchamber paper.

If this problem is due to some change in inner-well material, or some problem with a bad batch of material, I certainly don't want to send them in now.

Mark 1 · June 18, 2015

Don't swap out those old labels...my advice

jimbo_707 · June 18, 2015

I like old-label books, and I don't buy into the idea of replacing the microchamber paper every 7 years, but I also don't think it will last forever.

nearmint · June 18, 2015

I PM'd Paul about it, but then noticed on Facebook that he's been on vacation in Iceland for a few weeks.

jimbo_707 · June 19, 2015

In terms of moisture being a possible culprit with the Next Men no. 21, was the book pressed prior to slabbing? I understand that books are humidified as part of the pressing process, so it stands to reason that some of that trapped moisture might escape into the inner well after slabbing.

jpepx78 · June 30, 2015

The chemistry & physics of comic collecting: Deformed slabs and puddling

The hot summer weather had me thinking of people's concerns about deformed CGC slabs and I may have some plausible explanations and I believe the cause is exposure of the Barex case to extreme heat and not the quality of the Barex material. First some key terms need to be defined and some key concepts require some explanation before discussion.

key definitions

melting point: the temperature at which a solid turns into a liquid

heat deflection (or deformation) temperature for plastics: temperature at which a polymer or plastic is deformed under a specified load

thermal conductivity: the rate at which heat passes through a specified material, expressed as the amount of heat that flows per unit time through a unit area with a temperature gradient of one degree per unit distance

Barex: acrylonitrile-methyl acrylate polymer made by Ineos that is used in the inner well of CGC slabs, melting point 331 deg F (166 deg C), heat deflection temp 170 deg F @ 66 psi (77 deg C @ 455 kPa)

http://www.ineos.com/Show-Document/?Grade=Barex%20210%20Film%20Grade&BU=INEOS%20Barex&DocumentType=Technical%20Data%20Sheet

mylar: polyethylene terephthalate (PET) commonly used for protective plastic coatings, insulators, balloons and comic book protection, melting point 489 deg F (254 deg C), heat deflection temp 239 deg F @ 66 psi (115 deg C @ 455 kPa)

http://www.makeitfrom.com/material-properties/Unfilled-PET/

styrene-acrylonitrile (SAN): copolymer plastic consisting of styrene and acrylonitrile that is used in the outer case of CGC slabs, heat deflection temp 203 deg F @ 66 psi (95 deg C @ 455 kPa)

http://plastics.ulprospector.com/generics/47/c/t/styrene-acrylonitrile-san-properties-processing

heat conduction: heat transfer between substances that are in direct contact with each other

convection: heat transfer through a liquid or gas

radiation: heat transfer through electromagnetic waves

ultrasonic weld: an industrial technique where high frequency ultrasonic acoustic vibrations are locally applied to workpieces being held together under pressure to create a solid-state weld

http://www.dukane.com/us/PPL_whatisUPA.htm

thermoforming: a manufacturing process where a plastic sheet is heated to a pliable temperature, formed to a specific shape in a mold and trimmed to create a usable product

http://www.custompartnet.com/wu/thermoforming

key concepts

Solar radiation is radiant energy emitted by the sun, particularly electromagnetic energy. About half (52%) of the energy is in the near-infrared (700-2500 nm) , 43% is in the visible range (400-700 nm) and the remaining 5% is in the ultraviolet range. Two important types of ultraviolet radiation are UVA (320-400 nm) and UVB (290-320 nm). The portion of this ultraviolet radiation that is not absorbed by the atmosphere causes sunburns on people. When this electromagnetic energy, of which visible light is one part, reaches an object, it can be absorbed, reflected or transmitted through an object. Generally a combination of these occurs. Objects that absorb heat can emit thermal radiation.

UV spectrum energy chart

https://en.wikipedia.org/wiki/Sunlight

Deformed Slabs during Shipping

I believe nearmint's deformed slabs were exposed to extreme heat during shipping above the heat deflection temperature of 171 deg F for Barex as many people have suspected. It is unlikely Heritage would have subjected the slabs to such high temperatures in their possession. Nearmint supplied the itinerary of his US Postal shipment from Dallas to Newport Beach CA from June 1, 2015 to June 4, 2015. The mean temperature in Dallas was 72 deg F with a high of 86 deg F on June 1st. His shipment must have gone through the Phoenix Arizona area around June 2nd. The mean temperature for Phoenix was 90 deg F with a high of 104 deg F. Most postal trucks are not heavily insulated and if they are heavily packed, there would be little airflow for convective cooling.

One trucker in Kingman Arizona experienced 125 deg F with air conditioning on full and 141 deg F with the A/C off and heater on. Imagine how hot the trailer would be.

http://www.thetruckersreport.com/truckingindustryforum/threads/spoiled-rotten-company-owner-make-me-wanna-puke.141421/page-9

Here's an interesting research study by the International Safe Transit Association (ISTA) to monitor temperatures and humidity in trailers in the summer of 2001. The data was collected at 2.5 minute intervals for seven trips from Dallas to Phoenix via Abilene and El Paso Texas which would probably be very similar to the route nearmint's shipment would have taken. For the four week study of seven trips, ambient temperatures ranged from 71 deg F to 104 deg F, relative humidity ranged from 19% to over 90% and trailer temperatures ranged from 72 deg F to a high of 145 deg F. The high trailer temperature of 145 deg F was achieved when the ambient temperature of Phoenix was 105 deg F. The high trailer temperatures were achieved during the mid afternoon of the day and the trailer temperatures were usually around 30 to 40 degrees above the ambient temperature. Although the temperature extremes were brief, Barex would deform if it is exposed to the heat deflection temperature for a few seconds. Also Barex will deform at a lower deflection temperature if it is subjected to a higher pressure or weight. This small data set was collected targeting known high temperature environments and does not represent typical trailer environments but gives an idea of trailer conditions. This study is not conclusive evidence of what happened to nearmint's slabs but shows that very high temperatures during shipping can be reached for extreme heat exposure to cause distortion of the Barex sleeve. There would be concerns for shipments that pass through areas that happen to experience very high temperatures.

http://www.ista.org/forms/ISTA_Temperature_Report-2002.pdf

A typical CGC slab has a thick ultrasonic weld at the top between the label and the top of the book, thin welds along the left, right and bottom edges of the slab. Barex bends slightly as the temperature rises to or above the heat deflection temperature and solidifies as the temperature decreases. However the deformation of the Barex is more noticeable at the top of the slab because of the thick sonic weld and the Barex overhang for the label. As the thick weld softens and bends, the weld becomes disordered and distorts since it is not held under pressure by any form or mold and remains deformed as it cools. The deformation on the other welds are less noticeable since they are thinner and there is less Barex overhang.

Here are closeups of someone else's slabs where the Barex has deformed.

What can be done to limit exposure to extreme heat? Shipping by temperature controlled trailers probably would be costly and not always necessary. Shipping slabs in styrofoam boxes insulating against high temperatures would work but would require multiple sizes for different size shipments, would add bulk, increase shipping costs and is not environmentally friendly.

Aluminized mylar bags could be a viable option since they can withstand 255 deg F heat for 55 minutes, reflect about 90% of radiant heat and have a very low thermal conductivity. Wrapping slabs with bubble wrap to form an insulating air gap and covering with an aluminum mylar bag would greatly reduce exposure to extreme heat. Metallized mylar has been used in spacecraft, housing thermal insulation, food and pharmaceutical packaging. Also mylar has excellent moisture barrier properties. An aluminum mylar bag probably would be worth the small additional expense for heat protection and would ease concerns.

This site is for informational purposes and not an endorsement.

http://www.sorbentsystems.com/mylar.html

Here's a video explaining radiant foil insulation.

If aluminized mylar is good enough to protect spacecraft for NASA, then it is good enough for something infinitely more important such as comic book slabs.

Deformed Slabs from Sun Exposure

Comicwiz was puzzled when he found his slabs were deformed after about 4 hours in a display case under a covered tent on a sunny day. His slabs show more deformation than nearmint's slabs and the Barex was stuck to the covers for a few slabs. He said the ambient temperature was in the mid-30s (35 deg C = 95 deg F).

10419060_426531364152635_2793397461029040864_n1_zpsmeyasb2i.jpg

When he left his slabs in the display case I believe he experienced a greenhouse effect that is comparable to the high temperatures of car interiors attained under sunny skies. There have been many studies of the greenhouse effect in hot cars to highlight the dangers of leaving children and pets in cars. Temperatures can rise very quickly as solar energy is absorbed and trapped in car interiors as shown in this chart.

car%20temp%20sfsu_zpsexto4b40.jpg

This San Francisco State study shows interior car temperatures can rise quickly even within 10 minutes.

http://ggweather.com/heat/heat%20study.pdf

In this Australian study, car interior temperatures reached about 75 deg C where the ambient temperature was 31 deg C in about 2 hours. There was negligible temperature difference for car color, window tinting or sunshades and a small temperature difference for windows left slightly open.

http://www.google.com/url?sa=t&rct=j&q=&esrc=s&source=web&cd=13&ved=0CC0QFjACOAo&url=http%3A%2F%2Fwww.racq.com.au%2F~%2Fmedia%2Fpdf%2Fracq%2520pdfs%2Fcars%2520and%2520driving%2Fdriving%2F0814_temperature_in_cars_survey_2009.ashx&ei=qF-OVb6oJcnjoASg16CQAQ&usg=AFQjCNFSymeYq-WIEvKwHrzWNGc-t9teYw

Although his slabs were in a display case under under a covered tent not in direct sunlight, the light fabric covering was not fully UV protected. About 95% of radiant energy is in the near-infrared and visible spectrum. When solar radiation strikes an object it can be reflected, absorbed or transmitted. Let's break down the radiant energy as it passes through the tent cover to the display case. The white tent cover is thin so a small amount of energy is reflected, a negligible amount absorbed and most of it is transmitted. As the filtered energy strikes the display case, some energy is reflected and the energy transmitted through the clear case is absorbed by the display case material and its contents. The absorbed radiant energy accumulates and some energy is emitted into the case and reflected back by the clear case that results in a rising temperature. Although the back panel doors of the display case were left slightly open to allow hot air to escape, there is not enough airflow movement for convective cooling. Stagnant air acts as an insulator trapping heat. The enclosed display case was an unintentional but ideal greenhouse to cook the slabs and the heating effects are similar to that of hot car interiors under the sun. Mylar would not be affected because it has a much higher heat deflection temperature. Jimbo_707 is correct in assuming the CGC case itself would be a factor because it contains a pocket of air which would help retain heat within the case. Long time exposure to UV and visible light will cause colors to fade and UV radiation is responsible for 40-60% of the damage.

car%20gh1_zpse5ujjzw5.jpg

http://hyperphysics.phy-astr.gsu.edu/hbase/thermo/grnhse.html

I don't know if the display is made of glass or plexiglass (acrylic) but there are some property differences. Glass has 90% light transmission and acrylic is 92%. Glass blocks UVB and about 25% UVA. Acrylic blocks UVB and about 35% UVA. Acrylic is a better insulator since it has a thermal conductivity of 0.17 versus 0.8 (W/m*K) for glass.

It may be hard to believe that the insides of the display case can reach very high temperatures but a simple experiment can be done by checking the temperature with a thermometer in the display case with the panel doors closed after leaving it out on a sunny day after 4 hours.

There are a few simple ways to minimize or reduce the amount of solar energy if an outdoor setup is done again. Use thicker tent fabrics so that no visible light can pass through and to absorb some of the solar energy. If you can see light through the fabric, it is not UV protected. If the display case is used again, leave the panel doors fully open to allow for convective air cooling. Apply a reflective film to the clear case to reflect or block UV and IR radiation. There are some transparent films that can block up to 90% of infrared radiation and even 50-60% of heat.

I don't think CGC ever envisioned their slabs to be normally exposed to such high temperatures. Don't leave small children, pets or comic slabs in your car or outside for a long time.

Barex Well Puddling

Some people have noticed a slight indentation in the Barex wells or a puddling effect in the back of some of their slabs. Although this slight bulge is not detrimental to the encased comics according to CGC, some collectors have found this defect to be not aesthetically pleasing. Some have surmised that the Barex is of inferior quality, or a different material was used for the inner well or some chemical reaction has taken place. I don't believe any of these theories are accurate because vaultkeeper, a lab analyst at Barex manufacturer Ineos, has done tests and found no difference between Barex samples from a month and five years ago.

The defects are found only on the back of the Barex wells since they are made by a thermoforming process where the Barex sheet is heated to its softening point, stretched into a mold by vacuum, air pressure or mechanical pressure and held in place to the desired shape until it cools. The excess material is trimmed and the formed part is released. Problems can occur if the part is released too quickly or there is not enough vacuum or air pressure before the Barex is cooled sufficiently. I believe the indentations or puddling are a result of not allowing enough time for the Barex wells to cool down in the molds to "set" into the desired shape. CGC has acknowledged the problem but I don't recall if they explained the cause. I haven't read about any complaints of puddling in about a year, so I assume people are either tired of talking about it or the problem has been resolved by CGC's Barex supplier.

http://boards.collectors-society.com/ubbthreads.php?ubb=showflat&Number=6703699&fpart=1

Barex thermoforming data sheet

http://arboplastic.ch/dokumente/ThermoformingOfBarexsheet.pdf

Barex production shutdown

I mentioned earlier in the thread that Ineos announced that they are shutting their Barex production facility in Lima Ohio in early 2015 since it was a money losing business. Even though Barex is used in many food and pharmaceutical packages, it is considered a niche product at 220 kilotons per year (2010 Ineos annual report). Barex is produced in Asia and Europe but the starting material for Barex is only made in Lima Ohio. Unless some other company is willing to resume Barex production, CGC will eventually have to find a replacement material for the inner case.

http://www.chemicals-technology.com/news/newsineos-barex-to-close-resin-production-facility-in-ohio-us-4423745

http://civlimanews.wpengine.com/archive/15349/news-business-home_top-news-50600607-ineos-closing-barex-part-of-lima-business

http://www.plasticsnews.com/article/20141029/NEWS/141029713/ineos-closing-barex-plant-exiting-business

bc · June 30, 2015

Thanks for an extremely informative post for Comics General. (thumbs u

-bc

Domo Arigato · June 30, 2015

Not sure if this is the same phenomenon....but this scan is from the Comiclink auction that ended 6/24/2015

vaultkeeper · June 30, 2015

My initial testing of the Barex was 20 minute tests. (enough time to allow the temperature of the Barex to equilibrate in the oven). My results were in line with the Barex FMS (Finished Material Specifications).

I have done further testing, at lower temperatures, for longer times, to see if the Barex would start laminating at lower temps. The short answer is Yes.

The lowest temperature I was able to get adhesion was 70 Deg C (158 Deg F) over a 10 hour exposure time.

originalisbest · June 30, 2015

Very informative thread! It's odd to me that only recently has this seemed to be a noticeable issue, as I've little doubt CGC slabs in transit have been exposed to high ranges of heat in the past. Regardless, good info to be aware of.

Archived

These slabs from Heritage look funky...

142 posts in this topic

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites

Link to comment

Share on other sites