[Nhcoll-l] Update on jar lid liner issue

CAHawks at aol.com CAHawks at aol.com
Thu Aug 2 18:53:55 EDT 2012


Hi Scott,
 
Many thanks for the very useful information.
 
Cathy
 
Catharine  Hawks
Conservator, NMNH
(h) 703.876.9176
(o) 202.633.0835
mobile  703.200.4370
mobile 202.701.8458


In a message dated 8/2/2012 11:20:22 A.M. Eastern Daylight Time,  
Scott.Williams at pch.gc.ca writes:

There are many factors that could cause  one brand of foam to degrade while 
others do not, including blowing agents,  stabilizer additives, polymer 
properties (tensile strength, elasticity) and  foam properties (compression 
set, degree of crosslinking, cell size, presence  of integral skin).  The 
description of the Kohls foam as having a  different blowing agent may imply 
different degree of crosslinking.  I  think it is more common to use chemical 
blowing agents, not physical blowing  agents, for crosslinked foam.  This 
could make a big difference to  longevity.  Not all crosslinked polyethylene 
foams are chemically blown.  Volara and Plastazote are crosslinked polyethylene 
foams acceptable for  conservation applications that are physically blown.  
I do not know  whether Kohls or TriSeal liners have uncrosslinked or 
crosslinked  foam.

There are two types of  blowing agents – physical and chemical.  Physical 
blowing agents are  gases like nitrogen and carbon dioxide or low boiling 
solvent like pentane and  isopentane or in the old days CFCs (now no longer 
used by anyone), which are  dissolved in the molten plastic in a high pressure 
chamber in an upstream part  of the manufacturing process.  This pressurized 
molten plastic containing  blowing agent is ejected (extruded) through a 
die.  The downstream side  of the die is at atmospheric pressure, so the 
pressurized gas boils out of the  molten mass creating gas bubbles in the polymer 
matrix, just like carbon  dioxide bubbles out of champagne bottle when the 
cork is popped (or in my case  when the beer cap is removed).  The molten 
plastic freezes to trap the  bubbles and now you have a plastic foam. This 
foam contains only the plastic  (with required additives) and the gas.

Chemical blowing agents are solids which are dissolved  in the molten 
plastic.  The solids have the property of decomposing when  heated to produce gas 
degradation products (plus residual solid degradation  products) such as 
azodicarbonamide, or they are combinations of chemicals such  as sodium 
bicarbonate and citric acid which release gas when they react (plus  residual 
solid reaction products).  The solids react and gases are  produced and 
dissolved in the plastic in the hot high pressure chamber then  the plastic is 
extruded and foam is produced as described above.  

The main difference  between the two types of foam is that chemically blown 
foam has blowing agent  degradation and reaction products left behind in 
the foam but physically blown  foams do not.  These can affect long term 
stability and conservation  suitability of the chemically blown foams.  In 
general I recommend that  chemically blown foams be avoided because of potential 
problems related to  these residual degradation products.  

Generally the blowing gas originally present diffuses  out of the foam and 
is replaced by air that diffuses in.  The grade of  plastic used must be 
carefully selected or a carefully selected suite of  additives must be added to 
the plastic to control diffusion and permeation  rates (permeation control 
agents) so that the rate of diffusion of the blowing  gas out of the foam is 
the same as the rate of diffusion of air into the foam.  Otherwise the foam 
will collapse if the blowing gas diffuses out more  quickly.  It is a 
complicated and carefully balanced process.  It is  one of the reasons why 
manufacturers do not arbitrarily change the composition  of their products.  I 
think it is one of the reasons why there were  problems with degradation of 
some PE foams in the 1990s.  Manufacturers  were forced to abandon CFCs and 
some did not quite figure out the correct new  combinations of grade of plastic 
and suite of additives for using new blowing  agents like pentane and 
isopentane, with the result that some foams degraded.  Eventually they corrected 
this (or went out of business), so now that  problem no longer exists.

A  more detailed discussion polyethylene foam, including blowing agents and 
other  additives, is in my article Polyolefin Foams, AIC News 2002 Vol 27-1 
January  starting on page 26, 
_http://www.conservation-us.org/_data/n_0001/resources/live/02_jan_aicnews.pdf_ 
(http://www.conservation-us.org/_data/n_0001/resources/live/02_jan_aicnews.pdf)  and a very outdated article, 
Ethafoam and  Other Polyethylene Foams in Conservation, on CoOL at 
_http://cool.conservation-us.org/byauth/williams/foam.html_ 
(http://cool.conservation-us.org/byauth/williams/foam.html) .

R. Scott Williams
Senior Conservation Scientist (Chemist), Canadian  Conservation Institute
1030  Innes Road, Ottawa, Ontario, Canada K1A 0M5
tel: (613) 998-3721
fax: (613) 998-4721
email: scott.williams at pch.gc.ca

"Hawks, Catharine" ---2012-08-01 07:21:34 PM---Did  Kohls note what was 
used as the blowing agent? I've seen many polyethylene  foams that were blown

From: "Hawks, Catharine"  <HawksC at si.edu>
To:  Paul Callomon <callomon at ansp.org>,  "NH-COLL listserv 
(nhcoll-l at mailman.yale.edu)"  <nhcoll-l at mailman.yale.edu>
Cc: "Scott.Williams at pch.gc.ca"  <Scott.Williams at pch.gc.ca>
Date: 2012-08-01 07:21  PM
Subject: RE: Update on jar lid liner issue
 
____________________________________



Did Kohls note what was used as the blowing  agent? I've seen many 
polyethylene foams that were blown with gases other than  nitrogen that have 
discolored (yellowed) quite rapidly.

Scott, might  this contribute to the deterioration of the liners in Paul's  
collection?

Cathy
Catharine Hawks
Conservator
National Museum  of Natural History, MRC 106
Research & Collections, NHB  394
Smithsonian Institution
PO Box 37012
Washington, DC  20013-7012
Office 202.633.0835
SI Cell 202.701.8458
CH Cell  703.200.4370
hawksc at si.edu<_mailto:hawksc at si.edu_ (mailto:hawksc at si.edu) >


________________________________
From:  nhcoll-l-bounces at mailman.yale.edu 
[nhcoll-l-bounces at mailman.yale.edu] On  Behalf Of Paul Callomon [callomon at ansp.org]
Sent: Wednesday, August 01,  2012 1:33 PM
To: NH-COLL listserv (nhcoll-l at mailman.yale.edu)
Subject:  [Nhcoll-l] Update on jar lid liner issue

Colleagues,

Realizing  the possible implications for us all of age-related failure of 
jar lid liners,  I have been doing some survey work. The results are 
encouraging.


-  The supplier of the liners, O. Berk (KOLS  Containers in those days) 
have confirmed that the liner in question is a  generic version of the 
Tekniplex F217 liner that differs from the brand-name  version only in the blowing 
agent that is used to foam the center core. The  outer skins are solid 
low-density polyethylene, and the center is foamed  LDPE.

-          I retrieved and tested  several other jars using the same lid 
that were put into service in the same  or following year (2000-01). The lids 
thus came either from the same batch as  the failed one, or from another 
batch that was purchased shortly after. I  carried out a simple visual 
examination followed by a pliability test. For the  latter, I lifted the edge of the 
liner (it is glued to the inside of the lid)  in two places using a dental 
hook and folded a flap over until it touched the  surface of the liner 
(folded double). When it had returned, I inspected the  surface. The material 
showed some wrinkling from this treatment, as is normal,  but no cracking or 
crazing. This is the same thing that happens with a brand  new liner, and 
although the wrinkling remains to a certain extent, this does  not seem to 
compromise sealing.

-          By  contrast, the failed liner snapped when folded over, and its 
surface is  covered with a combination of fractal (branching) crazing as 
well as the  cell-like crazing one sees in old ceramic glazes. The material 
has thus  clearly undergone a major chemical change, and a colleague has 
generously  offered to run tests to try and diagnose this.

In conclusion, it seems  that this might have been a single incident. The 
next step is to trace the  history of the contents (13 separate specimen lots 
in glass tubes) and see  what treatments were used on them that might have 
caused this  problem.


Paul Callomon
Collections Manager in Malacology,  Invertebrate Paleontology and General 
Invertebrates
The Academy of Natural  Sciences of Drexel University
1900 Benjamin Franklin  Parkway
Philadelphia, PA  19103
callomon at ansp.org
Tel.  215-405-5096
ansp.org
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