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By Alex Jones

34 | PLASTICS ENGINEERING | SEPTEMBER 2008 | www.4spe.org


The term “microbe” is used as a general description

for any bacteria, fungus, mould, or mildew. In one

form or another, these microscopic organisms have

adapted to their environments and thrive even in

the harshest conditions. They have a unique ability

to quickly evolve and adapt and in some cases to

go dormant for extended periods, which has made

them extremely resilient. While the vast majority are

harmless, and indeed many are beneficial, there are

pathogenic strains that have gained notoriety, most

notably the hospital “superbugs” MRSA and

Clostridium difficile.

he role of biocidal agents is to

T
reduce the “bioburden” in certain
environments where, in worst-case
scenarios, unchecked microbial
growth can lead to food poisoning or potential-
ly fatal infections. The need to reduce the inci-
dence and proliferation of microbes is far-
reaching.
Antimicrobial polymer additives can be fit
into two broad categories: organic or inorganic.
These systems have different attributes and
therefore different ideal end-applications.
While many antimicrobial additives are
referred to as biocides, there are in fact two dif-
ferent methods of effect: biocidal (killing the
organism) and biostatic (preventing reproduc-
tion). Organic additives are biostatic, and inor- Alex Jones

www.4spe.org | SEPTEMBER 2008 | PLASTICS ENGINEERING | 35


ganic additives combine biocidal and rate, and the migratory molecules can can influence the migration rate and
biostatic properties. interact with large numbers of longevity of the active system.
microbes very quickly. This does, Soft PVC products are good exam-
Organic Systems however, affect the lifespan of activity, ples of where organic systems are suc-
Organic-based systems, which as the additives leach out over time, cessfully employed to guard against
include the organometallic class of leaving little in the polymer’s reser- microbial degradation such as black-
molecules, rely on small migratory voir. The addition rate and choice of pitting and pink-staining. PVC itself
molecules to introduce an antimicro- organic additive itself are functions of can intrinsically heighten microbial
bial effect at the polymer’s surface. the level of efficacy required and the growth, and this is exacerbated when
Once incorporated into plastic, they duration of action needed. it is used for applications in wet envi-
migrate, over time, out of the poly- Organic technologies often fit bet- ronments such as shower curtains,
mer matrix and onto the polymer ter commercially with disposable paddling pools, and waterproof lin-
surface, where an antimicrobial “film” items that have shorter lifespans than ings.
is formed. more durable and environmentally Many organic biocides are in the
Migration occurs as the molecules demanding products. Further limita- marketplace, but only a few have the
move down a concentration gradient tions include the lack of food-contact thermal stability required for surviv-
out of the plastic. The migration is approval for organic-based systems, ing the processing rigours of plastics.
driven by the inherent compatibility primarily because of the mobility and The most common organometallic
differences between the organic solubility of these additives in food antimicrobials are arsenic-based mate-
antimicrobials and the polymer sub- simulants. Therefore, when one is rials such as oxybisphenox arsine
strates in which they are dispersed. choosing a system for direct food (OBPA). While these additives are
The resulting film on the polymer’s contact, an inorganic-based technolo- very efficient and cost-effective, their
surface is replenished by additives gy is the only real option. use has been limited because of envi-
within the substrate whenever the Another consideration with organic ronmental concerns and market per-
surface is wiped or washed, or when systems is the effect of temperature ception regarding their long-term
the additive is lost to the environ- during processing. As temperatures toxicity. Even though OBPA has been
ment. increase, organic molecules become registered by the Environmental
The benefit of this mode of action more highly mobilised, resulting in Protection Agency (EPA) in the USA,
is that it can have a very high activity excessive loss rates from the plastic. these fears have unfortunately had a
Also, organic negative impact on market confi-
antimicrobials often dence.
have thermal- As a result, demand for non-
decomposition tem- arsenic-based formulations, such as
peratures similar to the non-metal-containing isothiaza-
the temperature of lone family of biocides, and other
the polymer-pro- types, such as triclosan (chlorinated
cessing window. diphenyl ether), is growing rapidly.
Polymers such as Growth is currently predicted to be
PVC and some low- between 10%/yr and 20%/yr in
temperature poly- Europe. Arsenic-based formulations
olefins are best suit- still tend to offer cost advantages over
ed to these addi- their non-arsenic counterparts,
tives. The environ- though.
mental temperature
in which finished Inorganic Systems
products will be Inorganic antimicrobials utilise metal
Antimicrobial activity of PE glove samples tested over an used should also be ions as their active biocidal agent,
eight-year period against E. coli. considered, as this and once incorporated into the poly-

36 | PLASTICS ENGINEERING | SEPTEMBER 2008 | www.4spe.org


them through a process of ion
exchange at the plastic’s surface.
The metal ions remain stored with-
in the polymer and are continuously
made available over the lifetime of
the particular finished product.
While there is no migration of the
ions, as with organic systems, it is
the delivery system that ensures a
constant replenishment at the sur-
Function of organic-based additive system in plastic substrate.
face. The additive-addition level and
delivery mechanism regulate how
mer matrix, these remain in-situ. The groups on the proteins, which func- quickly ions are released and the
most commonly used metal ion is sil- tion as enzymes in their critical meta- duration of the action. Some systems
ver; others include copper and zinc. bolic pathways. This denatures the favour rapid release, such as wound-
Silver ions are thought to disable enzymes, bringing about a loss of cell care applications, while others have a
bacterial cells by acting on them in functional ability, which leads to cell more controlled mode of action con-
several ways, and this multiplicity of death. tinuing over the lifespan of the sub-
action results in a strong biocidal The success of these systems relies strate.
effect. In the primary mode of attack, on the delivery of minute quantities Delivery systems on today’s market
ions bind to the cell membrane, of ionic metal at the cell membrane. include those relying on ceramic
affecting its ability to regulate the dif- The metal ions are usually bound glasses, doped titanium dioxides, and
fusion and transport of molecules in within a delivery system that stabilis- even zeolites as their carrier and
and out of the cell. Similarly, once es them, allowing their incorporation release mechanisms. Inorganic sys-
inside the cell, the ions target thiol into the polymer, and then releases tems tend to be much more thermal-

OLYMPUS NDT PRECISION THICKNESS GAGES


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a container can be moved by a magnetic probe held
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measurements and on corners and narrow grooves.

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www.4spe.org/productfocus/

www.4spe.org | SEPTEMBER 2008 | PLASTICS ENGINEERING | 37


ly stable than their organic counter-
parts, although some are subject to
discolouration. Their thermal stabili-
ty means there are a wide range of
polymers that can benefit from these
additives.
Variations on the inorganic theme
are metal-ion systems based around
nano-sized particles. These, for the
most part, have been developed to
explore the possibilities that rapid ion
release can offer (as a result of their Example of an inorganic system: residual levels of atmospheric moisture combine
high particulate aspect ratio). The with the hydrolytically reactive glass delivery system to release silver ions at the
active ingredient, the metal ion, surface of the plastic.
remains the same, but coupled with
this are adverse issues such as unquan- very high energies, such as those tems, as these freely move out of the
tified toxicity, excessive discolouration composed of silicone, are extremely plastic article and diffuse across the
resulting from rapid oxidisation, and hydrophobic and therefore less agar medium, creating a “zone of inhi-
the increased complexities of produc- attractive to colonising bacteria. bition.” This does not tell us if the bac-
ing nano-scale active grades. Currently, However, this hydrophobic charac- teria are dead or dormant; it tells us
nano-silver is not recognised by the teristic alone is not enough to pre- only if they have been inhibited from
Biocidal Products Directive (which vent growth; we only have to look at colony-forming.
implements Europe permissioning bathroom mould on silicone sealant It is a quick and cheap test, but diffi-
schemes for biocides and non-agricul- to prove that. Surfaces that are very cult to use for discerning quantitative
tural pesticides) or the EPA. smooth at a microscopic level can results; at best, a qualitative statement
While the incorporation of addi- also reduce the rate at which bacteria can be made based on the size of the
tives can successfully reduce the adhere and colonise. halo.
microbial loading on surfaces, the Inorganic systems, on the other
surfaces themselves can also play an Test Procedures hand, despite being highly efficacious,
important part, and this should be In discussions of the performance of will show only an extremely thin halo
given attention at the product-design the different systems on the market, it because of the lack of migration of the
stage. For example, surfaces with is important to outline the three com- additive, highlighting the limitation of
monly used types of test methods for this test method.
determining efficacy. The “Shake Flask” test ASTM
In the “Halo” or “Zone of E2149-01 is another method that
Inhibition” test, AATCC 147, an arti- demonstrates good results for migrato-
cle containing the antimicrobial addi- ry systems; however, only highly solu-
tive is placed in the centre of an agar ble inorganic systems can show reason-
plate that has been surface-inoculated able results. In this test, inherited from
with a strain of microbe. The plate is the textile industry, a specimen article
then incubated for a defined period. containing the antimicrobial additive is
The test measures the size of the cir- placed into a flask containing a known
cle or “zone of inhibition” surround- volume of nutrient agar broth chal-
ing the test piece where no microbial lenged with a defined number of bac-
growth has occurred following incu- terial cells. The flask is incubated on a
bation (see picture). shaker for a set period of time to allow
The “Halo” test, showing the effect of This test method is well suited to the bacterial proliferation, and then the
an organic antimicrobial. organic migratory types of additive sys- number of bacteria remaining in the

38 | PLASTICS ENGINEERING | SEPTEMBER 2008 | www.4spe.org


nutrient broth is determined. Examples of this test method include the market today generally deliver effi-
The third method, which is well ISO 22196 (JIS Z 2801), in which the cacy up to and above log 6
suited to all kinds of systems, measures plastic article is challenged with a (99.9999%) reduction in cell count
the antimicrobial effect on the surface nutrient broth containing a known cell against controls, depending on the pre-
of the plastic component itself. This is count. This is then incubated for a cise addition level of additive and the
therefore most appropriate when one is defined period before the number of delivery system used. In general, organ-
trying to determine the level of anti- remaining viable cells is determined. ic and inorganic systems find good effi-
bacterial efficacy on the surface of a The resulting efficacy is given as a log cacy at anywhere from 100 ppm to
finished article rather than its sur- or percentage reduction against a con- 2500 ppm in the plastic, depending on
rounding environment. It also has the trol, with a minimum 99% (log 2) the performance requirement.
advantage of generating data that can reduction being required to pass the While organic systems are often used
be quantitative, qualitative, and time- test specification. in PVC and very-low-temperature
related. Inorganic and organic systems on polyolefins, as previously mentioned,
inorganic systems perform well in
many different polymers and processes;

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The market for antimicrobial addi-
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Packaging use of silver as a biocide in polymeric
- Bags formulations alone is reported to have
- Shrink Film
risen in excess of 600% worldwide
- Separator Sheets
since 2001.
- Boxes / Foams / etc.
Whether incorporated in medical
gloves, packaging films, contact-lens
- Cost Reductions
cases, swimming-pool liners, food-

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wide range of sectors, a trend that is
definitely set to continue.

Based in the UK, Alex Jones is product


specialist for Wells Plastics’ Bactiglas range
of antimicrobial additive products
TM (www.wellsplastics.com). He has a BSc
(Hons) in Biological Sciences, has worked
www.Intercept-Technology.com
in consumer microbiology, and spent the
www.StaticIntercept.com
last five years in the polymer additives
industry.

Engineered Materials, Inc. ph: 847-821-8280


More Info contact: chrisdv@comcast.net

www.4spe.org/productfocus/

40 | PLASTICS ENGINEERING | SEPTEMBER 2008 | www.4spe.org