UV Stabilization of Greenhouse Film Covers - Experiences from an Additive Supplier

Patricia Ruiz1, Ivan Vulic2, Brent Sanders3 and John M. Zenner3

¹ Cyquim De Colombia, Bogota, Colombia

2
Cytec Industries B.V., Botlek-Rotterdam, Netherlands
3
Cytec Industries Inc., Stamford, CT, USA

Introduction
The stabilization of greenhouse films against light degradation remains an important challenge
for the additives industry. From a grower’s point of view, longer service greenhouse film covers offer
important savings both in labor cost and disposal fees. There are two main challenges associated
with greenhouse films lasting 3 or more seasons. The first is that the presence of chemicals often
used in agriculture severely impairs the performance of many of the most effective light stabilizers.
The second is that the UV screening effect that greenhouse films impart, which enhances the growth
of many crops, often diminishes over time. Thus crop yields may drop over time which can mitigate
any labor and waste disposal savings.

The stabilization of polyolefins against attack by UV light has advanced significantly during the
past 20 years but agricultural film applications continue to present a unique challenge. In spite of the
environmental rigors, highly effective light stabilizer formulations have been developed for greenhouse
films. Herein we describe systems designed for optimum visible light transmission, near-permanent
UV blocking effect, and maximum chemical resistance.

Background Before the introduction of hindered

Polyolefin films are found in a host of
agricultural applications. In uses ranging from
greenhouse films, mulch films and tunnel films to
shadeclothes and nettings, all are exposed to
the extremes of outdoor exposure as well as
occasional to chronic chemical exposure. The
use requirements of agricultural film demand the
preservation of flexibility, toughness, and in
some cases translucency throughout a service
lifetime ranging from 1 to 5 years. To meet
these demands, the UV stabilizer needs to have
a high inherent light stability, low volatility and
should not interact with other ingredients in the
additive package (i.e. antifogging agents,
thermal insulating compounds, etc.). The
lifetime of a stabilization package can be
shortened if the additives are too volatile, are
insoluble, or exhibit excessive migration in the
polyolefin matrix.1 In addition to the
requirements listed above, a successful UV
stabilization package in agricultural films must
be resistant to attack by pesticides.
amine light stabilizers (HALS), combinations of
UV absorbers (UVA) and nickel quenchers (NiQ)
were the stabilizers of choice for agricultural
films. Even today, this UV package is still
broadly used in agricultural films, especially
when sulfur based pesticides are being applied.
The UV absorber/nickel quencher blend, though
extremely resistant to pesticides, is not without
limitations. Reduced light transmittance from
the green colored nickel quencher limits the
concentration that can be used in greenhouse
films.2 Although NiQ’s can act as weak
absorbers, radical scavengers and
hydroperoxide decomposers, they are less
efficient than hindered amines as thermal
stabilizers.4 While it has been suggested that
NiQ’s are environmentally unsafe, the most
widely used compound (Ni-1084) is not a
carcinogen nor is it considered a hazardous
waste per 91/689 EEC.
Hindered amine light stabilizers (HALS)
seem well suited to the agricultural film market
because the catalytic radical scavenging
 mechanism by which hindered amines function
(Scheme 1), makes them highly effective even in
thin cross section materials.
Scheme 1
O
H
R'
N
N
N N [O]
N N
N
N N O O
N
H
n
R=O + ROH
However, in practice most HALS do not
adequately stabilize film in applications that are
subjected to aggressive pesticide use.2 HALS
are profoundly effected by acidic species
present in, or produced by the degradation of
agrochemicals. The deleterious effects of many
agrochemicals on conventional HALS stabilized
film are much greater than on UV
absorber/nickel quencher stabilized film.3,4 In
general, it is thought that acidic species can
react reversibly with the hindered amine leading
to the formation of an ammonium salt (Scheme
2).5 The conversion of the ammonium salt to the
nitroxyl radical active species is kinetically slow,
thus reducing the light-stabilizing efficacy. It has
been reported that sulfur based acid byproducts
of pesticides can negatively interact with HALS
in a similar manner. Epacher and Pukanszky
studied the effect of 24 different pesticides on
the lifetime of PE film containing HALS and
found that a large number of the pesticides did
not interact with the HALS. However, sulfur
containing compounds and organic halogenides
lead to faster deterioration of the HALS
stabilized film.6
Scheme 2
R' R' R'
HX
[O]
N N
H H
X
H O
R=O + ROH
As with nickel quenchers, HALS are
often used in combination with an UVA. UV
Absorbers protect the polymer by competitively
absorbing high energy photons and dissipating
the energy by non-destructive means. In
addition, they block all or part of the ultraviolet
spectrum of light entering the greenhouse. One
R
R'
needs to consider what effect modification of the
UV spectrum within the greenhouse has on plant
growth, fruit and flower quality, molds and
R
viruses, and pollination. Light between the
wavelengths of 280 and 400 nm is known to
ROO
cause polymer degradation and blockage of
these wavelengths provides optimum
stabilization benefits. However, some ultraviolet
light must penetrate through the film into the
greenhouse for satisfactory plant growth. The
light from 320 to 400 nm has a formative effect
on most plants while light from 280 to 320 is
detrimental to nearly all plants. Short
wavelength light (280-320 nm) also facilitates
fungus growth and rose petal darkening.7 In
addition to effects on plant and fungal growth
rates, many pollinating insects see in the UV
range below 360 nm.8
Within this context Cytec Industries Inc.
has worked to develop light stabilizer systems
for greenhouse covers that can withstand the
rigors of pesticide exposure. In doing so, the
strengths and limitations of each of the available
classes of light stabilizers must be considered
and systems devised that fully exploit the
benefits of each component in the system.
Experimental
Film Preparation
For benchmarking studies, masterbatches were
prepared of each compound. The LDPE used
was DSM Stamylan® 2100 TN 00, a tubular
reactor grade with a density of 0.921 g/cc and a
melt flow of 0.3 g/10 minutes. Film samples
were prepared on a Kuhne blown film line at two
R thicknesses, 50 and 150 µm. All films contained
R'
0.075 % of CYANOX® 2777 antioxidant as a
base stabilization package.
N N
O
R WOM Exposure
Film samples were cut to fit into standard 3" by 5
ROO
¾" WOM frames. Films were analyzed by FT-IR
for carbonyl content and a portion submitted for
mechanical testing before exposure. The
samples were placed in an Atlas Ci65A xenon
arc weatherometer operating under ASTM G155
conditions (63 °C black panel temperature, 42
°C chamber temperature, 0.35 W/m2 irradiance
intensity, 90 minutes dry followed by 30 minutes
of water spray). Samples were removed after
every 400 hours of exposure and analyzed by
FT-IR.
Carbonyl Measurement
Carbonyl intensity was measured using a Nicolet
Impact 410 FT-IR. These intensities were used
to calculate a "percent carbonyl" by the following
formula,
% Carbonyl = ((I1710-I1835)-Io)/(t*0.19)
where Io is the intensity difference at zero hours
and t is the film thickness in mils. The percent
carbonyl value was used to predict which
samples were nearing failure and should be
submitted for mechanical testing. It was found
that a value of 0.1 % marked the onset of
degradation and a value of 0.3 % roughly
correlated with a 50 % loss in tensile elongation.
Mechanical Testing
Film samples were cut into dog-bone shaped
specimens of type 5B (ISO 527-2) using a punch
press after WOM exposure. Samples were cut
so that the gauge portion of the tensile bar ran
perpendicular to the machine direction of the film
(i.e. the tensile bars were cut across the
machine direction). Five specimens were cut of
each sample. Samples were tested on an
Instron tensile tester at 50 mm/min crosshead
speed. The median value of the five samples
was used for all analysis. Time to 300 %
elongation was used as the primary indicator as
this eliminates the effect of problems with the
zero hour data and represents the lower limit of
utility of agricultural films.
Acid Treatment
The film samples were cut into small squares (2”
x 2”) and placed in 0.1 N sulfurous acid for 24
hours at room temperature. The samples were
then rinsed with water and patted dry on a cloth.
The samples were mounted in an Atlas WOM
operating under Miami exposure conditions.
Every 400 hours the samples were removed for
evaluation.
Pesticide Exposure
The film samples were dipped in a 3 % (wt/wt)
solution of Metham Sodium (Metham-Na) for two
hours and then placed in an Atlas
weatherometer. Conditions: 63 °C black panel
temperature, 42 °C chamber temperature, 0.35
W/m2 irradiance intensity at 340 nm, 102
minutes dry, 18 minutes water spray, relative
humidity (dry period) 50 %. The exposure to the
pesticide was repeated each week. The extent
of degradation was followed by FTIR and
mechanical properties as previously described.
Results and Discussion
As a rule, the most effective light
stabilizer systems for greenhouse films with
frequent exposure to agricultural chemicals is a
combination of a nickel quencher and a
benzophenone. However, this system has two
major limitations. First, films produced using
these light stabilizers take on a green caste that
reduces the overall light transmission and this
can lead to reduced photosynthesis. Second, it
is known that film failure often occurs as a result
of degradation at structural attachment sites, not
in the middle of the film. This happens because
NiQ systems do not provide adequate thermal
protection, so failure is first observed at these
‘hot spots.’ In addition, although the traditional
NiQ combination with benzophenones initially
provides beneficial blocking of UV light, this
effect is rapidly lost. Benzophenones (and
benzotriazoles) are lost as a result of
photodecomposition and volatilization, leaving
films nearly transparent in the UV range after
only a few months of use as the benzophenone
is depleted due to decomposition and/of
volatilization.
Hindered amines on the other hand
convey little or no color to the film and are
excellent thermal stabilizers as well as light
stabilizers. However, due to the basic nature of
HALS, they are susceptible to deactivation in the
presence of acidic species. Since the photolytic
decomposition products of many pesticides are
acidic, the presence of these chemicals is
known to severely reduce the light stabilizing
efficacy of hindered amines. This is shown
dramatically in Figure 1 below.
Figure 1. The effect of pesticide treatment
on the light stability of 50 micron LDPE film
containing 5000 ppm of a HALS (hours to
failure in xenon arc weatherometer).
3000
HALS-944
2500 HALS-3346
Lifetime (hours)
2000
1500
1000
500
0 60
untreated M etham -Na
Several different techniques have been
used to improve the resistance of HALS to
pesticides. One approach is to reduce the
basicity of the HALS through methylation of the
piperidinyl nitrogen to form a tertiary amine. It is
thought that the lower basicity will minimize any
acid/base reactions occurring between the
HALS and decomposed agricultural chemicals.
An added benefit is an increase in the steric
hindrance about the polar nitrogen, which further
inhibits undesired HALS/pesticide reactions.
HALS-3529 is a methylated, high molecular
weight FDA approved HALS designed for
agricultural films. A second approach is to use a
HALS along with co-additives that can neutralize
the acidic pesticide byproducts, thus minimizing
any reaction with the HALS. The sacrifice of the
acid neutralizer would, in theory, allow the HALS
to remain viable. Products that subscribes to
this method include HALS-494 and HALS-391.4
HALS-494 consists of a high molecular weight
tertiary HALS with zinc oxide and calcium
stearate. See Appendix 1 for the chemical
structures of all light stabilizers.
The effectiveness of these strategies
was evaluated in a 50 µm polyethylene film, and
in a non-pesticide environment, HALS-494 and
HALS-3529 perform similarly in retention of
elongation during the first 3000 hours of xenon-
arc weatherometer exposure, as illustrated in
Figure 2, but by 4000 hours, HALS-494 has lost
over 50 % of the original elongation while HALS-
3529 still has 70 % of it original elongation
remaining. It is postulated that the failure of the
HALS-494 is due to the fact that it comprises
only 80% active light stabilizer HALS and the
other 20% is an acid scavenger component that
is inactive as a light stabilizer.
Figure 2. Light stability of 50 micron films
stabilized with tertiary HALS and HALS +
acid scavenger system.
120 0.55% HALS-3529 0.55% HALS-494
Retention of Origenal
100
Elongation (% )
80
40
20
0
1000 1500 2000 2500 3000 4000
Exposure Tim e (hrs)
The true benefits of these acid scavenging co-
additives would be expected in films exposed to
pesticides. However, treating the films with
Metham-Na during exposure in a xenon-arc
weatherometer shows the same relative
performance between HALS-3529 and HALS-
494, though the overall time to failure was cut
roughly in half.
Recently NOR HALS have been
introduced to the agricultural film market . It was
expected that these light stabilizers would have
reduced sensitivity to agricultural chemicals
because they have very low basicity. While
tests do show this approach to be an
improvement over the HALS+acid scavenger
approach, these systems still do not deliver the
performance of NiQ/UVA systems under
rigorous chemical exposure conditions (Figure
3). The cost of NOR HALS is also significantly
more than NiQ/UVA systems and this has
limited the appeal of this technology in the
industry. Additionally, none of these HALS-only
systems absorb any UV light, therefore films
stabilized with this technology are transparent in
the UV range.
Figure 3. Hours to 300% elongation for 150
micron LDPE films during xenon exposure
with Metham-Na treatment once every 2
weeks.
1% N i-1084/U V A -531(2:1)
1.25 % H A L S-494 1.25 % H A L S-391
7000
600 0
6000
500 0
5000
4000 3 75 0
3000
2000
1000
0
The addition of UV absorbers to HALS-
based systems provides two main benefits; it
generally leads to improved greenhouse film
weatherability and it filters out some UV light
from getting into the greenhouse. For either
purpose the UV absorber must have a high
inherent light stability and a high permanence in
the plastic. UVA-531 is a benzophenone (BZP)
that has been used in agricultural film
stabilization for over 20 years. Initially it
provides adequate light blockage in the UV
transient nature of this class of UV absorber, as
well as benzotriazoles (BZT), makes them
unsuitable for films designed for 2 or more years
of service (Figure 4).
As seen above, each of the existing
stabilization strategies above has one or more of
the following limitations: reduced light
transmission, low thermal stabilizing efficacy,
1 % H A L S-371 low resistance to agricultural chemicals, or poor
UV-block permanence. Cytec’s strategy has
been to combine these stabilization strategies to
afford a film with the benefits of each while
mitigating the deficiencies inherent in any lone
chemistry. Combining NiQ, UV absorber and
HALS chemistries affords greenhouse films that
2 200
have adequate resistance to agricultural
chemicals, improved light transmission and
improved thermal resistance. The results of
weathering studies using films formulated in this
manner are shown in Figure 5 below. However,
one limitation in combining these traditional light
stabilizers remained to be overcome – the
transient nature of UV absorbers.
Figure 5. Performance of NiQ/UVA/HALS
combination in xenon arc weatherometer
with Metham-Na treatment (1x / 2weeks).
200 micron LDPE films. Failure is time to 300
% elongation.
7000 >6000
6000
5700

range, but upon prolonged exposure this UV

Hours to Failure

5000 4200
absorption is diminished. The
4000

Figure 4. Loss of benzophenone and 3000

benzotriazole UVA’s from agricultural film 2000
during xenon exposure. 1000

0
200 micron LDPE/EVA film containing 1.22% Ni-1084/UVA- Ni-1084/ UVA- HALS-492
HALS-3529 + 0.58% B ZP/BZT 531(2:1) 531/ HALS-3529
100
0 Hrs
(4:3:2)
80 1500 Hrs
2785 Hrs
60 3895 Hrs Cytec has found that triazine UV
%T

absorbers, such as UVA-1164, have remarkably

40
good permanence in plastics and coatings. As
20 shown in Figure 6, UVA-1164 remains in an
untreated polyethylene film significantly longer
0
than UVA-531 during outdoor exposure.
280 300 320 340 360 380 400 420
nm Furthermore, the rate of UV absorber loss is
independent of pesticide exposure. The rate of
loss of UVA-1164 and UVA-531 was unchanged
even when the film was periodically exposed to
Metham-Na, with the triazine UV absorber again
being much more persistent. The exceptional
retention of triazines in greenhouse films
translates into a much longer-lived UV screening
effect. As shown in Figures 6, though a film
containing 0.33 wt % of UVA-531 initially blocks
nearly all UV light below at 350 nm, after 12
months of exposure it blocks no more than 50%
of the light at this wavelength. In contrast, films
containing the same amount of UVA-1164 block
>70% of the light at 350 nm after almost 2 years
of exposure. Use of this technology creates a
very consistent growing environment over the
lifetime of a greenhouse film, even 3 year films.
Since filtering UV light leads to enhanced
growth rate effect that UV blocking effect, higher
yields for many crops by enhancing growth
and/or preventing mold growth or other
pestilence, Furthermore, by blocking UV light,
the rate of pesticide photolysis is decreased
within a greenhouse allowing more efficient
action. For these reasons the longevity of the
triazine UVA in agricultural films is clearly
beneficial.
Figure 6. Relative loss of UVA’s from 150
micron LDPE films exposed in France and
exposed to pesticide treatment.
100
90
80
Transmittance [%]
70
60
50
40
30
20
10
0
0 3 6 9 12
Months in Sanary-sur-Mer/Metham-Na
UVA-1164 (0.33 %)
The high permanence of triazines can be
explained on the basis of two physical
properties; light stability and low volatility. The
planar nature of the UVA-1164 molecule leads
to a stronger intramolecular hydrogen bond that
results in a more efficient UV absorber. Early
work by Pickett9 measured the degradation rates
of several UV absorbers. The UV absorber UVA-
1164 was observed to have the best inherent
light stability in several different polymer
matrices. In addition to the greater light stability
of the triazine molecule, the superior
permanence of UVA-1164 over UVA-531 is also
due to the lower volatility of UVA-1164. As
measured by weight loss in a dynamic TGA (10
o
C/min), 10% of the initial sample mass of UVA-
531 has volatilized when the temperature
reached 259 oC. When UVA-1164 is tested
under the same conditions, 10% mass loss does
not occur until the temperature reaches 347 oC.
The permanence of UVA-1164 not only
leads to a more consistent growing environment,
but films stabilized with a HALS/UVA-1164
combination are extremely resistant to
degradation. The synergy between HALS and
UV absorbers is well known but varies
significantly dependent upon the type of UV
absorber applied.10 In greenhouse films
stabilized with HALS-3529 plus a UV absorber,
the triazine (UVA-1164) far surpasses
benzophenones (UV-531) in terms of
durability.11 In Figure 7 a commercial product
comprising UVA-1164 and HALS-3529 known
as THT-6460 was evaluated against a system
comprising a HALS + acid scavenger +
benzophenone + benzotriazole. In 200 micron
greenhouse films exposed to pesticides and
weathered in a xenon arc weatherometer, the
THT-6460 lasted 50% longer in terms of
physical properties and the UV blocking efficacy
of the film was nearly unchanged through out
the exposure (Figure 8)
Figure 7. Hours to failure for 200 micron films
containing the specified light stabilizer package
and exposed under ASTM G155 conditions.
15 18 21 24
Films were treated 1x / 2 weeks with Metham-Na.
UVA-531 (0.33 %) THT-6460 (1.5% ) HALS-N391+UVA-531+BZT (1.7% )
7000 6500
hours of xenon exposure
6000
5000 4300
4000
3000
2000
1000
0
300% Elongation (Failure)
Figure 8. UV blocking effect versus xenon
exposure of 200 micron film containing THT- Conclusions
6460. There are a variety of different
200 m icron LDPE/EVA film containing technologies available for the stabilization of
100
1.5 w t % THT-6460 greenhouse films. The performance of each
0h
depends upon the crops and/or chemicals that
80
1500 h are being grown within the confines of the
60 2785 h greenhouse. In the absence of pesticides,
%T

40
3895 h
20
0 tehcnology is very resistant to agricultural
290 310 330
In some cases HALS/triazine technology
has shown enhanced resistance to agricultural
chemicals. Figure 9 below shows weathering
data for the HALS/triazine technology in
greenhouse films with and without pesticide
exposure. Base on carbonyl index, a measure
of the amount of film degradation, it appears that
exposure to Metham-Na or permethrin has very
little effect on the weatherability of the film.
Continued development of this technology may
eventually lead to nickel free formulations in
even the most chemically harsh growing
environments.
Figure 9. 200 micron greenhouse films
exposed outdoors in Florida. Condition A
was free of pesticide exposure, Condition B
had Metham-Na exposure 1x / month and
Condition C had permethrin exposure 1x /
month.
0.1
21 m o
delta carbonyl index
HALS are very effective light stabilizer, but
exposure to chemicals diminishes the
performance of hindered amines. NiQ/UVA
350 370 390 410 chemicals, but these films are less resistant to
nm thermal decomposition and can have lower light
transmission. Using a combination of HALS,
NiQ and UVA’s can lead to a good balance of
properties. Traditional UVA’s are rapidly lost
from agricultural films leading to a greenhouse
growing environment that changes over time.
Triazine UVA’s can be used to create a
consistent UV blocking environment in a
greenhouse. Triazines also have extremely high
synergy with HALS that give films stabilized with
this combination extreme resistance to light
degradation. Films stabilized with
HALS/triazines also have improved resistance to
agricultural chemicals compared to traditional
HALS/UVA combinations and HALS/acid
scavenger technology. The stability of
HALS/triazines in the presence of agricultural
chemicals can approach that of NiQ/UVA
systems. The combination of a triazine based
HALS with a triazine UV absorber is the basis of
CYASORB THTTM light stabilizers, a new line of
light stabilizers from Cytec Industries Inc.
Among these new products is THT-6460, a
27 m o 33 m o newly introduced product designed for

0.08
greenhouse film stabilization.
0.06

0.04

0.02

0
A B C
1.0% THT light stabilizer
 Appendix 1. Chemical Structures
H H

HALS-944 N N Chimassorb® 944a

N
N (CH2)6 N
N N

NH

H H
HALS-3346 N N CYASORB® UV-3346 light
stabilizerb
N
N (CH2)6 N
N N

HALS-3529 CH3
N
CH3
N
CYASORB® UV-3529 light
stabilizerb
N
N (CH2)6 N
N N

n
R N R

HALS-119 H
N N Chimassorb® 119a
R N N N R= N N CH3

N N

R
2

HALS-494 CaSt + ZnO + HALS-119 Tinuvin® 494a

HALS-N391 Hostavin® N391c

O
N OH
N
O
n
+ CaSt + ZnSt
and other reaction products

1,6-Hexanediamine, N,N’-bis(2,2,6,6-
HALS-371 tetramethyl-4-piperidinyl)-, polymer with Tinuvin® NOR 371a
2,4,6-trichloro-1,3,5-triazine, reaction
products with 3-bromo-1-propene, N-
butyl-1-butanamine and N-butyl-2,2,6,6-
tetramethyl-4-piperidinamine, oxidized,
hydrogenated
 O t-C 8H17
Ni-1084 CYASORB® UV-1084 light
n-C H9NH2
4
Ni S stabilizerb

O t-C 8H17

OH
O
UVA-531 C
CYASORB® UV-531 light
absorberb
OC8 H 1 7
CH 3

UVA-1164 CYASORB® UV-1164 light

H3 C absorberb
CH 3 N N OH

H3 C O– C8 H 1 7- n

THT-6460 HALS-3529+UVA-1164 CYASORB THTTM6460 light

(proprietary ratio) stabilizerb
a
Tinuvin® and Chimassorb® are products of Ciba Specialty Chemicals
b
CYASORB THTTM, CYASORB® light stabilizers and CYASORB® light absorbers are products of
Cytec Industries Inc.
c
Hostavin® is a product of Clariant Corporation

REFERENCES

1
Stretanski, J. A., “Stabilization of Agricultural Film”, China Agricultural Film Association Conf., Hangzhou, 1999.
2
Lichtblau, A and Zah, M., Kunstoffe Plast Europe, 1998.
3
Shachar, R., Stelman, R., Efrat, B., Ashkenazi, Y., and Lelli, N. “Experiments with HALS Stabilized LDPE Agrifilms in
Rose Greenhouses”, International congress for Plastics in Agriculture (CIPA), Tel-Aviv, Israel, March 9-14, 1997.
4
Guo, M., Horsey, D., Lelli, N., Bonora, “Stabilization on Agricultural Film: Past, Present, and Future”, SPE Polyolefins X
Conf., Houston, TX, 1997.
5
Henninger, F. and Gugumus, F., ”Evaluation of the Life Time of Greenhouse Cover Films”, Plasticulture et Qualite
Industrielle, Puy en Velay, France, 1992.
6
Epacher, E. And Pukansky, B, “Interaction of Pesticides and Stabilizers in PE Films for Agricultural Use”, SPE ANTEC,
NY, NY 1999.
7
Raviv, Michael. From “The effect of filtered light through polyethylene sheets on sporulation of Botrytis cinerea,”
unpublished results of R, Reuveni and M. Raviv, 1986-87. Presented in FVG America Technology Update: “The
development of a new polyethylene film for roses.”
8
Van Der Veen, R. and Merjer, G., Light and Plant Growth, Phillips Tech. Library.
9
Pickett, J. E. 16th Annual International Conf. On Advances in the Stab. and Degradation of Polymers, Luzern,
Switzerland, 1994.
10
a) Cangelosi, F.; Davis, L.; Samuels, S. A new generation of long term stabilizer for polyolefins. Polyolefins 2001, pp
455. Houston, TX. February 25-28, 2001. b) Davis, L.; Samuels, S.B.; Zenner, J.M. A revolutionary light stabilizer
system for polyolefins and other resins. Additives 2001, Hilton Head Island, SC. March 18-21, 2001.
11
a) Vulic, I.; Zenner, J. Environmental Influences on Film Durability. 15th International Congress for Plastics in
Agriculture and the 29th National Agricultural Plastics Congress. pp 373. Hershey, PA, USA. September 23-27, 2000. b)
Vulic, I.; Ungar, D.; Zenner, J.M. Light Stabilization of Agricultural Films. 30th National Agricultural Plastics Congress
pp 77. San Deigo, CA, USA. February 23-26, 2002.