16

EFFECT OF ADDITIVES ON WEATHERING

Additives are commonly used with processed polymers, often constituting more than
50% of the total composition. Although their effect on weathering resistance has either
been demonstrated in service or predicted based on theoretical assumptions, the num-
ber of weathering studies relatedto additives effect is rather small.
1-37
This is most prob-
ably because of the more pressing need to study polymers, which are the components
most responsible for the essential physical properties and material durability. The dis-
cussion belowtherefore includes only the limited scope of additives used by industry for
which references can be found in literature.
Titanium dioxide, the white pigment used in many products, is probably the best
studied additive. When titanium dioxide is irradiated with radiation wavelength less
than 405 nm, the absorbed energy is sufficient to promote electrons from the valence
band to the conduction band. Positive holes are formed in the valence band with both
holes and electrons able to move withinthe crystal lattice. During suchmovement, some
holes andelectrons will recombine, but these available onthe crystal surface caninitiate
chemical reactions. Electrons may combine with oxygen forming radicals, whereas posi-
tive holes combine with hydroxyl groups, forming hydroxyl radicals. These radicals may
then react with organic matter or water, initiating a radical reaction chain. In order to
limit possibility of such a reaction, producers of titanium dioxide pigments developed
methods to promote recombination reactions. This is done either by using admixtures of
transition metals (zinc or aluminum) or by coating TiO
2
particles with alumina or silica.
The presence of transition metals acts as a recombination center for both electrons and
holes. Coating helps to destroy the hydroxyl radicals by facilitating their recombination
to water and oxygen. Such measures improve the quality of titanium dioxide but they
are not able to completely eliminate radical formation.
The stabilizing effect of pigments added to polymers is discussed in Chapter 18.
Considering the fact that titanium dioxide plays the dual role of stabilizer and
sensitizer, one may anticipate that its effect depends not only on the type and quality of
Effect of additives on weathering 425
titanium dioxide but also on the properties of the binder (polymer). Figs. 16.1 and 16.2
showthe effect of titaniumdioxide onmass loss during the weathering of a durable anda
non-durable binder. The durable binder is sufficiently stable to withstand weathering
without the needfor UVstabilization. The additionof titaniumdioxide causes formation
of free radicals in the vicinity of its crystals in the binder, which triggers rapidly acceler-
ating degradative changes leading to the decreased weather stability of the material. A
non-durable binder (Fig. 16.2) is also the subject of radical formation in the vicinity of ti-
taniumdioxide particles but the protective effect of the pigment is sufficient to offset the
negative effect of radical process, resulting in a net improvement in weather stability of
the material. Since most of the changes in the material occur around titanium dioxide
particles, eventually the binder is sufficiently eroded to cause pigment and binder sepa-
ration or chalking (Fig. 16.3).
Different grades of titanium dioxide produce different effects. The mechanism of
chalking described by Fig. 16.3 results in changes in material gloss, as can be seen in
Figs. 16.4 and 16.5. Both durable and non-durable binder respond to an increasing con-
centration of titanium dioxide in similar ways.
Other parameters affect how titanium dioxide participates in degradative pro-
cesses. Inthe non-durable binder, titaniumdioxide acts to screenthe binder fromUVra-
diation. The efficiency of screening depends on the degree to which TiO
2
is dispersed.
Flocculated pigment has a lower screening power, as seen fromFigs. 16.6 and 16.7. Less
flocculated pigments inhibit both gloss deterioration and mass loss of the material.
426 G. Wypych
Fig. 16.1. Mass loss in the case of durable binder
vs. exposure time relative to pigment load.
[Adapted, by permission, from L. A. Simpson, Aus-
tral. OCCA Proc. News, 20(1983)6.]
Fig. 16.2. Mass loss in the case of non-durable
binder vs. exposure time relative to pigment load.
[Adapted, by permission, from L. A. Simpson, Aus-
tral. OCCA Proc. News, 20(1983)6.]
The temperature at which degradation occurs is also an important factor (Fig.
16.8). Gloss is better retained when samples are irradiated at lower temperatures. This
suggests that the rate of formation of free radicals is controlled by two processes: photon
absorption; reaction of the excited species followed by radical formation. The quantum
efficiency of radical formation is reduced when radicals recombine. Because radicals are
formedwithinrigidmatrix, it is difficult for themto escape (the cage escape efficiency re-
duced). At lowtemperatures, the matrix is more rigid than at high temperatures and re-
combination is the more probable outcome. Around T
g
, cage escape efficiency is rapidly
reduced.
The effect of pigment properties on photochemical activity is shown in Fig. 16.9.
Surface passivated titanium dioxide (RL90) and CdS both decrease the amount of car-
Effect of additives on weathering 427
Fig. 16.3. Model of binder degradation. [After J. H. Braun, Prog. Org. Coat., 15(1987)249.]
bonyl group formation as the concentration
of pigment increases. ZnOand untreated ti-
taniumdioxide also contribute to a decrease
in carbonyl group formation but only at low
concentrations. Above a certain level each
cause a rapid increase in the formation of
carbonyl groups. Treated TiO
2
and CdS
have poor photocatalytic activity and they
participate in photodegradative processes
by actively screening radiation. In the first
part of the curve (Fig. 16.9), there is a very
low quantum yield of photocatalysis due to
electron-hole recombination and ZnO and
untreated TiO
2
provide screening at low
concentrations. At higher concentrations,
their photocatalytic effect becomes predom-
inant and carbonyl concentrationincreases.
On the other hand, ZnO has long been
known to stabilize some polymers (Fig.
428 G. Wypych
Fig. 16.4. Gloss change in the case of durable
binder vs. exposure time relative to pigment load.
[Adapted, by permission, from L. A. Simpson, Aus-
tral. OCCA Proc. News, 20(1983)6.]
Fig. 16.5. Gloss change in the case of non-durable
binder vs. exposure time relative to pigment load.
[Adapted, by permission, from L. A. Simpson, Aus-
tral. OCCA Proc. News, 20(1983)6.]
Fig. 16.6. Gloss change vs. exposure time relative
to flocculation gradient. [Adapted, by permission,
from L. A. Simpson, Austral. OCCA Proc. News,
20(1983)6.]
16.10). No photo-catalytic influence of TiO
2
and ZnOwas detected by UVand IRspectra
during PVC degradation.
29
The tensile
strengthof the material andother mechani-
cal properties were better preserved when
pigment, regardless of the color, was added.
Studies of fourteen iron oxide pigments in a
PVC matrix showed that pigments, which
have a large inherent ESR spectrum
strength, have poor weatherability.
5
PVC
plates with an ESR spectrum strength
lower than 1 exhibited very good weather-
ability, equivalent to five years of outdoor
exposure. The type of pigment used in PC
greatly influenced the UV stability of the
polymer (Fig. 16.11). Gerlock et al.
1
studied
the effect of initiator concentration, used in
an acrylic copolymer synthesis, on the UV
stability of products. Nitroxide decay assay
Effect of additives on weathering 429
Fig. 16.8. Gloss of TiO
2
pigmented coating vs. ex-
posure time in a modified QUV-like weathering
chamber at different temperatures. [Adapted, by
permission, from J. L. Gerlock, D. R. Bauer,
L. M. Briggs, and J. K. Hudgens, Prog. Org. Coat.,
15(1987)197.]
Fig. 16.9. Carbonyl content in photooxidized EPco-
polymer film vs. pigment concentration (irradiation
260 h, 300 nm). [Adapted, by permission, from J.
Lacoste, R. P. Singh, J. Boussand, and R. Arnaud,
J. Polym. Sci., Polym. Chem., 25(1987)2799.]
Fig. 16.7. Mass loss vs. exposure time relative to
flocculation gradient. [Adapted, by permission,
from L. A. Simpson, Austral. OCCA Proc. News,
20(1983)6.]
was the method used (Fig. 16.12). Photoinitiation rate increases with the concentration
of initiator. In experiments, two initiators (cumene hydroperoxide and
t-butylperbenzoate) were used, showing that the type of initiator was not as critical as
its concentration.
Klemchuk
18
conducted broad studies on the effect of pigments and TiO
2
on the deg-
radation and stabilization properties of polymer matrices. These properties are impor-
tant: dispersibility, light absorbing characteristics, semi-conductor properties, metal
content, influence onpolymer matrix, surface properties, compositionof products of deg-
radation. This list could be expanded to include: pigment surface area, absorption of
components of matrix (e.g., stabilizers), wavelength of emitted radiation by pigment on
energy absorption, generationof singlet oxygen, hydrogenabstraction, effect onpolymer
morphology (some pigments interfere in crystallization), interaction with polymer, etc.
The way in which a pigment interacts with the polymer network is known to have an ef-
fect on the UV stability of the material but this effect can vary widely. For example, the
stability of a composition to radiation at 375 nmcan be increased by increasing pigment
concentration. But there are also exceptions. Ultramarine blue increases durability of
PP by 75% but does not absorb UV. TiO
2
has an absorption of UV similar to channel
black but only a fraction of its stabilizing activity. Some types of dyes, such as, for exam-
430 G. Wypych
Fig. 16.10. Effect of ZnO on UV stability of
plasticized PVC. [Data from B. D. Gupta and J.
Verdu, J. Polym. Eng., 8(1988)81.]
Fig. 16.11. Elongation retention vs. time of natural
exposure of colored PC. [Adapted, by permission,
from B. Dolezel and L. Adamirova, Plast. Kauc.,
20(1983)18.]
ple, azo condensation yellow, red and orange are known to decrease the stability of some
polymers (e.g., PP fiber). In some polymers (e.g. PVC) most pigments (especially inor-
ganic and carbon black) considerably increase durability. Phthalocyanine blue is a rela-
tively good stabilizer of PP fiber but a rather poor pigment for PVC. Some dyes behave
quite differently in lowrelative humidity than in moisture close to saturation. These ex-
amples show that there is a substantial amount of work to be done to explore the very
wide range of pigment, dye, and polymer combinations.
The addition of CaCO
3
to PP causes a slight reduction in carbonyl formation.
16
The
efficiency of some antioxidants, such as Irganox 1010, was found to be reduced by the
presence of CaCO
3
. In another study,
26
PP stability was increased by the addition of
CaCO
3
especially in combination with small addition of TiO
2
(0.5%) or HALS. In
polyurethanes, it was discovered that CaCO
3
acts as a heat sink.
33
The typical concentrations of silica do not affect radical decay, during the degrada-
tion of PMMAby UV, nor is radical composition affected.
20
Large additions (above 50%)
of silica modify the material structure due to matrix absorption on the silica surface
which also increases radical decay rate.
Fig. 16.13 shows the gloss retention of coatings. Samples J and K (in xylene) differ
from sample I (in 2-heptanone). This figure shows that UV stability is a multidimen-
Effect of additives on weathering 431
Fig. 16.12. Normalized photoinitiation rate vs. initia-
tor concentration in coatings. [Adapted, by permis-
sion, from J. L. Gerlock, D. R. Bauer, L. M. Briggs,
and J. K. Hudgens, Prog. Org. Coat., 15(1987)197.]
Fig. 16.13. Gloss of coatings vs. exposure time in
QUV. [Adapted, by permission, from J. L. Gerlock,
D. R. Bauer, L. M. Briggs, and J. K. Hudgens, Prog.
Org. Coat., 15(1987)197.]
sional property which depends on a great number of interrelated parameters. An initia-
tor, in radical form, can abstract hydrogen fromeither solvent. The radical thus formed
is likely to be incorporated as an end-group in the copolymer. An ketonic end-group is a
more photoactive source of free radicals than a benzyl end-group. Additionally, cumene
hydroperoxide may decompose to acetophenone and a methyl radical, either of which
will affect the photodegradation rate. The effect of solvent on the degradation rate goes
beyond factors involving its chemical compositionor its ability to formradicals or UVab-
sorbing groups. It can also increase chain mobility, which increases the probability of a
reaction occurring. These effects are discussed in more detail in Chapter 15.
Fig. 16.14 shows the effect of
p-xylene onESRsignal. This is as a result
of n-octane radical formation during the
degradation of PE.
22
The effect of
p- xyl ene i s l arger than that of
phenanthrene sensitizer. The p-xylene
radicals contribute to abstraction of hy-
drogen in the -position to double bonds
which results in the formation of allyl
radi cal s. Thus, p- xyl ene i s a
photoinitiator of PEdegradation. Solvent
type and concentration affect the rate of
ultrasonic degradation of PS.
28
The deg-
radation rate constant increases as the
polymer-solvent interaction parameter
decreases. PVCfilms were prepared from
sol uti ons i n tetrahydrofuran and
dichloroethane and subsequently re-
moved by thermal treatment.
36
Thermal
treatment caused PVC degradation
which was monitored by double bond for-
mation. Exposure of these samples
showed that a higher degradation rate
was caused by the prior thermal degrada-
tion.
Capocci
12
describes the effect of peroxide concentration in the polyol on the yellow-
ness index of a polyurethane made fromit (Fig. 16.15). Ahighyellowness index indicates
a high concentration of chromophores. This, in turn, means that, if these chromophores
are present before exposure, the polyurethane, when exposed to radiation, will degrade
more rapidly because of the inherently higher absorptivity. The initial color depends not
only on peroxide concentration but also on the type and the amount of amine catalyst
432 G. Wypych
Fig. 16.14. Spectral intensity of n-octane radical
formed during irradiation of PEat -196
o
Cfor 30 min vs.
concentration of p-xylene. [Adapted, by permission,
from H. Kubota and M. Kimura, Polym. Deg. Stab.,
38(1992)1.]
used in foam processing (Fig. 16.16). When
the polyol does not contain peroxides, the
effect of the catalyst is negligible. It is also
known from these and other polyurethane
studies that commonly-used tin catalysts
affect the UV stability of polymers. The ef-
fect of the catalyst is associated with the
presence of a heavy metal and this also in-
fers that other heavy metals present in
polymers may affect their stability. The
degradation rate of pure PMMA was unaf-
fected by temperature but the degradation
rate of monomer-doped PMMA increased
with increasing temperature (see Fig.
11.17).
24
Plasticizers are common additives
which can influence UV stability, as data
for PVC show (Fig. 16.17). Evidently, the
Effect of additives on weathering 433
Fig. 16.15. Effect of peroxide concentration in
polyether polyol on the initial color of polyurethane.
[ Dat a f r om G. Capocci , Pl ast . Compd. ,
10(1987)13.]
Fig. 16.16. Effect of amine catalyst on initial color of
polyurethane foam produced from polyol contain-
ing 207 ppm of peroxide. [Data from J. Lacoste,
R. P. Singh, J. Boussand, and R. Arnaud, J. Polym.
Sci., Polym. Chem., 25(1987)2799.]
Fig. 16.17. Dehydrochlorination of PVC plasticized
with 60 parts of various plasticizers. [Data fromH. J.
Bowley, D. L. Gerrard, K. J. P. Williams, and I. S.
Biggin, J. Vinyl Technol., 8(1986)176.]
degree of branching of the plasticizer affects the dehydrochlorination rate of plasticized
PVC exposed to UV. Other plasticizers seem to affect the degradation rate in a manner
which parallels their efficiency as plasticizers. In radiochemical PVC degradation, the
amount of plasticizer influenced the mechanism of degradation. As the plasticizer
amount was increased (from 15 to 30%), less crosslinking and more chains scission was
observed.
27
The effect of many other additives onpolymers UVstability is knownbut not quan-
tified, and frequently the reasons for their action are unknown. This includes many or-
ganic and inorganic compounds containing metals, such as copper, cobalt, iron,
cadmium, etc. Abroad range of admixtures is listed in Chapter 14, but clearly the effect
of additives common in polymer processing requires more extensive studies.
REFERENCES
1. J. L. Gerlock, D. R. Bauer, L. M. Briggs, and J. K. Hudgens, Prog. Org. Coat.,
15(1987)197.
2. J. H. Braun, Prog. Org. Coat., 15(1987)249.
3. S. Skledar, Mater. Plast., 21(1984)29.
4. L. A. Simpson, Austral. OCCA Proc. News, 20(1983)6.
5. M. Koyama, A. Tanaka, M. Ichijima, and Y. Oki, Kinzoku Hyomen Gijutsu,
37(1986)25.
6. L. D. Strelkova, G. F. Fedoseeva, S. N. Potepalova, L. I. Batueva, and W.P. Lebedev,
Plast. Massy, 1986,5,46.
7. B. Dolezel and L. Adamirova, Plasty Kauc., 20(1983)18.
8. A. Charlesby, J. Radioanal. Nucl. Chem., 101(1986)401.
9. H. J. Bowley, D. L. Gerrard, K. J. P. Williams, and I. S. Biggin, J. Vinyl Technol.,
8(1986)176.
10. A. L. Andrady and A. R. Shultz, J. Appl. Polym. Sci., 33(1987)1389.
11. J. E. Pickett, J. Appl. Polym. Sci., 33(1987)525.
12. G. Capocci, Plast. Compd., 10(1987)13.
13. J. Lacoste, R. P. Singh, J. Boussand, and R. Arnaud, J. Polym. Sci., Polym. Chem.,
25(1987)2799.
14. S. Skledar, Angew. Makromol. Chem., 137(1985)149.
15. B. D. Gupta and J. Verdu, J. Polym. Eng., 8(1988)81.
16. J. Pan, H. Xu, J. Qi, J. Ce, and Z. Ma, Polym. Deg. Stab., 33(1991)67.
17. P. Genova-Dimitrova, Polym. Deg. Stab., 33(1991)355.
18. P. P. Klemchuk, Polym. Photochem., 3(1983)1.
19. A. L. G. Saad and A. W. Aziz, Polym. Deg. Stab., 41(1993)31.
20. E. Ya. Davydov, V. P. Pustoschniy, A. P. Vorotnikov, and G. B. Pariyskiy, Intern. J.
Polym. Mater., 16(1992)295.
21. J. Imhof, P. Stern, and A. Egger, Angew. Makromol. Chem., 176/177(1990)185.
22. H. Kubota and M. Kimura, Polym. Deg. Stab., 38(1992)1.
23. T. B. Boboev, Kh. Dodomatov, and I. Ya. Kalontarov, Intern. J. Polym. Mater.,
19(1993)223.
434 G. Wypych
24. T. Ichikawa, K. -I. Oyama, T. Kondoh, and H. Yoshida, J. Polym. Sci., Polym. Chem.,
32(1994)2487.
25. E. Baimuratov, I. Y. Kalontarov, and D. S. Saidov, Intern. J. Polym. Mater.,
19(1993)193.
26. D. Rysavy and H. Tkadleckova, Polym. Deg. Stab., 37(1992)19.
27. F. Thominette, G. Metzger, B. Dalle, and J. Verdu, Eur. Polym. J., 27(1991)55.
28. G. J. Price and P. F. Smith, Eur. Polym. J., 29(1993)419.
29. J. -L. Gardette and J. Lemaire, Polym. Deg. Stab., 33(1991)77.
30. J. -L. Gardette and J. Lemaire, Polym. Deg. Stab., 34(1991)135.
31. Z. A. M. Ishak and J. P. Berry, Polym. Compos., 15(1994)223.
32. N. S. Allen, M. Ledward, and G. Follows, Eur. Polym. J., 28(1992)23.
33. S. K. Dolui, J. Appl. Polym. Sci., 53(1994)463.
34. P. Dave, R. A. Gross, C. Brucato, S. Wong, and S. P. McCarthy, Polym. Mater. Sci.
Eng., 62(1990)231.
35. C. David, M. Trojan, A. Daro, and W. Demarteau, Polym. Deg. Stab., 37(1992)233.
36. D. J. T. Hill, F. A. Kroesen, J. H. ODonnell, and P. J. Pomery, Mater. Forum.,
14(1990)210.
37. B. Ohtani, S. Adzuma, S. Nishimoto, and T. Kagiya, Polym. Deg. Stab., 35(1992)53.
Effect of additives on weathering 435