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UV Weathering and Related Test Methods - Cabot Corporation

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<strong>UV</strong> <strong>Weathering</strong> <strong>and</strong> <strong>Related</strong> <strong>Test</strong> <strong>Methods</strong>


2<br />

<strong>UV</strong> <strong>Weathering</strong> <strong>and</strong> <strong>Related</strong> <strong>Test</strong> <strong>Methods</strong><br />

Table of Contents<br />

Page<br />

I. Introduction to <strong>Weathering</strong> 3<br />

1. <strong>UV</strong> light spectrum <strong>and</strong> solar radiation 3<br />

2. Radiation energy – definitions 4<br />

3. Average solar radiation by country 5<br />

4. Light stabilizers for plastic materials 6<br />

a) <strong>UV</strong> light absorbers 6<br />

b) Quenchers 7<br />

c) Hindered Amine Light Stabilizers (HALS) 7<br />

II. <strong>Weathering</strong> <strong>Test</strong> <strong>Methods</strong> 8<br />

1. Natural weathering 8<br />

2. Artificial weathering chambers 9<br />

a) Q<strong>UV</strong> fluorescent light source 9<br />

b) Xenon lamp weathering (Ci65A chamber) 10<br />

c) Q<strong>UV</strong> versus Xenon lamp testing 11


Introduction to <strong>Weathering</strong><br />

Long term exposure to sunlight leads to the degradation of plastic<br />

materials. In particular, the non-visible <strong>UV</strong> radiation characterized by<br />

short wavelengths is responsible for photo-degradation, a process<br />

that generally results in breaking down the polymer chains. This<br />

frequently results in a deterioration of the physical properties,<br />

changes in color or chalking of the part surface. As an example, films<br />

lose their flexibility <strong>and</strong> disintegrate, garden furniture becomes brittle<br />

or stadium seats become chalky.<br />

In order to limit or postpone the onset of degradation, several types<br />

of <strong>UV</strong> light stabilizers can be added to the polymer. The most<br />

important stabilizer types work by screening out the harmful<br />

ultraviolet light - for instance <strong>UV</strong> absorbers such as benzophenones<br />

or small dispersed particles such as carbon black or inorganic<br />

pigments. Other very effective <strong>UV</strong> stabilizers are <strong>UV</strong> quenchers <strong>and</strong><br />

HALS (Hindered Amine Light Stabilizers). A brief description of these<br />

stabilizers is given in the next pages.<br />

One important factor, when the light stability of a given material or the<br />

performance of a <strong>UV</strong> stabilizer needs to be assessed, is the selection<br />

of a suitable test method. Besides outdoor exposure that closely<br />

reflects natural weathering conditions but requires long exposure<br />

times, artificial weathering tests have been developed using light<br />

sources such as Xenon arcs or fluorescent lamps under controlled<br />

temperature <strong>and</strong> humidity conditions.<br />

Ultraviolet light spectrum <strong>and</strong> solar radiation<br />

<strong>UV</strong>B VISIBLE INFRA RED<br />

280 nm 315 nm 385 nm 780 nm 3 µm<br />

SOLAR SPECTRUM<br />

The solar spectrum covers a broad range of radiation including short<br />

wavelength <strong>UV</strong>'s, visible light, as well as infrared radiation.<br />

3


4<br />

Radiation components<br />

<strong>UV</strong> radiation represents only 4.6% of the solar spectrum, but causes<br />

the most important damage to the polymeric materials. The complete<br />

solar <strong>UV</strong> spectrum ranges between 280 <strong>and</strong> 400 nanometers, but the<br />

most aggressive part is the <strong>UV</strong>B range with very short wavelengths<br />

between 280 <strong>and</strong> 315 nanometers.<br />

visible light<br />

45%<br />

<strong>UV</strong><br />

5%<br />

Radiation energy: definitions<br />

The irradiation is the radiation energy incident over a specific area<br />

for a given period of time. It is expressed either in W*s /m 2 , Joule/m 2<br />

or very often in Langley (Ly).<br />

1 Ly = 1 cal/cm2 = 4.184 E 4 Joule/m 2<br />

infrared<br />

50%<br />

Example : what is the total irradiation for a 3-year outdoor exposure<br />

in Belgium?<br />

➢ annual sunlight radiation in Belgium : 80 kLy (see table below)<br />

➢ total irradiation after 3 years : 80 x 3 = 240 kLy<br />

The global annual sunlight radiation level (kLy/year) for various<br />

countries is given in the table below. It corresponds to the radiation<br />

energy that can be transmitted to a plastic part in one year of<br />

continuous outdoor exposure.<br />

Note: values in this table are only indicative. Within certain (larger)<br />

countries, radiation levels can vary significantly from one area<br />

to another.


Average solar radiation per country in kLy (kcal/cm 2 /year)<br />

COUNTRY kLy<br />

Austria 80<br />

Afghanistan 180<br />

Alaska 70<br />

Algeria 160<br />

Angola 120<br />

Argentina 160<br />

Australia 180<br />

Bahamas 140<br />

Bahrain 200<br />

Belgium 80<br />

Burma 120<br />

Bolivia 140<br />

Brazil 120<br />

Bulgaria 100<br />

Canada 100<br />

Chad 200<br />

Chile 140<br />

China 140<br />

Columbia 100<br />

Costa Rica 140<br />

Cuba 140<br />

Cyprus 140<br />

Denmark 70<br />

Egypt 200<br />

Ecuador 120<br />

El Salvador 140<br />

Ethiopia 140<br />

Finl<strong>and</strong> 70<br />

France 120<br />

COUNTRY kLy<br />

Germany 80<br />

Great Britain 70<br />

Greece 120<br />

Guatemala 140<br />

Guyana 120<br />

Haiti 160<br />

Hong Kong 140<br />

Honduras 140<br />

Hungary 80<br />

India 180<br />

Indonesia 140<br />

Iraq 180<br />

Iran 180<br />

Israel 180<br />

Italy 120<br />

Jamaica 160<br />

Japan 100<br />

Jordan 180<br />

Kenya 140<br />

Kuwait 180<br />

Korea 120<br />

Lebanon 180<br />

Luxembourg 80<br />

Libya 180<br />

Madagascar 140<br />

Mali 200<br />

Malta 160<br />

Malaysia 140<br />

COUNTRY kLy<br />

Morocco 160<br />

Mauritania 180<br />

Mexico 160<br />

Mozambique 160<br />

Nepal 160<br />

Netherl<strong>and</strong>s 80<br />

Nicaragua 140<br />

Niger 200<br />

Norway 70<br />

New Zeal<strong>and</strong> 120<br />

Oman 160<br />

Pakistan 180<br />

Panama 40<br />

Paraguay 160<br />

Peru 140<br />

Philippines 140<br />

Pol<strong>and</strong> 80<br />

Portugal 40<br />

Rumania 100<br />

Russia (North) 70<br />

Russia (South) 140<br />

Sardinia 20<br />

Saudi Arabia 200<br />

Senegal 180<br />

Sicily 140<br />

Singapore 140<br />

South Africa 160<br />

Spain 140<br />

Sudan 220<br />

COUNTRY kLy<br />

Suriname 120<br />

Sweden 70<br />

Switzerl<strong>and</strong> 80<br />

Taiwan 140<br />

Thail<strong>and</strong> 140<br />

Tunisia 160<br />

Turkey 140<br />

Uruguay 160<br />

USA<br />

North 100<br />

Arizona 180<br />

Florida 140<br />

Ug<strong>and</strong>a 140<br />

Vietnam 140<br />

Venezuela 160<br />

Zambia 180<br />

5


6<br />

Light stabilizers for plastic materials<br />

To provide an appropriate protection against <strong>UV</strong> radiation, several stabilizing systems can be utilized in plastic materials.<br />

The most important types of light stabilizers are Ultraviolet Light Absorbers, Energy Transfer Agents or Quenchers, as<br />

well as Hindered Amine Light Stabilizers. A brief description of these different light stabilizers is given below.<br />

a) <strong>UV</strong> light absorbers<br />

Absorbers convert harmful ultraviolet radiation to harmless infrared<br />

radiation or thermal energy, which is dissipated through the polymer<br />

matrix. They can be either transparent as hydroxybenzophenone or<br />

opaque like carbon black.<br />

Carbon black<br />

Carbon black is one the most efficient <strong>and</strong> widespread light<br />

absorbers. Its efficiency as a <strong>UV</strong> absorber depends primarily on the<br />

primary particle size <strong>and</strong> structure. At the same loading, carbon black<br />

aggregates based on fine prime particles will present more surface to<br />

incident light - <strong>and</strong> hence a larger ultraviolet light absorbing efficiency<br />

- than a coarser grade.<br />

Primary particle<br />

Carbon black aggregate<br />

Primary particle size<br />

(typically 15 to 60 nanometers)<br />

Effect of primary particle size on weathering performance<br />

%RE at break<br />

125<br />

100<br />

75<br />

50<br />

25<br />

0<br />

Accelerated <strong>Weathering</strong> – ATLAS<br />

55 µm LDPE films with 2.5% CB<br />

0 250 500 750 1000 1250<br />

Exposure time (hours)<br />

The appropriate loading level depends on the part thickness, exposure<br />

conditions <strong>and</strong> type of carbon black. Usual loadings to impart<br />

optimum <strong>UV</strong> protection vary between 2 <strong>and</strong> 3% (it should be noted<br />

that these carbon black levels correspond to 4 to 7% masterbatch,<br />

depending on their loading).<br />

< 25 nm particle size<br />

60 nm particle size


Absorption Coefficient<br />

(Kilo Abs. Units/meter)<br />

Effect of loading levels on ultraviolet light absorption<br />

600<br />

500<br />

400<br />

300<br />

200<br />

100<br />

0<br />

The strong absorption characteristics <strong>and</strong> high opacity of carbon<br />

black make it the most cost effective <strong>UV</strong> absorber. Typical applications<br />

for carbon black as a <strong>UV</strong> stabilizer in plastics are exterior pipe,<br />

polyolefin agricultural film, pond linings, automotive parts <strong>and</strong> exterior<br />

cable jacketing (PVC, PE, etc…).<br />

Titanium dioxide<br />

Certain pigments such as rutile titanium dioxide absorb in the 300 to<br />

400 nm range. Hence, they contribute to the protection of the polymer,<br />

provided that the pigment has a suitable coating to prevent the<br />

photo-degradation processes usually observed with TiO 2 .<br />

Hydroxybenzophenone <strong>and</strong> hydroxyphenylbenzotriazole<br />

These well-known <strong>UV</strong> absorber types offer the advantage of being<br />

suitable for natural or transparent applications. To provide a good<br />

protection to the plastic material, a certain absorption depth is needed<br />

(part thickness) which makes these absorbers inefficient in thin<br />

items such as films (below 100 micron), fibers or tapes.<br />

b) Quenchers<br />

1 1.25 1.5 1.75 2 2.25 2.5 2.75 3 3.25 3.5<br />

% Carbon Black in LDPE films<br />

This type of light stabilizer functions by bringing ‘excited’ state<br />

polymer molecules (chromophores) back to their stable state,<br />

preventing bond cleavage <strong>and</strong> finally formation of free radicals. Nickel<br />

stabilizers are typical quenchers used, for instance, in agricultural film<br />

applications.<br />

c) Hindered Amine Light Stabilizers (HALS)<br />

These very efficient light stabilizers do not modify the color of the<br />

plastic material <strong>and</strong> are suitable for both thin <strong>and</strong> thick cross-section.<br />

HALS are not active by absorbing the <strong>UV</strong> radiation but rather by<br />

reacting with the radicals which are formed <strong>and</strong> thus by limiting the<br />

degradation reactions in presence of some chemicals (pesticides,<br />

insecticides, acidic chemicals, etc…).<br />

< 25 nm particle size<br />

60 nm particle size<br />

7


8<br />

<strong>Weathering</strong> <strong>Test</strong> <strong>Methods</strong><br />

Besides natural weathering, several test methods have been<br />

developed using artificial light sources to provide accelerated test<br />

procedures. All methods are based on the regular observation of<br />

characteristics reflecting an ageing process such as mechanical<br />

properties (elongation at break, tensile properties or impact strength)<br />

or visible characteristics, such as crack formation, chalking, changes<br />

in color or gloss.<br />

The main testing methods for plastic material ageing are the following:<br />

a) natural weathering stations<br />

b) artificial accelerated weathering chambers:<br />

• Q<strong>UV</strong> fluorescent light source<br />

• ATLAS Xenon lamp<br />

• SEPAP chamber (medium pressure mercury arcs)<br />

Outdoor testing racks are used by <strong>Cabot</strong> in Dukinfield (United Kingdom),<br />

Grigno (Italy), Berre (France), Hong Kong <strong>and</strong> Altona (Australia)<br />

representing a broad range of climate <strong>and</strong> irradiance levels. Q<strong>UV</strong><br />

fluorescent light chambers as well as Atlas Weatherometers (Xenon lamp)<br />

are located in the <strong>Cabot</strong> <strong>Weathering</strong> Center in Loncin (Belgium).<br />

Natural weathering<br />

Outdoor exposure is performed on samples mounted on testing racks<br />

oriented under st<strong>and</strong>ard conditions (typically facing South in the<br />

northern hemisphere, 45° vertical inclination). In this way, the material<br />

is exposed to the full radiation spectrum from the infrared to the<br />

ultraviolet ranges. Of course radiation, but also temperature, <strong>and</strong><br />

relative humidity levels strongly depend on the location, the seasons<br />

<strong>and</strong> can show some fluctuation from year to year.<br />

The average solar radiation levels for the different <strong>Cabot</strong> testing sites<br />

are the following:<br />

<strong>Cabot</strong> Natural / Outdoor Facilities<br />

Exposure site Climate Type Yearly Solar<br />

Dukinfield (UK) Oceanic temperate 65 kLy<br />

Grigno (I) Mediterranean 100 kLy<br />

Berre (F) Mediterranean 110 kLy<br />

Hong Kong Tropical 120 kLy<br />

Altona (Aus) Tropical 135 kLy<br />

1 kLy = 1 cal/cm 2 / 1 kLy = 41.84 MJ/m 2<br />

Natural weathering tests provide the most accurate <strong>and</strong> reproducible<br />

data. However, their duration can be very long, which frequently leads<br />

to the selection of an artificial weathering method.


Artificial weathering chambers<br />

a) Q<strong>UV</strong> fluorescent light source<br />

<strong>Weathering</strong> chambers have been developed to provide a Q<strong>UV</strong><br />

weathering.<br />

The Q<strong>UV</strong> simulates the effect of sunlight with fluorescent ultraviolet<br />

(<strong>UV</strong>) lamps, while rain <strong>and</strong> dew are simulated by the condensation of<br />

humidity. As stated previously, the <strong>UV</strong> light only represents roughly 5%<br />

of the sunlight but it is responsible for most of the polymer<br />

degradation. Also, materials are often tested with equipment, which<br />

simulate only the shortest wavelengths (<strong>UV</strong>).<br />

The <strong>UV</strong>-B range includes the shortest wavelengths found in sunlight.<br />

Therefore, for many applications, it is a fast <strong>and</strong> efficient method.<br />

Q<strong>UV</strong> equipment uses two main types of lamps: <strong>UV</strong>A-340 <strong>and</strong> <strong>UV</strong>B-<br />

313.<br />

As shown in Figures 1 <strong>and</strong> 2, while these lamps have different light<br />

emission spectrum, they are both characterized by a maximum of<br />

emission in the <strong>UV</strong> range.<br />

<strong>UV</strong>A provides a reasonable match of the <strong>UV</strong> region of the solar<br />

spectrum, but this match is no longer valid for the long wavelengths<br />

(visible, IR).<br />

<strong>UV</strong>B lamps also emit <strong>UV</strong> light, but the maximum of the emission<br />

spectrum is shifted towards short wavelengths compared to the <strong>UV</strong>A<br />

lamps. The <strong>UV</strong>B-313 lamp is a widely used type of fluorescent <strong>UV</strong><br />

lamp that provides fast test results. However, as shown in Figure 2,<br />

the spectrum contains short wavelengths, which are not present in<br />

the solar radiation.<br />

Irradiance (W/2/nm)<br />

1.2<br />

1.0<br />

0.8<br />

0.6<br />

0.4<br />

0.2<br />

0.0<br />

270<br />

Figure 1: <strong>UV</strong>A-340 spectrum Figure 2: <strong>UV</strong>B-313 spectrum<br />

<strong>UV</strong>A-340 versus Sunlight<br />

<strong>UV</strong>A-340<br />

290 310 330 350 370 390<br />

Wavelength (nm)<br />

Sunlight<br />

By courtesy of QPanel<br />

Irradiance (W/m2/nm)<br />

1.2<br />

1.0<br />

0.8<br />

0.6<br />

0.4<br />

0.2<br />

0.0<br />

<strong>UV</strong>B Lamps versus Sunlight<br />

<strong>UV</strong>B-313<br />

QFS-40<br />

270 290 310 330 350 370 390<br />

Wavelength (Nm)<br />

Sunlight<br />

By courtesy of QPanel<br />

9


10<br />

Q<strong>UV</strong> chambers, <strong>Cabot</strong> <strong>Weathering</strong> Center<br />

For customer support, <strong>Cabot</strong> typically uses <strong>UV</strong>B lamps characterized<br />

by their short wavelength spectrum in order to provide fast test<br />

results. Although these data might not always perfectly correlate with<br />

outdoor exposure results, Q<strong>UV</strong>-B is very useful for preliminary or comparative<br />

testing, as well as for very durable applications. For more<br />

realistic exposure conditions, ATLAS <strong>Weathering</strong> Chambers are generally<br />

preferred.<br />

b) ATLAS xenon arc weathering chambers<br />

Among all artificial <strong>UV</strong> sources, Xenon lights provide the best simulation<br />

of natural sunlight. As shown below, with an appropriate filter<br />

combination, their irradiance spectrum can be adapted to match<br />

closely the natural sunlight over a broad range of wavelengths.<br />

Irradiance (W/m 2/nm)<br />

2.0<br />

1.6<br />

1.2<br />

0.8<br />

0.4<br />

0.0<br />

Figure 3: Xenon arc versus Miami sunlight<br />

spectrum<br />

Xenon Arc With Boro/Boro Filter Combination<br />

”Average”<br />

Mia<br />

Xenon<br />

25 35 45 55 65 75<br />

Wavelength<br />

By courtesy of ATLAS


The Xenon arc weathering chambers have automatic control of light<br />

intensity, temperature <strong>and</strong> humidity. Specific programs allow the samples<br />

to be sprayed with water or exposed to alternating cycles of dark<br />

<strong>and</strong> light periods.<br />

ATLAS Ci65A <strong>Weathering</strong> Chamber, <strong>Cabot</strong> <strong>Weathering</strong> Center<br />

c) Q<strong>UV</strong> versus Xenon lamp testing<br />

Key characteristics Usual St<strong>and</strong>ards at <strong>Cabot</strong><br />

Q<strong>UV</strong> • Only match the short <strong>UV</strong> part of solar spectrum ISO 4892/3<br />

Fluorescent • Faster comparative results Light source : <strong>UV</strong> B (313nm)<br />

<strong>UV</strong> B lamps • Features : Light/ dark/ condensation/ Irradiance : 0.63 W/m2 at 313 nm<br />

no humidity control Cycle : 8 hours light at 60°C,<br />

4 hours condensation<br />

ATLAS • Emission spectrum closer to the entire solar ISO 4892/2<br />

Ci65A spectrum Referenced in the CEN norm for<br />

Xenon lamps • More "absolute" comparative results agricultural films<br />

• Features : Light/dark/spray/ Light source : xenon burner with<br />

condensation/humidity control 2 borosilicate filters<br />

Irradiance : 0.35 W/m2 at 340 nm<br />

Cycle: 102 min light (65°C,65%RH),<br />

18min light & spray<br />

<strong>Cabot</strong> Technical Support<br />

Our technical support team is ready to help you for any further questions<br />

you might have <strong>and</strong> can assist you in finding the appropriate<br />

solution to your problems <strong>and</strong> projects.<br />

11


North America:<br />

<strong>Cabot</strong> <strong>Corporation</strong><br />

Business <strong>and</strong> Technical Center<br />

157 Concord Road<br />

Billerica, MA 01821-7001<br />

USA<br />

Tel: (978) 663-3455<br />

Tel: (800) 462-2313 (Technical Service)<br />

Fax: (978) 670-7035 (Technical Service)<br />

Tel: (800) 526-7591 (North America Customer<br />

Service)<br />

South America:<br />

<strong>Cabot</strong> Brasil Industria e Comercio Ltda<br />

Av. Joao Castaldi 88<br />

04517-900 Sao Paulo, SP<br />

BRAZIL<br />

Tel: +55 11 5536 0388<br />

Fax: +55 11 5542 6037<br />

Middle East/Africa:<br />

<strong>Cabot</strong> Specialty Chem. Inc.<br />

Jebel Ali Free Zone<br />

LOB 15, Office 424<br />

Dubai<br />

UNITED ARAB EMIRATES<br />

Tel: +971 4 8871 1800<br />

Fax: +971 4 8871 1801<br />

Europe:<br />

<strong>Cabot</strong><br />

Interleuvenlaan, 5<br />

B - 3001 Leuven<br />

BELGIUM<br />

Tel: +32 16 39 24 00<br />

Fax: +32 16 39 24 44<br />

Pacific/Asia:<br />

<strong>Cabot</strong> Specialty Chemicals, Inc.<br />

Level 14, MNI Tower 2<br />

11, Jalan Pinang<br />

50450 Kuala Lumpur<br />

MALAYSIA<br />

Tel: +60 3 2164-8352<br />

Fax: +60 3 2162-0253<br />

Notice <strong>and</strong> Disclaimer. The data <strong>and</strong> conclusions contained herein are based on work believed to be<br />

reliable; however, <strong>Cabot</strong> cannot <strong>and</strong> does not guarantee that similar results <strong>and</strong>/or conclusions will be<br />

obtained by others. This information is provided as a convenience <strong>and</strong> for informational purposes only.<br />

No guarantee or warranty as to this information, or any product to which it relates, is given or implied.<br />

CABOT DISCLAIMS ALL WARRANTIES EXPRESS OR IMPLIED, INCLUDING MERCHANTABILITY OR<br />

FITNESS FOR A PARTICULAR PURPOSE AS TO (i) SUCH INFORMATION, (ii) ANY PRODUCT OR (iii)<br />

INTELLECTUAL PROPERTY INFRINGEMENT. In no event is <strong>Cabot</strong> responsible for, <strong>and</strong> <strong>Cabot</strong> does not<br />

accept <strong>and</strong> hereby disclaims liability for, any damages whatsoever in connection with the use of or<br />

reliance on this information or any product to which it relates.<br />

(c) <strong>Cabot</strong> <strong>Corporation</strong>, M.A.-U.S.A. All rights reserved<br />

www.cabot-corp.com/plastics<br />

<strong>UV</strong>.TEST/02.02/E

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