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UV Effect on Polyethylene
UV light characteristics All polyethylene (PE) is susceptible to degradation upon long-term exposure to sunlight. This degradation is brought about by physical changes, which occur in the polyethylene as a result of exposure to the ultraviolet (UV) portion of sunlight. Figure 1 shows that UV light contains shorter wavelengths than visible light. The shorter the wavelength, the more energy it contains and thus, the more damage it does. This is explained in the next section in more detail. Fluorescent lighting also contains a band of UV light, but only at an intensity of around 15% of normal sunlight. Figure 1: UV light and its position in the Electromagnetic spectrum
Visible gamma rays X-rays ultraviolet infrared heat wireless

extreme ultraviolet 60 10 10-14
22

microwaves 30 20 10 10-4 10
5 12

radio broadcast 10 0 10 102
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50 10
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40 10
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octaves

10 10-8

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10 10-6
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14

10 10-2

10

10 1

8

vib/s 104 m

10-12 Wavelengths

10-10 1

10 10 10

2

10

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10

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10

8

Angstroms

Why does PE change when exposed to UV light? Table 1 shows why UV light alters the physical characteristics of polyethylene (PE). It does this by breaking the carbon and hydrogen bonds, creating free radicals, which, in turn, break the PE into shorter molecules and thus, a more brittle polymer. Effectively, UV light creates a higher melt index polyethylene, especially on the exposed surface area. This shows up as a reduction in break elongation and impact properties, typical of higher melt index PE. The subsequent attachment of oxygen to these broken sites leads to further accelerated degradation and the formation of oxidized species such as carbonyl and carboxyl structures, which are often used as analytical indicators of UV degradation. Table 1 shows the importance of choosing the correct wavelengths for exposure testing that realistically simulates the weathering effects on PE.

Table 1: Why UV light changes PE Wavelength of light, nm 189 253 315 Energy contained at this wavelength KJ/m2 647 473 228 Type of bond or structure in PE Carbon-carbon (C-C) Carbon-hydrogen (C-H) Double bond carbon-carbon (C=C) Energy to break bond, KJ/mol. 347 413 607

1

Actual UV light is composed of a range of wavelengths as shown in Table 2. *ASTM test procedures may be modified to accommodate operating conditions or facility limitations. Miami. nanometer (nm) 320-380 280-320 180-280 280-800+ Test protocol for UV exposure We use both indoor. It uses a xenon arc lamp with a borosilicate inner and outer filter.2 0.0 0. Figure 2: Irradiance level vs. Thus. Summer solstice and “average” annual sunlight are shown.0 290 300 310 320 330 340 350 360 370 380 390 400 Wavelength (nm) Source: J. the more energy and thus. accelerated testing can be done in shorter time periods as the exposure is continuous and irradiation more intense. (1997) 217-236 (4524) + calculated summer noon measured summer noon x calculated annual average measured "average optimal" Calculated and measured sunlight in Miami.E. Carbon arc lights are unrealistic as they produce too much of the wavelengths between 325 to 425 nm. destructive power it has.K.2 1.6 0. UV light intensity is measured by irradiance and is usually expressed in watts per square meter at a given wavelength. Pickett.8 0. Die Angewandte Makromoldekulare Chemie 252.. which best simulates the UV band of natural sunlight. an industry accepted protocol. Webb. Table 2: UV light has a range of wavelengths Type of UV light UV-A UV-B UV-C Natural Sunlight Wavelength. accelerated weathering testing as well as outdoor exposure testing in Florida.6 1. Test conditions follow the guidelines outlined in ASTM G155 cycle 1*.4 0. it is important when doing indoor.The shorter the wavelength. K. QUV-B testers also are not as good for non-crosslinked polyethylene as they reduce the higher wavelengths of light. as illustrated in Figure 2. Indoor.35 watts/m2 and 340 nanometers (nm). The instruments we use for accelerated testing are Xenon Ci-65 and Ci-5000 Weather-O-Meters.4 Irradiance (W/m2/nm) 1. 2 . GE Electric Co. accelerated weathering exposure to use a lamp or light source that best matches natural sunlight. The weather-o-meters are run at 0. Florida conditions 1. which matches one of the conditions in Florida.

For this reason. Sunshine variations remain the key variable when correlating accelerated and outdoor exposure data. along with changes in climate and elevation. Gugumus. In fact. Another question to consider is the UV performance over water relative to land. the cooler temperature and generally increased cloudiness near coastal areas tend to offset the increased reflectance off the water surface. Figure 3: Correlation between Xenon Ci-65 exposure and Florida 10. Most of our Florida data is done at a 45 degree south exposure angle. Southern Florida = 660 KJ/cm2 per year (from Figure 4) Years of exposure = (325/660) x 8 = 3. Below is an example on how to use Figure 4 to relate years of exposure to weather-o-meter indoor exposure. September 18-20. Florida.The temperature of exposure is also important. A black panel in the machine measures this temperature and is set at 63°C. the more degradation will occur. 1985 UV performance depends on geographic location Geographic location. affect actual UV performance.000 T50 (h) Weather-O-Meter 8000 6000 4000 2000 Comparison Weather-O-Meter/Florida exposure 200 µm LDPE blown films. We have found that using thicker molded samples and running the weather-o-meter on a wet and dry cycle still gives a correlation of approximately 2000 hours.9 years 3 . Years = (325/your location’s isoline) x UV rating of resin Example: Resin with UV-8 rating (See definition in next section) in Southern Florida. the changes have been relatively minor when considering exposure to polymers. We have over 62 data points done over 15 years showing good agreement between our accelerated and outdoor test results in developing this correlation.5%. Polymer Stabilization and Degradation Symposium. started March 1979 T50 (E50): Time (energy) to 50% retained elongation 200 400 600 E50 plexiglass backing. which is typical of one year exposure in Miami. A kilolangley is a measure of UV exposure per square meter of surface area. as the higher the temperature. Figure 3 shows a correlation of Xenon testing with Florida exposure. While definitive studies on PE are not available to date. for every 0. our samples are unbacked both in the Ci-65 and in Florida. UV exposure increases by 3. This figure has been updated to reflect the increased severity in higher elevation areas. While well publicized. Figure 4 shows an updated chart outlining isolines of equal global UV radiation. kly Florida Source: Dr. being one year in Miami. knowing the UV rating of the resin. The backing on the sample may change the actual sample temperature. It shows that 2000 hours in the weather-o-meter is approximately 140 kilolangleys (kly) per year. Figure 3 was based on PE film samples. Manchester. This chart also reflects changes in ozone layers in the world.5 km increase in elevation. Ciba Specialty Chemicals.

de Jong.Figure 4: Isolines of UV performance Annual Global Radiation units: KJ/cm2 per year (to get MJ/m2. 1973. multiply by 10) Reference: B. Delft University Press. 4 Broad Band UV Exposure (295-385 nm) . Net radiation received by a horizontal surface at the earth.

Figure 5 is a representation of this data. but this tends to be vague.000 15. ASTM D-2565* 40 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10. For instance. such as long-term or short-term UV protection. Refer to our data sheets to determine the UV performance of each of our grades. most of the industry would currently think of short-term as UV-4 with UV-8 being long-term. 50% of the original break elongation is left. 5 . ASTM test procedures may be modified to accommodate operating conditions or facility limitations. is approximately 1 year Southern Canada 90 Retained Elongation (%) 80 UV-4 70 UV-8 UV-15 60 Failure Criteria 50 Xenon Weather-O-Meter test. The higher the number.How are our resins rated for UV? An often-used industry standard is UV-X. is approximately 1 year Florida 1250 hrs. Figure 5: What does UV-8* mean? UV Stability 100 2000 hrs. Generally. Some suppliers use qualitative ratings. where X is a multiple of 1000 hours of weather-o-meter exposure. UV-2 is 2000 hours of exposure. the longer the UV exposure and the better the polymer UV protection.000 Hours of Xenon Exposure *See text for further details. At this point. UV-8 means 8000 hours of weather-o-meter exposure.

Studies conducted at our labs have shown that overcuring of rotationally molded samples can reduce UV life from 25% to 70% of the rated performance. Some people feel that using rotomolded samples and allowing a higher level of break elongational decline is preferred. An example of this surface crazing is shown in Figure 6 below. In one study. tensile break elongation decline was more severe than tensile impact decline. as this will vary depending on the applications of your products. It is important to determine your own end point. we take a 50% decline from the original break value to be a “failure point” to establish the end of test. The trend towards embrittlement may be tested in many ways. The property of greatest concern is embrittlement. surface crazing (a crosshatched pattern caused when the sample is bent) is not often evident on our polymers and often field use goes well beyond 50%. 6 . By convention. which may provide evidence of polymer degradation.How is degradation determined? UV attack on polyethylene results in loss of physical properties. We will continue to apply best control capabilities and to try to improve repeatability in rotomolded samples to some day have confidence in reporting data on this basis. Thus. Figure 6: Surface crazing as a result of UV damage on the polyethylene surface Due to the variability of the molding process. our samples are currently prepared by compression molding to minimize data scatter. our testing tends to be based on break elongation decline. At the 50% point. It also was found that tensile break elongation decline was more sensitive than tensile strength decline or the formation of oxidized species at the exposed surface of the part. This introduces much variability into reporting UV performance based on rotational molded samples.

The amount. Martinovich for Plastic Technology November 63. 1% Phthalocyanine Blue 1% TiO2 (Rutile) 1% TiO2 (Anatase) 30 36 40 7 Months exposed in Arizona .How do pigments affect UV performance? Figure 7 shows the effect of color pigments on UV stability.5% 230 175 0 100 200 300 210 230 330 >700* 250 570 Polyolefin Thick Sections.J. affects the UV performance. All pigments should be melt compounded to obtain the proper dispersion necessary for UV protection. carbon black tends to be the best UV performer due to its high absorption of UV light. psi 4000 3000 2000 1000 0 0 6 12 18 24 Natural 1% Iron Oxide 1% Phthalocyanine Green 1% Cadmium Red 1% Cadmium Yellow Source: Right figure: Marlex HDPE Product Brochure. a pigment may fade while the base polymer remains unaffected by true UV degradation. impact and tensile properties are unaffected while the part appearance has changed. Thus.25% 0. As can be seen.25% 0. Generally. Sometimes. such as its organic or inorganic nature. but also one that will be color-stable when exposed to weathering. Phillips Petroleum.25% 0. Ensure your pigment supplier understands that you want not only a pigment that will enhance or not hinder UV performance.03% IRGANOX 1076 + 0. R. coated Rutile) Ultramarine Blue Iron Oxide Cd-Red Cd-Yellow Unpigmented 0.5% 0.25% 0.96 density unstabilized polyethylene resins 5000 1% Carbon Black Tensile Strength. Phthalocyanine Green Phthalocyanine Blue Azo-Red Organic Yellow (tetrachloroisoindolinone) TiO2 (stabilized. It is important to not confuse UV performance with color-fading problems when dealing with pigments.5% 0. Dry blending pigment has minimal effect as the dispersion and thus.5% 0.05% Ca-stearate Light Stabilization: 0. These pigments are generally referred to as UV grade pigments. Arizona 45° south (start November) 500 460 400 500 600 700 800 Polymer – HDPE (Ziegler) Basic Stabilization: 0. particle size and chemical type of pigment. the proper choice of pigment is important as it can have a detrimental or beneficial effect depending on the choice of pigment. Figure 7: Color pigment affect of UV performance Arizona exposure of pigmented HDPE plaques (1mm) Source: Left figure: Ciba: Stabilization of Polyolefins – Part 2.15% TINUVIN 770 kly Arizona *no sample left Effect of pigments on UV stabilization of .5% 0. Failure Criteria: 50% retained tensile impact strength. absorption characteristics are not sufficient to protect the base polymer.

provides it with a faster starting point for degradation when the part is exposed. Melt index (MI) does not directly affect UV stability. Again these factors are generally small. As discussed before. Thicker parts generally would have better UV performance due to reduced UV penetration as it travels through the part. and variations in heat history which different melt indexes of polyethylene may require to produce initial acceptable part properties. A more comprehensive understanding of these effects is the subject of continuing research. Thus. all things being equal. higher density resins. though the secondary effect of a lower MI providing a tougher part and thus. Also. which may shorten UV performance by providing elevated temperatures. These may result in dark material being deposited on the polymer surface. Other variables include higher particulate levels in the atmosphere such as found in industrial areas. Generally. provide better UV stability. and thus. A resin must be properly stabilized to minimize degradation during the rotational molding cycle. which could reduce protection as well as potentially affect the contents of the material being stored in the parts.What other factors affect UV performance? Table 3 outlines qualitatively other factors which may affect UV performance. the most important parameters which the molder may control is part time and temperature history. no further benefit would be expected. longer life to obtain the same absolute break point. thus extending service life of the product. is a factor. 8 . Once the part is sufficiently thick. Table 3: Other factors which affect UV performance Factor Molding cycle (higher temperature or longer time) Thicker part Higher density Lower melt index Directional affect on UV performance Negative Positive to neutral Positive • Negative due to need for higher time or temperatures to properly process part • Positive in the fact that the resin has inherently higher toughness Environmental conditions which may promote particulates depositing on parts Higher mechanical demands on the molded part Higher resin stabilization Negative Negative Positive Resin formulation is important. Sufficient UV stabilizers must be present throughout the product life cycle to protect the part. Overheating the part tends to shorten UV performance as it provides the same mechanisms that UV light promotes. These stabilizers should not migrate out of the part. some exposure conditions may interfere with UV wavelengths. The extent of this effect is difficult to quantify due to the variations of part thickness. higher density and lower MI PE’s enhance UV performance. which provide a larger crystal structure and less potential for entrapping oxygen.

Crewdson. “Correlation of Outdoor and Laboratory Accelerated Weathering Tests at Currently Used and Higher Irradiance Levels – Part 1. warrant.” “our. and other information. Manchester. Gugumus. Atlas Co. or injury directly or indirectly suffered or incurred as a result of or related to anyone using or relying on any of the information in this document. distribute. The terms. ExxonMobil does not guarantee the typical (or other) values. or otherwise guarantee. disclaimers. “Handbook of Material Weathering. accuracy. • George Wypych. damage.” ChemTec Publishing. fitness for a particular purpose.B. and accordingly typical values are not based upon a statistically relevant number of tests. Ciba Specialty Chemicals.” “ExxonMobil Chemical. Martin. The user is solely responsible for all determinations regarding any use and any process. The ExxonMobil Chemical Emblem and the “Interlocking X” Device are trademarks of Exxon Mobil Corporation. • L. or processes described. “we. Some product properties are not frequently measured. expressly or impliedly. or completeness of this information or the products.Further references Many excellent articles exist on this topic. Ltd. Below are some listings that the reader may find helpful in further understanding this topic. footers.L. Florida. 1995. Typical values only represent the values one would expect if the property were tested in our laboratories with our test methods on the specified date.” DSET Laboratories. suitability. ©2003 Exxon Mobil Corporation. Tokyo. Exxon Mobil Corporation. Wide Band Control in Accelerated Weathering Tests. including all of its headers. 9 . 2nd Edition.” 1st International Symposium on Weatherability. “Narrow Band vs.” or “ExxonMobil” are used for convenience. nor any endorsement of any product or process. • F. There is no warranty against patent infringement. and may include any one or more of ExxonMobil Chemical Company. We expressly disclaim liability for any loss. materials. The information in this document relates only to the named product or materials when not in combination with any other product or materials. The user may forward.” J. September 18-20. Miami.P. “Examples of use and misuse of accelerated testing of plastics. 1985. “Test Methods for Determining the Outdoor Durability of Coatings. or any affiliates they directly or indirectly steward. • K. but we do not represent. Scott. the merchantability. and we expressly disclaim any contrary implication. 1992. Techniques and Applications. May 12-13. • J. and/or photocopy this copyrighted document only if unaltered and complete. We based the information on data believed to be reliable on the date compiled. reliability. Polymer Stabilization and Degradation: Problems.” Symposium.

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