Protecting, Coloring and Testing Textile Sports Surfaces Two presentations to the International Association for Sports Surface Sciences (ISSS) in Rome, 16 th October 2008 Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM
Part 1 Factors affecting choice of Additives & Pigments for Textile Sports Surfaces Presentation to ISSS in Rome, October 2008 Daniel Mueller, Head Technical Center Polyolefines,, Ciba Inc, Basel Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM
Scope of presentation 1. Overview of Ciba, Industry Platform Plastics and core offerings 2. SynTurf applications The 3 P s a wider view of the needs of textile sports surfaces 1. P1 Need Performance during manufacture 2. P2 Need Performance in use 3. P3 Need Peace of mind in use and at End-of-life 3. Why are additives needed? 4. What are colorants? 5. Summing up Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 3
1) Ciba and Industry Platform Plastics Industries served by Ciba Presenting the Industry Platform Plastics (IPP) Overview of IPP product portfolio Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 4
Ciba Inc brief overview Global Presence Over 13 000 people committed to serving customers in 120 countries with leading edge innovation developed in 6 major R&D centers and made in 61 production sites Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 5
Ciba Inc brief overview 3 Segments focused on customer industries Plastic Additives Industries: Plastics (IPP) Lubricants (PLA) Home & Personal Care (H&PC) Coating Effects Industries: Coatings Printing Imaging Plastics Synthetic Fibers Electronics Information Technology Water & Paper Treatment Industries: Paper and Board Oil and Mining Water Treatment Detergents and Hygiene Agriculture Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 6
Ciba Inc brief overview IPP offers solutions for the plastics industry, including chemical fibers Agriculture Automotive Building & Construction Fibers Packaging & Consumer Goods Electrical & Electronics Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 7
Industry Platform Plastics for fiber too! Global Manufacturing operations Product development Global product offering for fibers Colorants Process, heat and light stabilizers Effect Additives Regional Technical Service labs Fiber and tape lines Advanced accelerated testing of weatherability National Sales offices Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 8
IPP offer for textile sports surfaces Stabilization retention of mechanical properties after processing and in-use. Coloration color retention or fading lifetime under various conditions Technical Centers - customer focused assistance, backed up laboratory work Application Centers - industry focused, development mandate IPP industry commitment know-how, sustainable practices, products Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 9
P1 Need Performance in processing Heat stability Ease of dispersion / long filter pack life No / low abrasion Throughput End product quality Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 10
P2 Need Performance in use Mechanical wear by: Players Maintenance Thermal shock (day / night; winter / summer for 10 years or more) Moisture gain and loss Chemical wear from: Sun (Heat, UV) Water (often involved in reactions started by UV) Material interactions Sulphur, oils, zinc, from infill Plasticizers Other chemical additives; incl. Cleaning solutions Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 11
P3 Need Peace of mind in use User exposure to dust or particulate matter from textile surface: Extraction of chemical identities by saliva etc Transfer to the environment Extraction of chemical identities by rainwater / cooling water and drainage to collection system or earth Both extraction mechanisms have been studied Studies have shown practically zero extraction (water) Negative perceptions in the general public exhibit extreme study resistance Care needed at formulation stage Consider in particular issues from using heavy metal pigments and metal complexes Comments Additives: with the right choice of the additive, difficult to extract after incorporation into the polymer, especially by water Pigments by definition insoluble and non-available but cannot be ruled out completely Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 12
P3 (cont d) Need Peace of mind after use Must have peace of mind for subsequent Recycling Incineration Landfill Nice NOT to have Negative value at end of life Disposal as dangerous waste Total formulation has to be safe for chosen disposal method. Do we know what safe is in 10 years? REACH is a starting point for Europe Will echo round the world Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 13
3) Why are stabilizers needed? Mechanical property retention Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM
Why do we have to stabilize polymers? General considerations Stabilizers are used to maintain the polymer's original strength, flexibility and toughness as well as the visual aspects like color or gloss. These properties need to be maintained in order to meet end use applications that have performance targets or customer specifications Low end performance: non-durable goods Mid-range performance: use it for a while High end performance: durable goods e.g. food wrapping e.g. heavy duty bags e.g. synthetic turf; water tanks Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 15
The Degradation of Polymers Inert polymer = technically impossible Impurities, catalyst residues, structural defects... cannot be avoided Oxidation is favored by: Energy (e.g. mechanical stress, heat, light) Metals / metal ions (catalyst residue, impurities, co-additives) Several oxidation products and chemicals (acids) Peroxides, peracids, alcohols, ketones, aldehydes, acids,... Oxidation is an autocatalytic process.!! AUTOXIDATION!! Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 16
The Degradation of Polymers 1 R-H (Polymer) Catalyst residues, oxygen, shear... UV/VIS light Different options to counteract depending on substrates needs and application (e.g. processing, thermal and/or light stabilizer) ROOH 2 RO + OH R RH HALS 1 no damage 2 pre-damage RH ROO R + ROH + H 2 O O-O Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 17
Degradation of polymers by sunlight* UV light Oxygen PHOTO-OXIDATION Polymer * and artificial light Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 18
Principles of Light Stabilization - UV absorbers absorb UV light transform UV radiation into thermal energy dependent on thickness of sample Law of Lambert-Beer protects bulk - Hindered amines scavenge radicals activated during light exposure independent on thickness of the article protects bulk and surface (HAS HALS Hindered Amine (Light) Stabilizers) Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 19
UV light management R-H (Polymer) Catalyst residues, oxygen, shear... HALS R UV/VIS light RH ROOH ROO UV absorbers, UV screeners & pigments UV Light Management RO + OH RH R + ROH + H 2 O HALS HALS O-O Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 20
NASA Global Irradiation (Kilolangleys) Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 21
Retention of mechanical properties w & w/o infill Choice of correct stabilizer system can minimize effects of rsbr (or other infill) Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 22
4) What are colorants? Organic and inorganic Organic based on carbon chemistry, without metal atoms as part of the molecular structure Inorganic based on metal chemistry, often mixed metals, usually oxides or insoluble salts Metal complex carbon chemistry with a metal atom in the structure Pigments and dyestuffs OR insoluble and soluble Pigments are colorants that are insoluble in the medium of use Dyestuffs are soluble in the medium of use, traditionally water Polymer soluble dyestuffs (polysols) are soluble in the polymer of use Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 23
Colorant performance overview Inorganic (pigments only) Excellent processing stability, end use fastnesses Low color strength, high opacity High loading needed Depending on type, issues with abrasion Organic (pigments and polysols) High color strength Processing stability, end-use fastnesses wide ranging dependant on chemistry and polymer of use In polyolefines normally non-reactive Limited selection can withstand processing in nylons Metal complex (pigments and polysols) Combine the high color strength of organics With the high stability of inorganics But sometimes have issues with regard to the metal atom used Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 24
Important colorant properties Color Space Hue, lightness, and chroma Migration Gray scale (5 = good, 1 = poor) Heat Stability Generally tested for a 5 min. dwell up to 300 C Lightfastness Blue wool scale (8 is best, 1 is poor) Weatherability Rated on gray scale Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 25
Environmental considerations Any examination of the lead and chrome issue should take into account the entire value chain for the colorants Chemicals (RM s) containing Pb (Lead), Cr (Chromium), Ni (Nickel) Transportation and losses due to normal use & processes Worker exposure Pigments based on these RM s Transportation and losses due to normal use & processes Small particles: OSHA standards for hexavalent chromium moved from PEL of 50 ug/m3 down to ~1 ug/m3 in 2004. Incorporation into plastics Losses due to normal processing Disposal of wastes Recycling cradle to cradle Upcoming Regulations US SARA Synthetic Turf Council - Lead (Pb) EMEA REACH Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 26
Color retention of green formulations w & w/o infill Correct choice of yellow can minimize effects of rsbr (or other infill) on color retention Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 27
5) Summing up Stabilization can be adjusted for Exposure profile (sunlight, chemical influences) Lifetime needs Coloration can be adjusted for Exposure profile (sunlight, chemical influences) Lifetime needs Environmental sustainability issues Complete manufacturing and use cycle Sensitive issues can be managed by Correct choice of main colorants & co-colorants Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 28
PART 2 Thoughts on the accelerated artificial UV Testing of Textile Sports Surfaces Presentation to ISSS in Rome, October 2008 Daniel Mueller, Head Technical Center Polyolefines,, Ciba Inc, Basel Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM
Review of weathering testing Testing = source of weathering + standardized methods for sample preparation, use of source and determination of the effect. Weathering long term effects of light plus water (vapor) plus heat Textiles can be weathered Naturally e.g. Florida, South France Light intensity, water vapor, rain, temperature etc are typical but not constant Artificially xenon arc, fluorescence lamp, Depending on the apparatus used, parameters can be controlled. Light intensity is often raised above natural levels to accelerate effect Weathered textiles can be measured Mechanical properties are tested and compared to bench mark Appearance is measured, visually or electronically, and compared to bench mark Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 30
Methods Basic parameters Light source and filters Black panel temperature Continuous or intermittent exposure Turn off light Turn samples With or without moisture With or without direct irrigation (rain: wet/dry cycle ) Special treatments (e.g. contact with infill) Standards to be fulfilled Examples for artificial turf: ISO 4892-2/3; EN 14836; FIFA Method, DIN V 18035-7 Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 31
Light sources Source: Atlas Material Testing Technology LLC 1 2 1: critical UV light: activity of UVA and screeners mechanical effects 2: visible light: activity of pigments visual effects http://www.atlas-mts.com/download/what_light_is_right.pdf Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 32
Testing for Formulation development Natural weathering to keep contact with reality Accelerated weathering to keep time-lines short Accelerated vs. Natural needs to be predictable Ciba uses: Measurement with Xenon arc: Closest to real sunlight in the UV/VIS part Best fit with outdoor weathering Long term experience Pretreatment before weathering: contact with potential environment, e.g. infill Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 33
Ciba uses: WOM wet, cycle 7 (DIN-53387) 18 102 minutes Light 0.35 W/m 2 340-420 nm Xe 6500W Boro/Boro-S BP: 18-24 C 95% r.h. BP: 58-62 C 28-32% r.h. 34
Reasons for using Xenon Arc Source: Atlas Material Testing Technology LLC UVB 313 even below 290nm http://www.atlas-mts.com/download/what_light_is_right.pdf Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 35
Testing for Quality control Active substance extraction is not always possible (e.g. pigments insoluble) Multi-component formulations have complex interactions Must have reproducible results from one test to another No need for link to natural Ciba uses: analytical methods via wet chemistry: time consuming, expensive FTIR: needs for calibration curves, limited accuracy, easy and quick AAS for element analysis: Easy, quick, but only qualitative (fluorescence to check according to standards, calibration preferred) Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 36
Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM Examples
Influence of the UV system Stabilizers clearly increase the light stability of PE-LLD products 12000 Hours in WOM 10000 8000 6000 4000 no LS LS1 LS2 LS3 2000 0 Time to 50% retained tensile strength PE-LLD tapes: green pigmented; 150 micron (1:3); 1% of HALS based LS systems WOM weathering, no pretreatment Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 38
Influence of the UV system The contact to rubber is reducing the light stability of PE-LLD. The choice of the LS system defines the mechanical performance 5000 Hours in WOM 4000 3000 2000 1000 no LS LS1 LS2 LS3 0 Time to 50% retained tensile strength PE-LLD tapes: green pigmented; 150 micron (1:3); 1% of HALS based LS systems Treatment with recycled SBR; WOM weathering Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 39
Influence of the Pigment Pigments influence the light stability of PE-LLD even in terms of mechanical properties 12000 >11000 h Hours in WOM 10000 8000 6000 4000 Green 1 Green 2 Green 3 2000 0 Time to 50% retained tensile strength PE-LLD tapes: green pigmented; 150 micron (1:3); 1% of a HALS based LS systems WOM weathering, no pretreatment Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 40
Influence of the Pigment The contact to rubber is reducing the light stability of PE-LLD. The performance with different pigments can change compared to non treated samples, see slide before. 5000 Hours in WOM 4000 3000 2000 1000 Green 1 Green 2 Green 3 0 Time to 50% retained tensile strength PE-LLD tapes: green pigmented; 150 micron (1:3); 1% of a HALS based LS systems Treatment with recycled SBR; WOM weathering Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 41
Effect of Pigment and SBR on UV Stability The contact to rubber is reducing the light stability of PP. The choice of the pigment is important even for the mechanical performance % retained tensile strength 120 100 80 60 40 20 0 Green R1 Green R2 Green R1, Rubber Green R2, Rubber 0 1000 2000 3000 4000 5000 6000 Hours in WOM wet PP tapes: pigmented; 50 micron; 0.8% of a HALS based LS system Treatment with recycled SBR; WOM weathering Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 42
Effect of Pigment and SBR on UV Stability The contact to rubber is reducing the light stability of PP. The choice of the pigment is important for the visual performance Delta E 30 25 20 15 10 5 0 Green R1 Green R2 Green R1, Rubber Green R2, Rubber 0 2000 4000 6000 8000 Hours in WOM wet PP tapes: pigmented; 50 micron; 0.8% of a HALS based LS system Treatment with recycled SBR; WOM weathering Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 43
Development versus quality check An Index test (standard) alone is not giving an indication for life time. It should only be used as a quality control. 12000 >11000 h 120 Results after 3000h Hours in WOM 10000 8000 6000 4000 2000 0 WOM WOM/ rubber Time to 50% retained tensile strength % retained tensile strength 100 80 60 40 20 0 QUVA PE-LLD tapes: green pigmented; 150 micron (1:3); 1% of HALS based LS systems Treatment with recycled SBR; WOM weathering Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 44
Correlation Florida versus Xenon Artificial Weathering Comparison of Florida exposure and xenon arc Weather-Ometer exposure LDPE blown films 200 µm; T 50 = time to 50% retained elongation E 50 = energy to 50% retained elongation Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 45
Correlation Florida versus QUV-B Artificial Weathering Comparison of Florida exposure and QUV exposure LDPE blown films 200 µm; T 0.1 = time to 0.1 carbonyl absorbance E 50 = energy to 50% retained elongation Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 46
Summing up Weathering Outdoor Product development Time, reality Artificial exposure The choice of the right equipment according to the purpose Product development Time consuming, but accelerated; close to reality Quality check Quick test; away from reality Side factors like Infill has to be taken into consideration Failure criteria Mechanical properties Visual properties Polymer degradation Color fading Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 47
Disclaimer Copyright 2006 Ciba Specialty Chemicals Inc. All rights reserved. All trademarks mentioned are either property of or licensed to Ciba Specialty Chemicals and registered in relevant countries. IMPORTANT: The following supersedes Buyer s documents. SELLER MAKES NO REPRESENTATION OR WARRANTY, EXPRESS OR IMPLIED, INCLUDING OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. No statements herein are to be construed as inducements to infringe any relevant patent. Under no circumstances shall Seller be liable for incidental, consequential or indirect damages for alleged negligence, breach of warranty, strict liability, tort or contract arising in connection with the product(s). Buyer s sole remedy and Seller s sole liability for any claims shall be Buyer s purchase price. Data and results are based on controlled or lab work and must be confirmed by Buyer by testing for the intended conditions of use. The product(s) has (have) not been tested for, and is (are) therefore not recommended for, uses for which prolonged contact with mucous membranes, abraded skin, or blood is intended; or for uses for which implantation within the human body is intended. Please note that products may differ from country to country. If you have any queries, kindly contact your local Ciba Specialty Chemicals representative. Further information at website: http://www.cibasc.com For further information on any aspect of this presentation or for more details of the Ciba offer for Synthetic Turf please contact: anthony.judge@ciba.com Industry Platform Plastics, Technical Center Polyolefines, Oct 2008 / DM 48