DOCSLIB.ORG

Lifetime and Degradation Studies of Poly (Methyl Methacrylate) (Pmma) Via Data-Driven Methods

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Lifetime and Degradation Studies of Poly (Methyl Methacrylate) (Pmma) Via Data-Driven Methods LIFETIME AND DEGRADATION STUDIES OF POLY (METHYL METHACRYLATE) (PMMA) VIA DATA-DRIVEN METHODS by DONGHUI LI Submitted in partial fulfillment of the requirements For the degree of Doctor of Philosophy Department of Materials Science and Engineering CASE WESTERN RESERVE UNIVERSITY May, 2020 Lifetime and Degradation Studies of Poly (Methyl Methacrylate) (PMMA) via Data-driven Methods Case Western Reserve University Case School of Graduate Studies We hereby approve the thesis1 of DONGHUI LI for the degree of Doctor of Philosophy Dr. Roger H. French Committee Chair, Adviser 03/17/2020 Department of Materials Science and Engineering Dr. Laura S. Bruckman Committee Member 03/17/2020 Department of Materials Science and Engineering Dr. Mark R. De Guire Committee Member 03/17/2020 Department of Materials Science and Engineering Dr. Michael J. A. Hore Committee Member 03/17/2020 Department of Macromolecular Science and Engineering 1We certify that written approval has been obtained for any proprietary material contained therein. To my parents, Jinxing Li & Xuemiao Chen, and my sister, Dongjie Li. Without them, none of this would’ve been possible. Table of Contents List of Tables vi List of Figures vii Acknowledgements xvi Abstract xvii Abstract xvii Chapter 1. Introduction1 PMMA: Applications and Degradation1 Lifetime and Degradation Science: Applicability to Polymers2 Thesis Overview3 Chapter 2. Literature Review5 PMMA and Its Applications5 Long-term Durability of Polymers: PMMA6 How to study polymer degradation scientifically 16 Photostabilization of Polymers: PMMA 21 Data-driven Lifetime Study 22 Statistical Learning Methods in Weathering Studies: State of Art Modeling 29 Chapter 3. Experimental 1 38 PMMA formulations 38 Exposures 38 Evaluations 41 Urbach analysis of absorption edges and Lorentzian fitting 42 iv Chapter 4. Results 45 Stabilizers in baseline samples of the 6 grades of PMMA 46 Yellowness Index and Haze 49 Absorbance and Induced Absorbance to Dose 57 Urbach fit results for 6 grades of PMMA 71 Self-organizing map as a tool to explore degradation patterns in 6 grades of PMMA 74 Chapter 5. Discussion 83 Urbach edge analysis 83 The effect of exposure types on degradation rate 85 Comparison of the durability of the 6 grades of PMMA 86 Degradation pathway models of PMMA 87 Chapter 6. Conclusion 90 Appendix A. Preparation of this document 92 Appendix B. Figures 93 Absorbance data for highly stabilized formulations 93 GC-MS data of the 6 grades of PMMA 94 Pairs plots for UVT and FF1 sample exposed in Hot QUV. 98 Appendix. Complete References 100 v List of Tables 2.1 General properties of unfilled PMMA.1 6 3.1 Exposure based on ASTM G154 and ASTM G155 standards 40 3.2 Spectral characteristics 40 4.1 Additives information for PMMA in Hot QUV at 0 hour. The ’-’ stands for that the stabilizer was not detected and the ’?’ stands for the stabilizer should be in formulation based on UV-Vis spectroscopy but was not detected by GC/MS. 46 4.2 Additives information for PMMA in Hot QUV at 0 hour with brand name and label for self-organizing map. The ’-’ stands for that the stabilizer was not detected and the ’?’ stands for the stabilizer should be in formulation based on UV-Vis spectroscopy but was not detected by GC/MS. 75 5.1 Urbach edge fit parameters for PMMA in Hot QUV at 0 hour 84 5.2 Urbach edge fit parameters for UVT PMMA in Hot QUV 84 5.3 Urbach edge fit parameters for FF1 PMMA in Hot QUV 85 vi List of Figures 2.1 Poly(methyl methacrylate) (PMMA) and monomer methyl methacrylate (MMA) structure5 2.2 The cause-and-effect diagram of PMMA degradation: the diagram is like a fish’s skeleton with the problem, the performance loss of PMMA, at the head and the causes for the performance loss feeding into the spine. General performance loss includes discoloration, embrittlement and haze formation.8 2.3 Decomposition of the ester group: ester groups on the side chain of PMMA absorbing light and the degradation of ester group involves three reaction. Reaction (1) is the most important process/2. 10 2.4 Main chain scission: a ¯-scission with formation of tertiary alkyl radical 11 2.5 PMMA:Disproportion reaction by hydrogen abstraction 11 2.6 Mechanisms for the generation of the secondary alkyl radical by the hydrogen abstraction reaction of backbone with methyl formate radical 11 2.7 PMMA main chain degradation: structure (1) and (2) are the results of homolytic main chain scission. The primary radical (2) can abstract hydrogen from the main chain to form a secondary radical (3). 12 2.8 Main chain radical termination 12 2.9 Degradation of PMMA in the presence of oxygen: the three types of alkyl readicals react rapidly with oxygen to generate peroxyl radicals. vii The CH , secondary and tertiary alkyl radicals react with oxygen to ¢ 3 yield peroxyl radicals3 13 2.10 Termination of peroxyl radical happens when at least one of the peroxyl radical is primary or secondary. The termination undergoes a Russell-type reaction to generate a ketone or aldehyde with an alcohol 14 2.11 Alkoxyl radicals generated by non-terminating reaction of two tertiary peroxyl radicals 14 2.12 The ¯-scission of Alkoxyl radicals 14 2.13 Monomer reactions: 3 pathways to degradation, where I is the free ¤ radical initiator generated from the degradation of the monomer and M and M represent the propagating radical and monomer ¤ respectively. 15 2.14 The monomer residual’s effect on degradation: reaction to generate tertiary alkyl radical 15 2.15 Spectral power distributions (280-4000nm) of The ASTM G173-03 AM 1.5, fluorescent UVA-340 and xenon arc full spectrum light sources 19 2.16 Spectral power distributions (280-400nm) of The ASTM G173-03 AM 1.5, fluorescent UVA-340 and xenon arc full spectrum light sources 20 2.17 Photostabilizations in photooxidative process 21 2.18 Data-driven method to study the durability of polymer materials 22 2.19 FTIR spectra for extruded PMMA sample. 24 2.20 Block diagram for Gas chromatography–mass spectrometry using electron ionization for collection of mass spectrum. 25 viii 2.21 CIE color space, top view 27 2.22 Spectrophotometer for haze measurement. 28 2.23 The Jablonski diagram for fluorescence. 30 2.24 Computational environment for data analysis: several open source software tools and R packages for visualization and spectral analysis. 30 2.25 An artificial network with 3 layers: input layer, hidden layer, and output layer 32 2.26 Training process of a self-organizing map 32 2.27 An example of structural equation model. Boxes contain variables that can be measured in the data. Circles contain variables that cannot be measured. Residuals and variances are drawn as double headed arrows pointing into an object. 36 2.28 An example of path modeling 36 2.29 An example of network modeling for yellowness index prediction with induced absorbance to dose as mechanism variable. 37 3.1 The exposure routes for the degradation study of the 6 grades of PMMA. 41 4.1 Stabilizers in the 6 grades of PMMA detected by GC/MS 48 4.2 The optical absorbance for UV absorbers4. 49 4.3 Yellowness index data for the stablilizer-free PMMA (UVT). 50 4.4 Yellowness index data for the 6 grades of PMMA. 50 4.5 Yellowness index data for the 5 grades of PMMA without UVT. 52 ix 4.6 Haze data for the 6 grades of PMMA. 52 4.7 Haze data for the 6 grades of PMMA exposed in QSUN. 53 4.8 Haze data for the 6 grades of PMMA in Hot QUV and Cyclic QUV. 53 4.9 Surface morphology of UVT samples at 0 hour 55 4.10 Surface morphology of UVT samples at 3200 hours exposure in QSUN. 55 4.11 Surface roughness of irradiated side (front) and non-irradiated side (back) in QSUN 56 4.12 ¢E data for the 6 grades of PMMA. 56 4.13 The panel plots for the baseline sample without any exposure. Each panel has 8 UV-Vis spectral data of samples. At baseline measurement, all the panel plots in one column should have similar results, indicating each grade of PMMA has low samplt-to-sample variation. 58 4.14 The process of quantification of degradation rate by induced absorbance to dose calculation: UVT exposed in Hot QUV as an example. 59 4.15 Abs/cm spectra for UVT under Hot QUV exposure. 60 4.16 Induced absorbance to dose (IAD) spectra for UVT under Hot QUV exposure. 60 4.17 Abs/cm spectra for UVT under Cyclic QUV exposure. 61 4.18 Induced absorbance to dose (IAD) spectra for UVT under Cyclic QUV exposure. 61 4.19 Abs/cm spectra for UVT under QSUN exposure. 62 x 4.20 Induced absorbance to dose (IAD) spectra for UVT under QSUN exposure. 63 4.21 Abs/cm spectra for FF1 under Hot QUV exposure. 65 4.22 Induced absorbance to dose (IAD) spectra for FF1 under Hot QUV exposure. 65 4.23 Abs/cm spectra for FF1 under Cyclic QUV exposure. 66 4.24 Induced absorbance to dose (IAD) spectra for FF1 under Cyclic QUV exposure. 66 4.25 Abs/cm spectra for FF1 under QSUN exposure. 67 4.26 Induced absorbance to dose (IAD) spectra for FF1 under QSUN exposure. 67 4.27 Abs/cm spectra for UVO under Hot QUV exposure. 68 4.28 Induced absorbance to dose (IAD) spectra for UVO under Hot QUV exposure. 68 4.29 Abs/cm spectra for UVO under Cyclic QUV exposure. 69 4.30 Induced absorbance to dose (IAD) spectra for UVO under Cyclic QUV exposure.
Load more

Recommended publications
  • Study of Polystyrene Degradation Using Continuous Distribution Kinetics in a Bubbling Reactor
    Korean J. Chem. Eng., 19(2), 239-245 (2002) Study of Polystyrene Degradation Using Continuous Distribution Kinetics in a Bubbling Reactor Wang Seog Cha†, Sang Bum Kim* and Benjamin J. McCoy** School of Civil and Environmental Engineering, Kunsan National University, Kunsan 573-701, Korea *Department of Chemical Engineering, Korea University, Seoul 136-701, Korea **Department of Chemical Engineering and Material Science, University of California, Davis, CA 95616, USA (Received 3 April 2001 • accepted 10 September 2001) Abstract−A bubbling reactor for pyrolysis of a polystyrene melt stirred by bubbles of flowing nitrogen gas at at- mospheric pressure permits uniform-temperature distribution. Sweep-gas experiments at temperatures 340-370 oC allowed pyrolysis products to be collected separately as reactor residue(solidified polystyrene melt), condensed vapor, and uncondensed gas products. Molecular-weight distributions (MWDs) were determined by gel permeation chro- matography that indicated random and chain scission. The mathematical model accounts for the mass transfer of vaporized products from the polymer melt to gas bubbles. The driving force for mass transfer is the interphase differ- ence of MWDs based on equilibrium at the vapor-liquid interface. The activation energy and pre-exponential of chain scission were determined to be 49 kcal/mol and 8.94×1013 s−1, respectively. Key words: Pyrolysis, Molecular-Weight-Distribution, Random Scission, Chain-end Scission, Continuous Distribution Theory INTRODUCTION Westerout et al. proposed a random-chain dissociation (RCD) model, based on evaporation of depolymerization products less than Fundamental and practical studies of plastics processing, such a certain chain length. In a subsequent paper [Westerout et al., 1997b] as energy recovery (production of fuel) and tertiary recycle (recov- on screen-heater pyrolysis, the RCD model was further described.
    [Show full text]
  • Pathways for Degradation of Plastic Polymers Floating in the Marine Environment
    Environmental Science Processes & Impacts View Article Online CRITICAL REVIEW View Journal | View Issue Pathways for degradation of plastic polymers floating in the marine environment Cite this: Environ. Sci.: Processes Impacts ,2015,17,1513 Berit Gewert, Merle M. Plassmann and Matthew MacLeod* Each year vast amounts of plastic are produced worldwide. When released to the environment, plastics accumulate, and plastic debris in the world's oceans is of particular environmental concern. More than 60% of all floating debris in the oceans is plastic and amounts are increasing each year. Plastic polymers in the marine environment are exposed to sunlight, oxidants and physical stress, and over time they weather and degrade. The degradation processes and products must be understood to detect and evaluate potential environmental hazards. Some attention has been drawn to additives and persistent organic pollutants that sorb to the plastic surface, but so far the chemicals generated by degradation of the plastic polymers themselves have not been well studied from an environmental perspective. In this paper we review available information about the degradation pathways and chemicals that are formed by degradation of the six plastic types that are most widely used in Europe. We extrapolate that information Creative Commons Attribution 3.0 Unported Licence. to likely pathways and possible degradation products under environmental conditions found on the oceans' surface. The potential degradation pathways and products depend on the polymer type. UV-radiation and oxygen are the most important factors that initiate degradation of polymers with a carbon–carbon backbone, leading to chain scission. Smaller polymer fragments formed by chain scission are more susceptible to biodegradation and therefore abiotic degradation is expected to Received 30th April 2015 precede biodegradation.
    [Show full text]
  • Biodeterioration of Untreated Polypropylene Microplastic Particles by Antarctic Bacteria
    polymers Article Biodeterioration of Untreated Polypropylene Microplastic Particles by Antarctic Bacteria Syahir Habib 1, Anastasia Iruthayam 1, Mohd Yunus Abd Shukor 1 , Siti Aisyah Alias 2,3 , Jerzy Smykla 4 and Nur Adeela Yasid 1,* 1 Department of Biochemistry, Faculty of Biotechnology and Biomolecular Sciences, Universiti Putra Malaysia, Serdang 43400, Selangor, Malaysia; [email protected] (S.H.); [email protected] (A.I.); [email protected] (M.Y.A.S.) 2 Institute of Ocean and Earth Sciences, C308 Institute of Postgraduate Studies, University of Malaya, Kuala Lumpur 50603, Malaysia; [email protected] 3 National Antarctic Research Centre, B303 Level 3, Block B, IPS Building, Universiti Malaya, Kuala Lumpur 50603, Malaysia 4 Institute of Nature Conservation, Polish Academy of Sciences, Mickiewicza, 33, 31-120 Kraków, Poland; [email protected] * Correspondence: [email protected]; Tel.: +60-(0)3-9769-8297 Received: 7 September 2020; Accepted: 22 October 2020; Published: 6 November 2020 Abstract: Microplastic pollution is globally recognised as a serious environmental threat due to its ubiquitous presence related primarily to improper dumping of plastic wastes. While most studies have focused on microplastic contamination in the marine ecosystem, microplastic pollution in the soil environment is generally little understood and often overlooked. The presence of microplastics affects the soil ecosystem by disrupting the soil fertility and quality, degrading the food web, and subsequently influencing both food security and human health. This study evaluates the growth and biodegradation potential of the Antarctic soil bacteria Pseudomonas sp. ADL15 and Rhodococcus sp. ADL36 on the polypropylene (PP) microplastics in Bushnell Haas (BH) medium for 40 days.
    [Show full text]
  • Degradation and Recyclability of Poly (Ethylene Terephthalate)
    Chapter 4 Degradation and Recyclability of Poly (Ethylene Terephthalate) S. Venkatachalam, Shilpa G. Nayak, Jayprakash V. Labde, Prashant R. Gharal, Krishna Rao and Anil K. Kelkar Additional information is available at the end of the chapter http://dx.doi.org/10.5772/48612 1. Introduction The physical and chemical properties of polymers depend on the nature, arrangement of chemical groups of their composition and the magnitude of intra or intermolecular forces i.e primary and secondary valence bonds present in the polymer. Degradation process occurs due to the influence of thermal, chemical, mechanical, radiative and biochemical factors occurring over a period of time resulting in deterioration of mechanical properties and colour of polymers. The degradation occurs due to changes accompanying with the main backbone or side groups of the polymer. Degradation is a chemical process which affects not only the chemical composition of the polymer but also the physical parameters such as colour of the polymer, chain conformation, molecular weight, molecular weight distribution, crystallinity, chain flexibility, cross-linking and branching. The nature of weak links and end groups in the polymers contribute to stability of polymers. The degradation process is initiated at the terminal units with subsequent depolymerization. For example paraformaldehyde with hydroxyl terminal starts to degrade at about 170°C whereas the same polymer with acetyl terminals decomposes at about 200°C [1]. Replacement of carbon main chain with hetero atoms like P, N, B increases the thermal stability e.g. PON polymers containing phosphorus, oxygen, nitrogen and silicon. The exposure of polymeric materials to environmental factors over a period of time will lead to deterioration of physical, chemical, thermal and electrical properties.
    [Show full text]
  • Effect of Polymer Degradation on Polymer Flooding in Heterogeneous Reservoirs
    polymers Article Effect of Polymer Degradation on Polymer Flooding in Heterogeneous Reservoirs Xiankang Xin 1 ID , Gaoming Yu 2,*, Zhangxin Chen 1,3, Keliu Wu 3 ID , Xiaohu Dong 1 and Zhouyuan Zhu 1 ID 1 College of Petroleum Engineering, China University of Petroleum, Beijing 102249, China; [email protected] (X.X.); [email protected] (Z.C.); [email protected] (X.D.); [email protected] (Z.Z.) 2 College of Petroleum Engineering, Yangtze University, Wuhan 430100, China 3 Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, AB T2N 1N4, Canada; [email protected] * Correspondence: [email protected]; Tel.: +86-27-6911-1069 Received: 3 July 2018; Accepted: 31 July 2018; Published: 2 August 2018 Abstract: Polymer degradation is critical for polymer flooding because it can significantly influence the viscosity of a polymer solution, which is a dominant property for polymer enhanced oil recovery (EOR). In this work, physical experiments and numerical simulations were both used to study partially hydrolyzed polyacrylamide (HPAM) degradation and its effect on polymer flooding in heterogeneous reservoirs. First, physical experiments were conducted to determine basic physicochemical properties of the polymer, including viscosity and degradation. Notably, a novel polymer dynamic degradation experiment was recommended in the evaluation process. Then, a new mathematical model was proposed and an in-house three-dimensional (3D) two-phase polymer flooding simulator was designed to examine both polymer static and dynamic degradation. The designed simulator was validated by comparison with the simulation results obtained from commercial software and the results from the polymer flooding experiments. This simulator further investigated and validated polymer degradation and its effect.
    [Show full text]
  • ASPHALTENE GRAFT COPOLYMER by FT-IR SPECTROSCOPY CT&F Ciencia, Tecnología Y Futuro, Vol
    CT&F Ciencia, Tecnología y Futuro ISSN: 0122-5383 [email protected] ECOPETROL S.A. Colombia León-Bermúdez, Adan-Yovani; Salazar, Ramiro SYNTHESIS AND CHARACTERIZATION OF THE POLYSTYRENE - ASPHALTENE GRAFT COPOLYMER BY FT-IR SPECTROSCOPY CT&F Ciencia, Tecnología y Futuro, vol. 3, núm. 4, diciembre, 2008, pp. 157-167 ECOPETROL S.A. Bucaramanga, Colombia Available in: http://www.redalyc.org/articulo.oa?id=46530410 How to cite Complete issue Scientific Information System More information about this article Network of Scientific Journals from Latin America, the Caribbean, Spain and Portugal Journal's homepage in redalyc.org Non-profit academic project, developed under the open access initiative SYNTHESIS AND CHARACTERIZATION OF THE POLYSTYRENE - ASPHALTENE GRAFT COPOLYMER BY FT-IR SPECTROSCOPY Ciencia, Tecnología y Futuro SYNTHESIS AND CHARACTERIZATION OF THE POLYSTYRENE - ASPHALTENE GRAFT COPOLYMER BY FT-IR SPECTROSCOPY Adan-Yovani León-Bermúdez1* and Ramiro Salazar1 1Universidad Industrial de Santander (UIS) - Grupo de Polímeros, Bucaramanga, Santander, Colombia e-mail: [email protected] (Received April 30, 2008; Accepted Nov. 27, 2008) he creation of new polymer compounds to be added to asphalt has drawn considerable attention because these substances have succeeded in modifying the asphalt rheologic characteristics and physical properties Tfor the enhancement of its behavior during the time of use. This work explains the synthesis of a new graft copolymer based on an asphalt fraction called asphaltene, modified with maleic anhydride. Polystyrene functionali- zation is conducted in a parallel fashion in order to obtain polybenzylamine resin with an amine – NH2 free group, that reacts with the anhydride graft groups in the asphaltene, thus obtaining the new Polystyrene/Asphaltene graft copolymer.
    [Show full text]
  • Predictive Lifetime Models of Polymer Insulation Degradation and Biorenewable Thermosets Through Cati
    Iowa State University Capstones, Theses and Graduate Theses and Dissertations Dissertations 2013 Polymer damage mitigation--predictive lifetime models of polymer insulation degradation and biorenewable thermosets through cationic polymerization for self-healing applications Peter Raymond Hondred Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/etd Part of the Mechanics of Materials Commons Recommended Citation Hondred, Peter Raymond, "Polymer damage mitigation--predictive lifetime models of polymer insulation degradation and biorenewable thermosets through cationic polymerization for self-healing applications" (2013). Graduate Theses and Dissertations. 13105. https://lib.dr.iastate.edu/etd/13105 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Polymer damage mitigation—predictive lifetime models of polymer insulation degradation and biorenewable thermosets through cationic polymerization for self- healing applications by Peter Raymond Hondred A dissertation submitted to the graduate faculty in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Major: Materials Science and Engineering Program of Study Committee: Michael R. Kessler, Major Professor Nicola
    [Show full text]
  • Properties of Poly(Vinyl Chloride) Modified by Cellulose
    Polymer Journal, Vol. 37, No. 5, pp. 340–349 (2005) Properties of Poly(vinyl chloride) Modified by Cellulose y Halina KACZMAREK, Krzysztof BAJER, and Andrzej PODGO´ RSKI Faculty of Chemistry, Nicolaus Copernicus University, Gagarin 7, 87-100 Torun´, Poland (Received July 30, 2004; Accepted February 9, 2005; Published May 15, 2005) ABSTRACT: Compositions of poly(vinyl chloride) with 2–10 (w/w) cellulose were prepared by extrusion. The mechanical properties and water absorptiveness of modified PVC have been measured. For the purpose of estimating the susceptibility to microorganisms’ attack, all samples were being composted in garden soil for up to 14 months. Mi- crobial analysis of soil used has been made. The biodegradation efficiency was estimated in terms and by means of weight loss, ATR-FT IR spectroscopy, as well as changes in mechanical resistance. Moreover, thermal stability of virgin and composted samples was studied by ther- mogravimetry. It has been found that the addition of a small amount of cellulose to PVC changes only slightly its properties. Inter- molecular interactions and also some thermal crosslinking taking place during the processing of samples’ preparation retard the biodegradation of PVC + cellulose blends. [DOI 10.1295/polymj.37.340] KEY WORDS Poly(vinyl chloride) / Cellulose / Blend Properties / Biodegradation / Thermal Stability / Polymeric materials have considerably influenced amounts (2–10 w/w) of cellulose, and to check the and enhanced the development of numerous branches susceptibility of samples to biodegradation. Accord- of industry owing to their various and diverse proper- ing to the published data,10 even a low content of nat- ties which can be additionally modified in a wide ural component in polymeric composition can induce range aimed at meeting the commercial and utility re- and facilitate its biodegradation.
    [Show full text]
  • Current Status of Methods Used in Degradation of Polymers: a Review
    MATEC Web of Conferences 144, 02023 (2018) https://doi.org/10.1051/matecconf/201814402023 RiMES 2017 Current Status of Methods Used In Degradation of Polymers: A Review Aishwarya Kulkarni1 and Harshini Dasari1 1Department of Chemical Engineering, Manipal Institute of Technology, Manipal, Manipal Academy of Higher Education, India. Abstract. Degradation of different polymers now a day is the most crucial thing to carry out. It possesses threats to human health as well as to the environment. Different polymers like PVA, PVC, and PP with high density and low density are one of the most consumed by population and also their degradation is a bit difficult. For this many people have started working on effective methods of degradation of these polymers. This can be done by thermal degradation and pyrolysis which requires high temperature, bio degradation using starch, bacteria etc and photo degradation. Traditional gravimetric and respirometric techniques are the methods currently used in testing. They fit readily for degradable polymeric materials usually. Also they are well suited for biodegradable components with polymer blends. But the recent polymer generation is comparatively resistant to bio degradation of polymers hence they cannot be used here. The polymer matrices are readily present in the plasticizers boosting the strength of polymeric material hence in addition; there is the mechanism of degradation. The information on various methods discussed in this review is planned to illustrate a best fit of methods for those who are interested in testing the degradation of polymers under different environmental conditions and selection of appropriate technique for specific combination of mixture of polymer and catalysts which helps to degrade the polymeric material.
    [Show full text]
  • Photo-Oxidative Degradation of Abs Copolymer a Thesis Submitted to the Graduate School of Natural and Applied Science of Middle
    PHOTO-OXIDATIVE DEGRADATION OF ABS COPOLYMER A THESIS SUBMITTED TO THE GRADUATE SCHOOL OF NATURAL AND APPLIED SCIENCE OF MIDDLE EAST TECHNICAL UNIVERSITY BY AYLİN GÜZEL IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE OF MASTER OF SCIENCE IN POLYMER SCIENCE AND TECHNOLOGY SEPTEMBER 2009 Approval of the thesis PHOTO-OXIDATIVE DEGRADATION OF ABS COPOLYMER Submitted by AYLİN GÜZEL in partial fulfillment of the requirements for the degree of Master of Science in Polymer and Technology Department, Middle East Technical University by, Prof. Dr. Canan Özgen Dean, Graduate School of Natural and Applied Sciences Prof. Dr. Cevdet Kaynak Head of Department, Polymer Science and Technology Prof. Dr. Teoman Tinçer Supervisor, Chemistry Dept., METU Prof. Dr. Cevdet Kaynak Co-Supervisor, Metallurgical and Materials Eng. Dept., METU Examining Committee Members: Prof. Dr. Leyla Aras Chemistry Dept., METU Prof. Dr. Teoman Tinçer Chemistry Dept., METU Prof. Dr. Cevdet Kaynak Metallurgical and Materials Eng., Dept. METU Prof. Dr. Savaş Küçükyavuz Chemistry Dept., METU Assoc. Prof. Dr. Atilla Cihaner Chemistry Group, ATILIM UNIVERSITY Date: I hereby declare that all information in this document has been obtained and presented in accordance with academic rules and ethical conduct. I also declare that, as required by these rules and conduct, I have fully cited and referenced all material and results that have not original to this work. Name, Last name : Aylin Güzel Signature : iii ABSTRACT PHOTO-OXIDATIVE DEGRADATION OF ABS COPOLYMER Güzel, Aylin M.S., Department of Polymer Science and Technology Supervisor: Prof. Dr. Teoman Tinçer Co-Supervisor: Prof. Dr. Cevdet Kaynak September 2009, 55 pages Acrylonitrile-butadiene-styrene (ABS) polymer is one of the most popular copolymer having an elastomeric butadiene phase dispersed in rigid amorphous styrene and semi-crystalline acrylonitrile.
    [Show full text]
  • New Focus on Peek
    NEW FOCUS ON PEEK INTRODUCTION Polyether ether ketone, or PEEK, is a high-performance and highly popular engineered thermoplastic. PEEK is a member of the polyaryletherketone (PAEK) family which includes other familiar semi-crystalline polymers such as polyetherketone (PEK), polyetherketoneketone (PEKK), and polyetherether-ketoneketone (PEEKK). This family of polymers is known for such performance characteristics as excellent mechanical properties and chemical resistance. PAEK family polymers retain these attributes even at high temperatures, and thus their thermal stability has become one of their hallmarks. Although relatively new to the commercial synthetic polymer market (ca. 1978), PEEK has now found its way into such diverse applications as tubing, molded parts ranging from bearings to plates to gears, insulation such as motors parts and coating for wires, to prosthetics and implantables for use within the human body. For performance plastics, PEEK is often compared to fluoropolymers because it shares several high-performing and beneficial features with several of the best-performing fluoropolymers – including a service temperature up to 260 °C (500 °F). PEEK, however, provides more diversity options to attain properties that may be out of reach for some fluoropolymers. Today, PEEK is the most widely commercialized PAEK family polymer, and new uses continue to come to the fore. SYNTHESIS AND STRUCTURE PEEK was first synthesized in 1977 and was industrialized in 1981 [1, 2]. PEEK is produced most immediately from difluorobenzophenone and disodium hydroquinone (Fig. 1). Often viewed in a class with fluoropolymers such as PTFE or PFA, PEEK polymer, however, does not contain fluorine. Initial synthesis of PEEK was difficult due to its insolubility in most organic solvents [2, 3].
    [Show full text]
  • INTRODUCTION to POLYMER ADDITIVES and STABILIZATION Bobbijo Van Beusichem , Ph.D., Senior Staff Scientist, Expert Services, Michael A
    INTRODUCTION TO POLYMER ADDITIVES AND STABILIZATION Bobbijo van Beusichem, Ph.D., Senior Staff Scientist, Expert Services, Michael A. Ruberto, Ph.D., Head of Regulatory Services, NAFTA, Expert Services Ciba Expert Services, Ciba Specialty Chemicals Introduction Polymer Auto-oxidation Cycle Role of Additives Stabilizers (cont’d) Phenolic AO Oxidation Chemistry R-H Melt Processing Energy . O (Polymer) O OH O• Polymers are used in ALL aspects of our lives, including pharmaceutical packaging and Catalyst Residues • Most polyolefins contain one or more antioxidants Additives provide to Plastics: + RO• medical device preparation. HO CH CH O CH -] -C + RO• at levels of 0.05 – 0.10% 2 2 2 4 -ROH -ROH Oxygen Stabilization ¾ Primary antioxidants are generally radical Irganox 1010 R R Cycle II Cycle I scavengers or H-donors H R* R • R R Quinonemethide RO • + • OH ROO • To retain the original molecular architecture of the – i.e. hindered phenols such as BHT, Irganox 1010, or Irganox 1076 HO CC OH R • polymer under the effect heat, light etc. Coupling + – Long-term protection for the polymer ROOH + 2 RO• and ¾ Secondary antioxidants are typically O O -2 ROH Path of R • Alkyl radical P Degradation RO • Alkoxy radical hydroperoxide decomposers Without the use of the proper stabilization package, polymers will degrade. Interaction ROO • Peroxy radical O R R ROOH Hydroperoxide Functionalization – i.e. trivalent phosphorus compounds with oxygen and light can cause significant degradation of the polymer. These degradation O products are potential leachables and extractables. such as Irgafos 168 O CC Often, blends of stabilizers will be used to protect the Auto-oxidation: Most labile hydrogens To provide additional attributes to the polymer which – Process stabilization (protects the primary Irgafos 168 polymer at various stages throughout the polymer lifecycle.
    [Show full text]