This project supports a cooperative research project by Dr. Witold Brostow of the Department of Materials Science & Engineering and Dr. Jose Perez, Department of Physics at the University of North Texas (UNT), Denton and Dr. Ayman Mohamady Atta at the Egyptian Petroleum Research Institute (EPRI) in Cairo, Egypt. They plan to study the Synthesis and evaluation of porous polymers for absorbing petroleum spills based on recycled poly (ethylene terephthalate) (PET)

Intellectual Merit: The practical importance of absorption of petroleum spills is obvious well recognized. However, understanding of interactions between petroleum and absorbents is poor. One of the consequences is a small number of absorption - desorption cycles that extant petroleum sorbers can survive. The PIs will synthesize a variety of sorbents involving alkyl acrylates (octyl, dodecyl and octadecyl) copolymerized in turn with styrene, acrylic acid, methacrylic acid and olefines. Poly (ethylene terephthalate) (PET) will be recycled and fibers made from the recyclate. Subsequently, the copolymers will be grafted on nonwoven fibers of PET by two procedures: thermal and photochemical grafting. Properties of the prepared sorbents will be evaluated, including crosslink density, sorption time, sorption capacity, effects of repetitive sorption-desorption cycles and flexibility. Absorbed compositions will be studied by Raman spectroscopy and Fourier-transform infrared spectroscopy to characterize interactions of petroleum components with each polymer sorber. Connections of the sorption capacity to sorber material porosity, surface roughness and surface area will be determined by atomic force microscopy at the UNT. The UNT team has several capabilities indispensable for the project for characterization of the sorbers in particular. The EPRI partners have previous experience in dealing with oil spills and thus have a clear set of requirements for oil sorbers, and also have a track record in polymer synthesis including development of porous polymers. They will be able to provide unique resources for the project in addition to those from the UNT.

Broader impacts: Two potential outcomes from this project can be pertinent for protection of the environment: one is development of polymers with oil absorption capability and the second is using PET which is now being thrown out into the environment as waste. There are large amounts of PET waste; here in the US all 2 liter soft drink bottles are made from PET, and of course not only in this size and not only bottles. Using recycled PET as one of the starting materials will result in less petroleum used in making virgin polymers, lower cost of making polymeric sorbers than from virgin polymers only and less PET thrown into environment as waste. Advantages of the development of sorbers that can be used in more absorption- desorption cycles are clear. Five US graduate and undergraduate students will participate in the research project at UNT and at EPRI in Egypt, and will gain an international outlook on science and technology. Instructional articles in the Journal of Materials Education are expected to result from the project, providing the educators and students with pertinent knowledge on petroleum composition and properties, on oil spills, on development of porous polymers and on characterization of polymer-based materials.

Project Report

In spite of efforts to create electric cars, cars running on gasoline are with us and will so remain in the foreseeable future. The current batteries with their weight and efficiency will not provide us with electric airplanes any time soon. While gasoline is obtained from petroleum, petroleum has another application of comparable or perhaps greater importance: as a raw material for synthesis of polymers. With population of the globe that exceeded 7 billions and keeps growing, the demand for petroleum will continue to increase – and along with it the danger of oil spills [1 – 3]. We read about oil spills around Usinsk, Russia [3]: "Oil spills in Russia are less dramatic than disasters in the Gulf of Mexico or the North Sea, more the result of a drip-drip of leaked crude than a sudden explosion. But they're more numerous than in any other oil-producing nation including insurgency-hit Nigeria, and combined they spill far more than anywhere else in the world, scientists say". Economic Development Ministry of Russia in a 2010 report estimated spills in that country as up to 20 million tons per year [3]. Clearly materials that can absorb spilled oil have a large potential worldwide. Working on development of petroleum absorbing materials, we were confronted with several issues: a) such materials have to be porous as well as flexible to achieve the basic objectives; this suggest that porous polymers are the answer; b) in contrast to metals that oxidize and corrode easily, polymers which are thrown out into the environment as waste do not degrade easily; therefore, recycling is important; since our plan was to create porous polymers, using recycled polymers as starting materials was at least an option to explore. We have achieved in the Project significant progress in the development of porous sorbers for petroleum [4 – 6]. Specifically: A. Since it was not known a priori which class of polymers could fulfill the requirements well, we have worked with a variety of polymers that can be made porous, including polyurethanes (PUs), copolymers of octadecyl acrylate (ODA) with acrylic acid (AA) (ODA/AA), and crosslinked octadecylacrylate/maleic anhydride copolymers. B. We have used recycled poly(ethylene terephthalate) (PET) bottles in the process. PET bottles are produced worldwide in large quantities as containers for soft drinks, including the 2 liter bottles popular in the US. Therefore, large numbers of the bottles are thrown out into the environment. Our processes of making oil sorbers thus mitigate the contamination of the environment. C. Both bulk polymerization and suspension polymerization techniques were used since it was not known a priori which shall provide better oil sorbers. The latter process turned out to be better. There are several technical aspects of our work such as the use of appropriate solvents, monomer ratios, the use of crosslinking agents, determination of glass transition temperatures and more, which are not included in this General Public Report. D. Petroleum + toluene absorption capacities reaching 100 g of the liquid per 1 g of the polymer sorber have been reached. E. Removing the petroleum, toluene or their mixture from a spill by our polymeric sorbers can be performed repetitively (sorbtion-desorption cycling). F. Removal of oil spills cleans the environment and mitigates the need for more petroleum. The use of recycled PET contributes to protection of the environment in a different way. This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content. References: 1. extent-of-oil-spillage. 2. 3. 4. A. M. Atta, W. Brostow, T. Datashvili, R.A. El-Ghazawy, H.E. Hagg Lobland, A.-R.M. Hasan & J. M. Perez, Porous polyurethane foams based on recycled poly(ethylene terephthalate) for oil sorption, Polymer Internat. 2013, 62, 116. 5. A.M. Atta, W. Brostow, H.E. Hagg Lobland, A.-R.M. Hasan & J. M. Perez, Porous crosslinked copolymers of octadecyl acrylate (ODA) with acrylic acid (AA) as sorbers for crude petroleum spills, Polymer Internat. 2013, 62, in press. 6. A.M. Atta, W. Brostow, H.E. Hagg Lobland, A.-R.M. Hasan & J. M. Perez, Preparation of new oil sorbers based on PET fibers coated with crosslinked octadecylacrylate and maleic anhydride copolymers, in preparation.

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Osman Shinaishin
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