Issuu

(Ebook PDF) Materials, Mechatronics and Automation IV 1st edition by Dehuai Zeng 3038351172 full chapters pdf download https://ebookball.com/product/ebook-pdf-materials-mechatronicsand-automation-iv-1st-edition-by-dehuai-zeng-3038351172-fullchapters-25452/

Explore and download more ebooks or textbooks at ebookball.com

Get Your Digital Files Instantly: PDF, ePub, MOBI and More Quick Digital Downloads: PDF, ePub, MOBI and Other Formats

Materials Characterisation IV Computational Methods and Experiments 1st Edition by Mammoli, Brebbia ISBN 1845641892 9781845641894

https://ebookball.com/product/materials-characterisation-ivcomputational-methods-and-experiments-1st-edition-by-mammolibrebbia-isbn-1845641892-9781845641894-14522/

(Ebook PDF) Mechatronics Electromechanics and Contromechanics 1st edition by Denny Miu 0387978933 978-0387978932 full chapters

https://ebookball.com/product/ebook-pdf-mechatronicselectromechanics-and-contromechanics-1st-edition-by-dennymiu-0387978933-978-0387978932-full-chapters-25462/

Measuring Technology and Mechatronics Automation in Electrical Engineering 1st Edition by Zhixiang Hou 1461421845 9781461421849

https://ebookball.com/product/measuring-technology-andmechatronics-automation-in-electrical-engineering-1st-edition-byzhixiang-hou-1461421845-9781461421849-18346/

Recent Research on Mechanical Engineering Mechatronics and Automation 1st edition by Mehran Shahhosseini 3038351628 9783038351627

https://ebookball.com/product/recent-research-on-mechanicalengineering-mechatronics-and-automation-1st-edition-by-mehranshahhosseini-3038351628-9783038351627-18444/

(Ebook PDF) Mobile Robot Automation in Warehouses 1st edition by Alp Yildirim, Hendrik Reefke, Emel Aktas 3031123077 9783031123078 full chapters https://ebookball.com/product/ebook-pdf-mobile-robot-automationin-warehouses-1st-edition-by-alp-yildirim-hendrik-reefke-emelaktas-3031123077-9783031123078-full-chapters-21928/

(Ebook PDF) Electrical Engineering Materials 1st edition by Basak T. K. 1906574073 9781906574079 full chapters

https://ebookball.com/product/ebook-pdf-electrical-engineeringmaterials-1st-edition-by-basak-t-k-1906574073-9781906574079-fullchapters-22848/

(Ebook PDF) Materials for Biomedical Engineering 1st edition by Alexandru Grumezescu 0081028156 9780081028155 full chapters

https://ebookball.com/product/ebook-pdf-materials-for-biomedicalengineering-1st-edition-by-alexandrugrumezescu-0081028156-9780081028155-full-chapters-22434/

(Ebook PDF) Interdisciplinary Mechatronics Engineering Science and Research Development 1st edition by Maki Habib, Paulo Davim 9781848214187 full chapters https://ebookball.com/product/ebook-pdf-interdisciplinarymechatronics-engineering-science-and-research-development-1stedition-by-maki-habib-paulo-davim-9781848214187-fullchapters-25450/

(Ebook PDF) Sensors and Actuators in Mechatronics Design & Applications 1st edition by Andrzej M Pawlak 1351837524 9781351837521 full chapters https://ebookball.com/product/ebook-pdf-sensors-and-actuators-inmechatronics-design-applications-1st-edition-by-andrzej-mpawlak-1351837524-9781351837521-full-chapters-25460/

Materials, Mechatronics and Automation IV

Edited by Dehuai Zeng

Materials, Mechatronics and Automation IV

Selected, peer reviewed papers from the 2014 4th International Conference on Materials, Mechatronics and Automation (ICMMA 2014), April 10-11, 2014, Singapore

Edited by

Dehuai Zeng

Copyright  2014 Trans Tech Publications Ltd, Switzerland All rights reserved. No part of the contents of this publication may be reproduced or transmitted in any form or by any means without the written permission of the publisher. Trans Tech Publications Ltd Kreuzstrasse 10 CH-8635 Durnten-Zurich Switzerland http://www.ttp.net

Volume 950 of Advanced Materials Research ISSN print 1022-6680 ISSN cd 1022-6680 ISSN web 1662-8985

Full text available online at http://www.scientific.net

Distributed worldwide by

and in the Americas by

Trans Tech Publications Ltd Kreuzstrasse 10 CH-8635 Durnten-Zurich Switzerland

Trans Tech Publications Inc. PO Box 699, May Street Enfield, NH 03748 USA

Fax: +41 (44) 922 10 33 e-mail: sales@ttp.net

Phone: +1 (603) 632-7377 Fax: +1 (603) 632-5611 e-mail: sales-usa@ttp.net

Preface International Conference on Materials, Mechatronics and Automation (ICMMA) is the most comprehensive Conference focuses on the various aspects of advances in Materials, Mechatronics and Automation. Our Conference provides a chance for academic and industry professionals to discuss recent progress in the area of Materials, Mechatronics and Automation. Since 2011, when the first edition of what is now called ICMMA 2011 took place in Melbourne, Australia, participants from several countries who work on materials, mechatronics and automation realized this type of conference should proceed, involving as much as possible, professionals and academics exchanging experience and scientific knowledge in the subject. Nanchang, China (ICMMA 2012) organized the next one and then Singapore hosted the conference this year on April 21‐22.Last year, 2013 International Conference on Materials, Mechatronics and Automation (ICMMA2013) was successfully held on April 21‐22, 2013 in Singapore. This year ICMMA 2014 will be held on April 10‐11, 2014, Singapore. The goal of ICMMA 2014 is to bring together the researchers from academia and industry as well as practitioners to share ideas, problems and solutions relating to the multifaceted aspects of Materials, Mechatronics and Automation. The subjects covered several areas and were gathered into seven chapters for publication: Chapter 1: Materials Science and Materials Processing Technology Chapter 2: Applied Mechanics Chapter 3: Design and Manufacturing Chapter 4: Algorithms and Methodology of Research Chapter 5: Mechanical Engineering and Controls Chapter 6: Information Technology Chapter 7: Management Application Without the reviewing of the manuscripts by those anonymous reviewers, ICMMA 2014 is impossible to be held. Their valuable comments are very helpful for the authors and conference committees. We express our sincere and grateful thanks to all reviewers. Also thanks to other staffs assisting in the various stage of the editorial work, especially the international committees of our conference. Finally, special thanks are due to the authors, reviewers and the international committee for your support. We hope that the contents of this volume will prove useful for researchers in the related fields.

Dehuai Zeng

ICMMA2014 Committee Honorary Chair Yuan Lee, Northestern University, USA General Chairs Jun Zhang, Huazhong University of Science and Technology, China Minli Dai, Suzhou University, China Organizing Chairs Khine Soe Thaung , Maldives College of Higher Education, Maldives Biswanath Vokkarane, Society on Social Implications of Technology and Engineering , Maldives Program Chair Andrew Parvel, Information Engineering Research Institute, USA Dehuai Yang , Huazhong Normal University, China Publication Chair Dehuai Zeng, South China University of Technology, China International Committee Minli Dai, Suzhou University, China Ying Zhang, Wuhan Uniersity, China Zhenghong Wu, East China Normal University Tatsuya Akutsu, ACM NUS Singapore Chapter, Singapore Aijun An, National University of Singapore,Singapore Yuanzhi Wang, Anqing Teachers' University, China Yiyi Zhouzhou,Azerbaijan State Oil Academy,Azerbaijan Khine Soe Thaung , Maldives College of Higher Education, Maldives Biswanath Vokkarane, Society on Social Implications of Technology and Engineering Jessica Zhang, Information Engineering Research Institute, USA David Meng, Information Engineering Research Institute, USA Kath David, Information Engineering Research Institute, USA

Table of Contents Preface and Committee

Chapter 1: Materials Science and Materials Processing Technology Electrospun Porous ZnO Nanofibers for Glucose Biosensors J.Y. Huang, M.G. Zhao and Z.Z. Ye Investigation of the Properties of Al Incorporated into Sb2Te3 Phase Change Material F.F. Wei, T. Kong, L. Shi, R. Huang, J. Zhang and G.S. Cheng Hyaluronic Acid Production by Genetic Modified GRAS Strains X. Fang, R.S. Duan, H.Y. Yang and J.F. Liu Improvement of Inflammability and Biodegradability of Bio-Composites Using Recycled Polypropylene with Kenaf Fiber Containing Mixture Fire Retardant N.S. Suharty, H. Ismail, K. Dihardjo, M. Nizam and M. Firdaus Morphological Study of Bacterial Cellulose (BC)/Polyvinil Alcohol (PVA) Nanocomposite as Bone Scaffold A.Z. Abidin and H.P.R. Graha Extraction of Di-Methyl Phthalate Using Smarta Nanoscavengers N.H. Khdary Preparation and Characterization of Al2O3/PVDF-HFP Based Polymer Electrolyte H. Shi and Q. Zhu Investigation of Au Plated Connector Materials in Corrosion and Sliding Environment Z.G. Kong and Y.G. Kong Preparation of Doped Graphene Quantum Dots with Bright and Excitation-Independent Blue Fluorescence H. Li, H.P. He and Z.Z. Ye The X-Ray Powder Diffraction Patterns and Crystal Structure for Al2M3Y(M=Cu, Ni) D.G. Li, M. Qin, L.Q. Liang, Z. Lu, S.H. Liu, B. He, P.L. Qing and L.M. Zeng X-Ray Powder Diffraction Data for the Al7Cu5Y Ternary Compound B. He, M. Qin, L.Q. Liang, Z. Lu, D.G. Li, C.S. Qin, C.B. Li and L.M. Zeng Effects of Water on the Morphology of Wool Scales F.G. Ning, J. Wang and W.D. Yu

3 7 13 18 24 29 33 38 44 48 53 57

Chapter 2: Applied Mechanics Digital Image Technology – Based Simulation for Internal Components and Mechanical Behavior of Asphalt Concrete B. Hu and X.N. Zhang Design and Kinematic Analysis of a New 3-DOF Hybrid Mechanism Z.Y. Xue, B. Zhang and D.B. Zhang Effects of Ozone Treatment on Wool Morphology and Mechanical Properties J. Wang, F.G. Ning and W.D. Yu A Method for Static Interval Analysis of Uncertain Structures with Interval Parameters J.G. Zhang Reconstruction of Bottom Surface of Shoe Last Based on Foot Pressure Distribution X.N. He and X.Y. Qi Kinematics Analysis on the Throwing Skills of Elite Chinese Male Hammer Athletes S. Wang, J.H. Zhou and C. Jia Kinematics Analysis of Basket with Full Turn to Handstand of Chenglong Zhang on Parallel Bars D.X. Xu, J.H. Zhou and J.P. Kang An Investigated of Single Point Incremental Forming Formability K. Rattanachan and C. Chungchoo

63 69 75 79 86 91 93 96

Materials, Mechatronics and Automation IV

Chapter 3: Design and Manufacturing Design of Experiment for Incremental Forming of Artificial Skull on Titanium Grade 2 N. Sornsuwit and S. Sittisakuljaroen Ergonomic Design and Evaluation of Laparoscopic Instrument Handle Based on Anthropometry C.Y. Sun, S.Y. Wang and B.C. Wang Design of the Gas Flow Integrating Instrument F.G. Zhou, F.Z. Li and L.C. Dai State and Input Observer Design for Nonlinear Impulsive Systems via LMI Approach T. Shao, K. Peng, Z.S. Chen and Y.J. Liu A Design of WSN and EPON Applied in Online Monitoring for Transmission Line X. Chen, Z. Du, X.G. Yin, W. Pan and L.Q. Xu Analysis and Realization of Critical Points on Hardware Design of FPGA C.F. Wu A Novel Surface Reconstruction Method for Noisy Cloud Points Based on Support Vector Machine D.L. Yu A Efficient Surface Reconstruction Method for Noisy Samples Based on Bilateral Filtering and down Sampling W.R. Wan Study of Organic Solar Cells Conversion Efficiency C.L. Zhang The Design and Implementation of Testing System for Network Equipment Configuration Status and Light Power M.B. Liu, G.S. Zhang, H.C. Gao and Q. Li Design Method and Parameters Matching of Electric Motors for Hybrid Construction Equipment F.W. Meng and Y.B. Hu Application of Numerical Simulation and New Fining Index in Operating Parameters Optimization of Float Glass-Melting Furnace Y. Yang, M. Liu and J.H. Hao

103 109 114 119 125 133 139 145 150 155 160 165

Chapter 4: Algorithms and Methodology of Research Does Trade Liberalization Improve the Environment in China? Evidence Form the Dynamic Panel Data of Chinese Prefecture City L.M. Hong A Hierarchical Scheme for Open System Environments Review F.X. Zhang An Energy-Aware Dynamic Algorithm Based on Variable Interval DVFS Technology C. Xu, J. Xiao, L.N. Zeng, Y. Liu and M.M. Peng The Improvement of Passive Location Algorithm Based on Time Sequence Estimation H.W. Bai, Y.W. Wang and Y. Jiang Deducing Stream Function N-S Equation from Classic N-S Equation and its Verification G.X. Yan, W. Wu and S.J. Zhu Applying Upwind Difference and Central Difference to Discrete N-S Equation Described by Stream Function F.H. Wang, G.X. Yan and S.J. Zhu A Mixed Scheduling Algorithm about Hard Periodic and Soft Aperiodic Real-Time Tasks on Heterogeneous Multiprocessor H. Wang, C. Xu, L.N. Zeng and Y. Liu A New Long-Term Forecast Method of Wind Power Y. Lin Matching Pursuit Optimization Based on Quantum Genetic Algorithm L. Chen, L.B. Zheng and S.P. Qin

175 181 185 196 201 205 209 214 221

Advanced Materials Research Vol. 950

Blind Detection of Frequency Hopping Signal Using Numeral Characteristics of Compressive Samplings C.L. Zhang and L.C. Li A Method of Recognition of Human Hand and Body Gestures for Task-Level Learning from Demonstration V. Popov

227 233

Chapter 5: Mechanical Engineering and Controls Study on the Control of Anti-Lock Braking System Simulation Based on Fuzzy PID Control B.Y. Dang Control of 2D Minimally Persistent Formations with the Fault Tolerance of Three CoLeaders in Cycle H. Cao, Q. Qu, X.K. Ying, Y. Liu, Z. Su, T. Ma, H. Li, B.Q. Xu, R.Y. Zhao, Y.L. Liu, Y.J. Zhang and Y. Xing Virtual Experiment Platform of Automatic Control Principle Based on MATLAB/Simscape W.J. Yuan Application of Fuzzy Immune PID Controller Based on Particle Swarm Optimization in Power Plant Steam Temperature Control System F. Hu and W.N. Zhou Smart Control of DC Servo Motor Based on Fussy-PID X.J. Wang, W.M. Xu, Y.Q. Wu and H.Y. Gao Vortex Generators Contribution to the Enhancement of the Aerodynamic Performances H. Tebbiche and M.S. Boutoudj Heavy-Duty Car Multi-Body Dynamics Simulation and Optimization Research M. Cai and L. Gu

239

245 253 257 263 268 275

Chapter 6: Information Technology Multimedia Technology Used to Reduce Costs and Time L.T. Kawamoto Júnior and W.O. Kawamot Validation in a Real Situation of a Virtual Multimedia Training Environment to Improve Performance and Behavior L.T. Kawamoto Júnior and W. Orchulhak Kawamoto Virtual Multimedia Environment to Teach Safety Procedures in Laboratories A. Candiago and L.T. Kawamoto Júnior Recognition of Lanes on Complex Roads Based on Video Image R.B. Chen, W. Hou, Y. Li, X.E. Ye and W.Y. Ma Ultrasonic Tomographic Velocity Field Imaging Based on Interlaced Chord Network J.N. Liu, B.X. Wang, Y.Y. Cui and H.Y. Wang The Study of Chopper in the LVRT of Direct-Drive Wind Energy Generation System J. Jia, X.X. Hu, P.P. Han and Y.P. Hu Manipulator of a Platform Type Robot SHOLKOR K.S. Sholanov Flow Measurement and Control System in the Campus Network Q.X. Zhang and C. Song DCGF in Ji’Nan: Construction and Issues L.Q. Chang, J.H. Li, L.Z. Tian, P. Lin, Y. Wu and W.Z. Zhong The Impact of Music on Learning Brainwaves F.C. Kao, S.P.R. Wang, C.H. Huang, Y.K. Lin and C.C. Chen The Brainwave Concentration Analysis of Direction Recognition F.C. Kao, S.P.R. Wang, C.C. Chen, Y.K. Lin and C.H. Huang

Chapter 7: Management Application

283 288 293 298 306 314 321 327 333 339 345

Materials, Mechatronics and Automation IV

The Research of Loyalty Card Schemes Management in Chinese Food Retail EnterprisesBased on the Experiences of British Retailers W.Y. Du Research on the Value Orientation of Supply Chain Partners' Adverse Selection L. Nie and Z. Qiao Brand Classification Using Distributed Representation T. He and J. Liu Empirical Research on Building Shenzhen into a Regional Logistics Economy Center G. Li

353 356 361 365

CHAPTER 1: Materials Science and Materials Processing Technology

Advanced Materials Research Vol. 950 (2014) pp 3-6 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.950.3

Electrospun Porous ZnO Nanofibers for Glucose Biosensors Jingyun Huanga, Minggang Zhao, Zhizhen Ye Department of Materials Science and Engineering, State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou 310027, China Email: huangjy@zju.edu.cn Keywords: ZnO; Electrospinning; Porous; Biosensor; Glucose

Abstract. Porous 1 dimensional (1D) ZnO nanofibers were synthesized by electrospinning technology and sequent annealing process. The ZnO nanofibers have many nanopores in it and connect to each other to form a porous film. The diameters of the nanofibers are about 100 nm, and their lengths are so long as tens of millimeters. Owing to the porous nanofibers based matrix has 1D channels and high isoelectric point, the prepared ZnO porous film is wonderful platform to immobilize glucose oxidase enzyme for glucose biosensing. The as-fabricated biosensor exhibited high sensitivity (69 µA/mMcm-2), fast response (3 s) and low detection limit (10 µM), due to the nanomaterial with large surface-to-volume ratio for enzyme immobilization and excellent electrical properties. The biosensors can be fabricated controllably and repeatedly. These excellent results indicate the biosensors are attractive for application. Introduction Glucose is a fundamental carbohydrate in biology. When glucose levels in the bloodstream are not properly regulated, diseases such as diabetes can develop [1]. It is well known that the number of diabetes patients increases rapidly all over the world, so monitoring glucose concentration is necessary and important. Many researches have focused on developing strategies for accurate determination of glucose concentration. The most popular glucose sensors are the electrochemical enzymatic biosensors, which have been widely investigated and developed in the field of clinical detection, biological analysis, environmental monitoring, and food processing industries [2-4]. The effective immobilization of enzymes onto the electrode is a crucial factor for fabricating biosensors [5]. Porous nanomaterials that can afford large specofic surface and suitable morphology have attracted wide attention in fabricating enzymatic biosensors. ZnO is a versatile semiconductor material with direct band gap (3.37 eV) and large exciton binding energy (60 meV), which has wide applications such as optics, optoelectronics, sensors and actuators [6]. ZnO has biocompatible properties and excellent electrical and optical properties. In particular, it has high isoelectric point (IEP ~ 9.5) tht makes it suitable for absorptiing proteins with low IEPs, such as glucose oxidase (GOx) (IEP ~ 4.5), by electrostatic interactions with high binding stability [7-9]. In addition, ZnO is inexpensive and can be easily prapared into various nanostructures. Therefore, ZnO is promissing in fabricating biosensors. In this work, we report the synthesis of porous ZnO nanofibers by electrospinning technology. The porous nanofibers connected to each other to construct a porous film, which was used as matrix to immobilize GOx enzyme. High loading and long term stability were achieved, and the biosensor showed high sensitivity and fast response to glucose. Experimental section The ZnO nanofibers were prepared by electrospinning and and annealing. The polyvinyl alcohol (PVA) sol solution with the concentration of 9 wt% was prepared first. Then zinc acetate (2.5 g) was added into 35 ml as-prepared PVA sol solution with stirring. During the time, the solution was heated and suitable amount of alcohol was added into the solution drop by drop. Finally, the prepared viscous precursor sol solution was used for electrospinning. The obtained composite nanofibers were annealed at 650 oC for 1.5 h in air and porous ZnO nanofibers were finally got. The

Materials, Mechatronics and Automation IV

construction of the electrode is shown in Figure 1. The ZnO nanofibers were deposited on one end of the Au film coating on SiO2 chip and the middle area of the chip was encapsulated in polymethyl methacrylate. The GOx enzymes were successfully immobilized in the porous ZnO nanoﬁbers by electrostatic adsorption interaction and CHIT-assisted cross-linking technique [10,11]. Three electrodes system was adopted for measurement. The as-prepared GOx enzymes modiﬁed electrode was used as working electrode, a Pt electrode as counter electrode, and an Ag/AgCl electrode as reference electrode. All the experiments were carried out in 0.01 M phosphate buffer saline (PBS, PH = 7.4) at room temperature Results and discussion

Fig.1 Schematic illustration of the GOx enzyme modified glucose biosensor The scanning electron microscopy (SEM) images of ZnO nanofibers are shown in Fig. 2. A low-magniﬁcation image is shown in Fig. 2a, it is observed that the whole morphology is a porous film consisting of nanofibers distributed in disorder. The nanofibers with the length about tens of micrometers connect to each other to form an integrated film. All the nanofibers have the similar diameter. Fig. 2b shows the high-magniﬁcation image of a single ZnO nanofiber, the diameter of the nanofiber is about 100 nm and many pores (about tens of nanometers) distribute in it. It is known that the diameter of GOx enzyme molecule is less than 20 nm, so they can be adsorbed into the pores. That means the GOx enzymes can not only be immobilized on the surface of the nanofiber, but also into it. As a result, high loading can be achieved. Furthermore, the porous environment can enhance the stability of the device.

Fig.2 The SEM images of prepared porous ZnO nanofibers

Advanced Materials Research Vol. 950

Fig. 3a shows the typical current–time response curve for successive addition of 0.4 mM glucose step by step under stirring. It can be seen that the biosensor shows rapid and sensitive amperometric response to the added glucose. The current increases as the addition of glucose and rapidly reaches to the steady-state within 3 s. The result indicates that the prepared biosenor can be used to detect glucose. The electrode has well catalytic ability toward the reduction of glucose, which means that the GOx enzymes were effectively immobilized and had well bioactivity. From Fig. 3b, it is observed that the linear detection range is from 1×10-5 M - 3.2 ×10-3 M. The sensitivity is caculated as 69 µA/mMcm-2, which is much higher than many previous reports [12-14].

Fig.3 Real time electronic response of biosensor to glucose. The applied voltage is 700 mV. (a) Typical current–time response curve for successive addition of glucose with a step of 0.4 mM under stirring. (b) The calibration curve of the glucose concentration versus current. Selectivity is an important analytical factor for a biosensor. We use uric acid, ascorbic acid and dopamine for interference test. It is found that the presence of the potential interferent causes no substantial change toward the response signal. It indicates the biosensor has well selectivity toward glucose detection. The long term stability was investigated after one month storage at 4 oC, and almost 85% of its initial value was remained. The high stability can be attributed to the pores in the nanofibers, which provide porous microenvironment for holding GOx and retaining their activity. Conclusion In summary, porous ZnO nanofibers were prepared by electrospinning and annealing. The nanofibers connected to each other to form a porous film, which was successfully used as matrix for immobilizing GOx enzyme for glucose biosensor. The nanopores on the nanofibers can provide porous microenvironment for holding GOx and retaining their activity. The prepared biosensor showed high sensitivity, fast response, well selectivity and high stability to glucose. It is an attractive material for fabricating enzymatic biosensors. Acknowledgments This work was partly supported by the National Natural Science Foundation of China and the Doctorate Fund of the Ministry of Education. References [1] B. Fanga, C. Zhang, G.Wang, M. Wang, Y. Ji, Sens. Actuators B, Vol. 155 (2011), p. 304. [2] N.A. Rakow, K.S. Suslick, Nature, Vol. 406 (2000), p. 710. [3] R.W. Keay, C.J. McNeil, Biosens. Bioelectron., Vol. 13 (1998), p. 963. [4] Y.M. Sung, K. Noh,W.C. Kwak, T.G. Kim, Sens. Actuators B, Vol. 161 (2012), p. 453. [5] F. Li, Z. Wang, W. Chen, S.S. Zhang, Biosens. Bioelectron., Vol. 24 (2009), p. 3030.

Materials, Mechatronics and Automation IV

[6] M. Zhao, Z.g Li, Z Han, K. Wang, Y. Zhou, J. Huang, Z. Ye, Biosen. Bioelectron., Vol. 49 (2013), p. 318. [7] E. Topoglidis, E. Palomares, Y. Astuti, A. Green, C.J. Campbell, J.R. Durrant, Elec. Anal., Vol. 17 (2005), p. 1035. [8] S.M. Usman Ali, O. Nur., M. Willander, B. Danielsson, IEEE Tran. Nanotech., Vol. 8 (2009), p. 678. [9] Z.J. Wang, Y.H. Yang, J.S. Li, J.L. Gong, G.L. Shen, R.Q. Yu, Talanta, Vol. 69 (2006), p. 686. [10]A. Wei, X.W. Sun, J.X. Wang, Y. Lei, X.P. Cai, C.M. Li, Z.L. Dong, W. Huang, Appl. Phys. Lett., Vol. 89 (2006), p. 123902. [11]Q. Xu, C. Mao, N.N. Liu, J.J. Zhu, J. Sheng, Biosen. Bioelectron., Vol. 22 (2006), p.768. [12]Y. Lei, X. Yan, N. Luo, Y. Song, Y. Zhang, Colloids Surf. A:Physicochem. Eng. Aspects, Vol. 361 (2010), p. 169. [13]Z.W. Zhao, X.J. Chen, B.K. Tay, J.S. Chen, Z.J. Han, K.A. Khor, Biosens. Bioelectron. Vol. 23 (2007), p. 135. [14]A. Umar, M.M. Rahman, S.H. Kim, Y.B. Hahn, J. Nanosci. Nanotechnol. Vol. 8 (2008), p. 3216.

Advanced Materials Research Vol. 950 (2014) pp 7-12 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.950.7

Investigation of the Properties of Al Incorporated into Sb2Te3 Phase Change Material Fenfen Wei1, 2 a, Tao Kong1 b, Lin Shi1 c, Rong Huang1, 2 d, Jie Zhang 1, 2 e, Guosheng Cheng1, f* 1

Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, 398 Ruoshui Road, Suzhou Industrial Park, Jiangsu 215123, China 2

University of Chinese Academy of Sciences, No. 19A Yuquan Road, Beijing 100049, China a

ffwei2011@ sinano.ac.cn, btkong2009@sinano.ac.cn, clshi2007@sinano.ac.cn, rhuang2009@sinano.ac.cn, e jzhang2011@sinano.ac.cn, f gscheng2006@sinano.ac.cn.

Keywords: Phase change; Chalcogenide material; Crystallization; Electrical properties

Abstract. We report that crystallization property of amorphous Sb2Te3 can be significantly improved via Al doping. However, the effect of Al on the structure and electrical properties of crystalline Sb2Te3 is not clear, which is valuable for phase change memory. In this work, we find that Al addition could increase the crystallization temperature and change the structure. The results show that both nucleation and growth of crystallite are suppressed by Al doping. Based on ab initio calculation, we have validated the formations of Al-Sb and Al-Te bonds in doped films and the effect of Al on the structure and properties of crystalline Sb2Te3. Especially for 10 at% Al doped Sb2Te3 (Al-Sb-Te) film, which exhibits better thermal stability and might be a good candidate material for phase change memory. Introduction Phase transitions constitute a vast and important field of solid-state physics from both academic and industrial viewpoints. As a well known prototype phase change material (PCM), antimony telluride (Sb2Te3) is the basic ingredient of pseudo-binary compound of GeTe-Sb2Te3 alloys, which are commercially used in rewritable optical memory (CD, DVD) and electronic non-volatile memory (NVM) technology. [1, 2] These materials are reported to show rapid and reversible transitions between the crystalline and amorphous state by an application of intense laser or electric pulse. Although the phase change phenomenon has been found by Ovshinsky about four decades ago, the mechanism is still under debate. The device properties of PCM depend mainly on phase change behaviors of the embedded chalcogenide materials, such as Ge-Sb-Te (GST) alloys, have been widely studied. [3] However, GST-based materials have high RESET currents, relatively slow amorphous-to-crystalline transition speeds and low thermal stability in the amorphous. [4] In contrast, Sb2Te3 materials have many advantages such as high crystallization speed and fast-growth. [5,6] However, it is difficult to meet the requirement of data-retention time above 80 ℃ due to its relatively low crystallization temperature. [7] One method is to dope the Sb2Te3 materials with other elements. So far, dopants of Zn, Ge, In, N and Ag have been studied; [8-12] and they can significantly improve the crystallization property of amorphous Sb2Te3. Nevertheless, the effect of crystallization and the local chemical state of the Sb2Te3 have not been studied in detail, which are essential to understanding the performance of phase change materials. In this paper, by on ab initio calculation, we studied the structure and chemical bonding of Al-Sb-Te, in which Al is assumed to occupy Sb or Te sites. The results show that structural and electronic changes induced by Al doping. What is more, Al atoms bonded to Sb and Te atoms to suppress the phase transformation from amorphous to crystalline states. The present results play a key role on comprehensive understanding of crystalline Al-Sb-Te related phase change materials and are good for the practical application.Experimental Details

Materials, Mechatronics and Automation IV

Al-Sb-Te films (100 nm) were fabricated on SiO2 substrates by co-sputtering method using Al and Sb2Te3 targets at room temperature. The sputtering power of Sb2Te3 target was fixed at 50W, while the sputtering powers of Al target were controlled at 0, 30, 40 and 45 W. The background pressure before sputtering and Ar gas pressure during sputtering were 5.0×10-5 Pa and 3 mTorr, respectively. The chemical compositions of various Al-Sb-Te films were determined by means of energy dispersive spectroscopy (EDS). The as-deposited Al-Sb-Te films were then annealed for 5 min in a rapid thermal processor at 350 ºC. The structure of as-deposited and annealed Sb2Te3 and Al-Sb-Te thin films was examined by X-ray diffraction (XRD) and Raman spectra. To understand the chemical bonding states of the Al-Sb-Te film, we have performed x-ray photoelectron spectroscopy (XPS) measurements. In order to exclude the influence of the oxidation of the film surface, XPS was performed after Ar+ ion etching (4 kV) for 1min.Results and discussion

Fig.1 The XRD patterns of Al-Sb-Te samples with different concentrations of Al,(a) for as-deposited and (b) for annealed samples. The XRD peak (110) observed from Fig. 1(a) indicates that the as-deposited Sb2Te3 ﬁlm crystallized during sputtering at room temperature, which well agrees with low crystallization temperature of Sb2Te3 ﬁlm. [7] With the increase of Al concentration varing from 0 to 10 at %, the intensity of Sb2Te3 peak decreased. In Fig. 1 (b), all the XRD peaks of the annealed samples accord with a Sb2Te3 rhombohedral phase, and no Al peak presented which indicates Al has been doped effectively. In comparison to Sb2Te3 film, the diffraction peaks of Al-Sb-Te have a decrease in the intensity and an increase in the width. Furthermore, some peaks have a shift to smaller diffraction angle implying lattice parameters variation, and even disappear. The broad diffraction peaks imply that the crystalline process of Sb2Te3 is inhibited remarkably by incorporating Al. The crystal lattice of Sb2Te3 consists of repeated groups of atomic layers along c axis, Te-Sb-Te-Sb-Te, with van der Waals bonding connecting two repeated groups. Impurity atoms can be incorporated into the Sb2Te3 crystal lattice by substituting for Sb or Te, by occupying interstitial lattice sites, or possibly by entering the van der Waals gaps. It can be deduced from the fact that the lattice strain decreases as the Al content increases that some Al atoms go into Sb/Te lattice sites by substituting for Sb or Te rather than by the other two possibilities and that the Al-Sb and Al-Te contents may exist as microcrystalline grains around the crystalline Sb2Te3 grains. These microcrystalline grains serve as centers for suppression of the amorphous-to-rhombohedral phase transition, consequently improving the system stability.

Fig.2 Raman scattering spectra of (a) as-deposited undoped and Al-Sb-Te, (b) 350 ℃-annealed undoped and Al-Sb-Te film.

Advanced Materials Research Vol. 950

Raman spectra also provide important information about phase transformation. Fig. 2(a) and (b) show the Raman spectra of the as-deposited and 350°C-annealed un-doped and Al-Sb-Te films, respectively. We have carefully used appropriate measurement parameters to avoid any structural modification of the Sb2Te3 layers by the laser beam, and achieved the spectra with good signal-to-noise ratio. Basically, the Raman spectra consist of these features: (1) with Al concentration in as-deposited Sb2Te3 films increasing, peak A at ~70 cm−1 remains almost unchanged while peak B at ~110 cm−1 and peak C at ~160 cm−1 gradually disappear and a new sharp peak D at ~140 cm−1 appears, as shown in Fig. 2 (a). The relatively broad peak is attributed to disorder present in the amorphous films. Differently, the peak B locates at ～110 cm-1 and peak C locates at ～160 cm-1 in Raman spectra of un-doped Sb2Te3 films, while the Raman spectra of the 10% Al-Sb-Te film features a broader peak D at ～140 cm-1. All Al-Sb-Te films exhibit similar Raman spectra in terms of peak position. However, two broad peaks overlap with each other in the region 90-180 cm−1 with increasing Al content, suggesting that the addition of Al leads to a higher degree of disorder in the amorphous phase of the material. In fact, this is in agreement with the high crystallization temperature of the Al-Sb-Te film. In fact, the higher the disorder level of the Al-Sb-Te amorphous state, the higher the energy required to arrange it in an ordered crystalline form. [13] (2) For the films annealed at 350°C, obviously, with the increase of the annealing temperature to 350°C, the broad band is divided into three different sharp peaks, which is marked as A, B&C in Figs. 2(b). The peak B is located at ～ 112 cm-1 associated with the E2g mode and kept almost unchanged with the increase of Al doping, while peak A downshifts from ～70 to ～66 cm-1 and peak C downshifts from ～167 to ～165 cm-1 in 10% Al-Sb-Te film compared with pure Sb2Te3 films, implying a significant change in the local bonding arrangement around Sb and Te atoms has occurred in the Sb2Te3 film but the phenomenon can be restrained by Al addition due to the suppression of phase transformation from fcc to hex. On the other hand, although there is a change in the intensity of peak B at 110 cm−1 in Fig. 2 (b), its position seems not to be significantly influenced by the crystallization process, which is in good agreement with the general consensus about unchanged local arrangement of atoms around Te and Sb on crystallization. [14] In order to collect additional support, Raman spectra for annealed films were obtained, as shown in Fig. 2(b). During crystallization process, then dangling bonds and defects in the amorphous films are gradually annealed out, and a great fraction of saturated bonds are produced with the formation of Al-Sb and Al-Te bonds. The most important finding is that the intensity of the three peaks is suppressed in 10% Al-Sb-Te films compared with pure Sb2Te3 films. It reveals that the disorder level of the crystalline films is increased with high Al content. The results also correspond to the results of XRD, since the XRD peak intensities are decreased with more Al-doping concentration. We argue that these characterizations reveal that the structure of the film can be stabilized with proper Al doping.

Fig.3 Sb 3d and Te 3d XPS spectra of as-deposited amorphous and crystallized Sb2Te3: 10 at%Al samples.

Materials, Mechatronics and Automation IV

Further insight into the chemical bonding state of elements, we have performed XPS measurements. Fig. 3 shows the XPS spectra of the as-deposited film, and annealed films. For Sb2Te3, there is no significant difference upon crystallization in the spectra, which means there were only small changes in the atomic position and the bonding state. However, the 3d level of Sb and Te spectra exhibit a pronounced different between the amorphous and crystalline phases. As the figure shows, the Sb 3d and Te 3d peak positions tend to shift to lower binding energy even in an amorphous state. After the annealing treatment, the peak position is shifted to a lower binding energy than that of the Sb2Te3 film, indicating that the chemical states of Sb and Te in the Al-Sb-Te films are significantly affected by the incorporation of Al during the deposition and annealing processes. In the film annealed at 350 °C, the peak position shifts toward a low binding energy by 0.43 eV, compared to that of the as-grown film, which can be concluded that Al-Sb and Al-Te exists in the Al-Sb-Te films. Simultaneously, the more Al atoms doped, the larger the binding energy decreases. Besides, we noted that the binding energy of Sb-Te decreases after Al incorporation, which implies weaker Sb-Te bonding. As shown in the XRD data of Fig. 1. As a result, the XPS data provide strong support for the generation of a new crystalline phase owing to the difference in bonding energy.

Fig. 4 Structures of Al-Sb-Te alloys in conventional hexagonal supercell. Initial configuration of (a) Sb2Te3; (b) Sb2Te3 with Sb sites for 6 Al atom; (c) Sb2Te3 with Te sites for 6 Al atom Sb2Te3 crystallizes in a five-layer structure (Te1-Sb-Te2-Sb-Te1) within the D3d5 (R-3m) space group. The rhombohedral is set for the unit cell, the pure material has three inequivalent atoms per cell and five atoms in total. Therefore, this structure is referred to as the primitive unit cell. According to the hexagonal setting corresponds to the conventional unit cell, we will refer to it as 1×1×1. Pictorial representations of the pure crystal structure and the first Brillouin zone can be found in Ref. [15]. We used different kinds of super-cells in order to allow for several concentrations of doping. In this work, we used 2×2×1 super-cells for the investigated structures as shown in FIG. 4. The supercell of 60 atoms was constructed, with Al concentration of 10%.

Fig. 5 The partial density of states for Te2 (a) Sb2Te3; (b) Al substituted for Sb atoms; (c) Al substituted for Te1 atoms. The Fermi level was set to 0 eV.

Advanced Materials Research Vol. 950

A deeper understanding on the chemical bonding character of Al-Sb-Te can be gained by partial density of states (PDOS). Ab initio calculations were fulfilled based on the established crystal model using density functional theory (DFT) by using Vienna ab initio simulation package (VASP). [16] The Projector Augmented Wave (PAW) pseudopotentials with the generalized-gradient approximations (GGA) were used. [17, 18] Herein, a 60-atom super-cell was used for rhombohedral Sb2Te3, with Al concentration of 0% and 10%. The valence electron configurations for Sb, Te, and Al were 5s25p3, 5s25p4, and 3s23p2, respectively. The electron density distributions of the most stable Al-Sb-Te configurations were calculated. The PDOS of Te2 Atoms was shown in Figure 5 as a representative. Fig. 5(a-c) showed the PDOS of Sb2Te3 and Al-Sb-Te films, from which one can see that the lower lying energy states are dominated by the s states, while the valence states are predominated by the p states. It is clear that the covalent bonds of Sb-Te and Al-Sb in Al-Sb-Te films are mainly p-p bonding. Compared with ideal rhombohedral Sb2Te3, the peak indensity of s and p states are reduced by Al doping, when Te is substituted by Al, the content of Sb-Te decreased, a new covalent bond Al-Sb formed, consistent with the results of the XRD and XPS. It can be induced that as the Al doping concentration increases, the electron localization of Te gradually weakened and the electrons are more evenly distributed in the energy range. As the Al doping concentration increases, the binding energy of Al-Sb-Te films decreases. Meanwhile, the electro-negativity of Al (1.61) is smaller than that of Te (2.1), the bonds which Sb forms with Al in Al-Sb-Te films are quite different with those formed with Te in Sb2Te3. On the other hand, as the Al doping concentration increasing, the Fermi level moves downward with respect to the top of valence band, showing the increase in empty shallow states. Similar behaviors can be observed in Fig. 5(c). We have identified that Al substituted the Sb sites. As the Al doping concentration increases, the binding energy of Al-Sb-Te films decreases. Besides, it is equivalent to substitution, so the Fermi level changes slightly when Al substituted the Sb sites. After Al doping, the degree of overlap decreases for the electron cloud between Sb and Te atoms, to weaken the interaction energy of the doping system, which indicates the weakening of the Sb-Te bonding. As a result, it is benefit to improve the system's electrical performance when Al elements replace of Te and atoms in Sb2Te3 crystal phase. Summary In summary, through XRD, Raman spectra, and XPS measurements, we demonstrated that the phase transition of Sb2Te3 film from fcc to hex structure was suppressed by Al implantation. XRD results show that the amorphous/crystalline ratio is also enhanced by Al dopant. Raman spectra also provide important information relative to phase transformation which is in well agreement with XRD data. Al atoms are found to significantly increase crystallization temperature of Al-Sb-Te films. At the same time, XPS analysis reveals the existence of Al-Te and Al-Sb bonding, which is useful for phase-change memory application. Acknowledgments This work was partially funded by the International Science and Technology Corporation Program from the Ministry of Science and Technology of China (MOST) under award number 2010DFB53890, National Natural Science Foundation of China (Grant numbers: 11104317 and 10834004) and Suzhou Science and Technology Program (SYG201332). We are grateful for the professional services of Platforms of Characterization & Test and Nanofabrication Facility at Suzhou Institute of Nano-Tech and Nano-Bionics, Chinese Academy of Sciences and and Supercomputing Center, CNIC, CAS.

Materials, Mechatronics and Automation IV

References [1] M. Wuttig and N. Yamada, Nature Mater. 6, 824 (2007). [2] H. S. P. Wong, S. Raoux, S. Kim, J. L. Liang, J. P. Reifenberg, B. Rajendran, M. Asheghi, and K. E. Goodson, Proc. IEEE 98, 2201 (2010). [3] M. Chen, K. A. Rubin, R. W. Barton, Appl. Phys. Lett. 49, 502 (1986). [4] Y. Lu, S. Song, Y. Gong, Z. Song, F. Rao, L. Wu, B. Liu, and D. Yao, Appl. Phys. Lett. 99, 243111 (2011). [5] H. R. Martijn, M. Lankhorst, L. Pieterson, M. Schijndel, B. Jacobs, and J. Rijpers, Jpn. J. Appl. Phys. 42, 863 (2003). [6] B. Liu, Z. Song, S. Feng, and B. Chen, Microelectron. Eng. 82,168 (2005). [7] N. Yamada, E. Ohno, K. Nishiuchi, N. Akahira, and M. Takao, J. Appl. Phys. 69 (5), 2849 (1991). [8] X. Shen, G. X. Wang, R. P. Wang, S. X. Dai, L. C. Wu, Y. M. Chen, T. F. Xu, and Q. H. Nie, Appl. Phys. Lett. 102, 131902 (2013). [9] Z. Wu, G. Zhang, Y. Park, S. D. Kang, H. K. Lyeo, D. S. Jeong, J. H. Jeong, K. No, and B. K. Cheong, Appl. Phys. Lett. 99, 143505 (2011). [10] M. H. Jang, S. J. Park, D. H. Lim, S. J. Park, M. H. Cho, D. H. Ko, M. Y. Heo, H. C. Sohn, and S. O. Kim, Appl. Phys. Lett. 96, 052112 (2010). [11] Y. Yin, H. Sone, and S. Hosaka, J. Appl. Phys. 102, 064503 (2007). [12] H. J. Wu and S. W. Chen, J. Alloy. Compd. 509, 656 (2011). [13] G. B. Beneventi, L. Perniola, V. Sousa, E. Gourvest, S. Maitrejean and J. C. Bastien, Solid State Electron. 197, 65 (2011). [14] A. V. Kolobov, P. Fons, A. I. Frenkel, A. L. Ankudinov, J. Tominaga and T. Uruga, Nature. Mater. 3 703(2004). [15] S. K. Mishra, S. Satpathy, and O. Jepsen, J. Phys.: Condens. Matter. 9, 461(1997). [16] J. Hafner, J. Comput. Chem. 29, 2044 (2008). [17] J. P. Perdew and Y. Wang, Phys. Rev. B. 46, 12947 (1992). [18] J. P. Perdew, K. Burke, and M. Ernzerhof, Phys. Rev. Lett. 77, 3865 (1996).

Advanced Materials Research Vol. 950 (2014) pp 13-17 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.950.13

Hyaluronic Acid Production by Genetic Modified GRAS Strains Xiao Fang a, Rongshuai Duan b, Haiying Yang c, Jingfeng Liu d Shandong Institute of Commerce and Technology, Jinan, China a

fx410@163.com, brsduan@yeah.net, cyanghaiying0814@163.com, d376023858@qq.com

Keywords: Hyaluronic acid; GRAS; Hyaluronansynthase

Abstract. Hyaluronic acid is an important polysaccharide of various physiological functions. Nowadays, it is produced mainly through microbial fermentation of Streptococcus zooepidemicus. HA production in more safe and efficient genetic modified GRAS strains is a hot research area. Bacillus subtilis, Lactococcus lactis, Streptococcus thermophiles, Agrobacterium sp. , and some Escherichia coli strains, which were GRAS strains, had been selected for genetic engineering to express hyaluronic acid. Here, we provide a comprehensive review of HA production by these genetic modified GRAS strains. Introduction Hyaluronic acid (HA) is a widely distributed macromolecular in vivo, which belongs to the family of glycosaminoglycan. It has unique advantages as a biomaterial because of its good viscoelasticity, plasticity, permeability and biocompatibility. HA plays an important physiological role in water retention, lubrication, and adjusting osmotic pressure, as well as in the signal recognition and conduction. Therefore, HA has a wide range of applications in pharmaceutical, food, and cosmetics industry and the commercial market of HA is great around the world. Currently, microbial fermentation method has replaced the traditional animal tissue extraction method to be the main method of HA production. The large-scale microbial fermentation of HA is mainly through fermentation of Streptococcus zooepidemicus, which has its limitations. S. zooepidemicus is an opportunistic pathogen to human and HA production from S. zooepidemicus fermentation is of safety concern. Thus fermentation of HA by genetically modified GRAS (generally recognized as safe) strains is of great interest. Current situation of industrial microbial fermentation of HA Since the 1980s, HA industrial production has been mainly carried out using microbial fermentation and the main fermentation strains were group A or C streptococci, especially S. zooepidemicus. After about 30 years research, HA fermentation by S. zooepidemicus has been a robust and high-yield fermentation model. With wild-type or high HA-producing mutant strain as fermentation strain, it was easy to obtain a high yield of HA (5 ~ 10 g/L). Higher concentration of HA in fermentation was not practical because of the broth viscosity limitations. Therefore, the aim of microbial breeding of Streptococcus zooepidemicus and optimizing of HA fermentation was focused on the quality of HA, such as purity or molecular weight distribution, rather than the HA yield [1]. Improvements in Streptococcal HA fermentations include: Available non-hemolytic and hyaluronidase deficient mutants. A high molecular weight HA-producing Streptococcus equi mutant was derived by the serial selection after NTG treatment, which had nonhemolytic, hyaluronidase-negative, kanamycin-resistant, and highly viscous characteristics. With this strain in a 100 L fermenter, HA with a molecular weight of 3.2 × 106 was accumulated at a concentration of 6 ~ 7 g /L [2]. Effective control of HA molecular weight. Chen et al. [3] reported that HA molecular weight was controlled by UDP-N-acetylglucosamine concentration. High molecular weight could be achieved through regulation of metabolic pathways to an appropriate balance of UDP-N-acetylglucosamine

Materials, Mechatronics and Automation IV

and UDP-glucuronic acid. Adjusting fermentation parameters could also be used to control the molecular weight, especially for low molecular weight [4]. Improved fermentation techniques. Broth compositions [1], fermentation patterns such as continuous culture [5], and other parameters such as ventilation, pH control [6-8] had been optimized. While the aforementioned improvements might to some extent improve the quality of HA, it was difficult to overcome the underlying problem that S. zooepidemicus itself was an animal pathogen which brought safety risks. Limited genetic manipulation methods of S. zooepidemicus brought disadvantages as well. Advances in HA fermentation by GRAS strains HA synthases were found in a variety of microorganisms [9] and the biosynthetic pathway of HA had been clarified in some bacteria (Fig. 1) [1-2]. With these findings and the growing public demand of GRAS HA products, efforts were made to the genetic modification of GRAS strains to produce HA.

Fig.1 The biosynthetic pathway of HA in Streptococcus Microbial HA synthase consisted of two groups, i.e. HASs which were produced by a variety of gram-positive A/C streptococci and pmHAS which was produced by gram-negative type A Pasteurella multocida [9]. Accordingly, based on the transferred HA synthase, HA recombinant expression systems could be divided into two categories, namely the use of HASs of Gram-positive bacteria including Bacillus subtilis [10-12] and Lactococcus lactis [13-15], and the use of pmHAS of Gram-negative bacteria Agrobacterium sp. [16]. Gram-negative Escherichia coli was rather special, both HASs and pmHAS had been experimentally transferred [17-18]. In addition, Izawa et al. [19] reported that some of the Gram-positive Streptococcus thermophilus could produce HA as well. B. subtilis, L. lactis, and S. thermophilus belonged to the family of GRAS strains. Agrobacterium was used extensively for the fermentation of curdlan as food additives. Some E. coli strains such as

Advanced Materials Research Vol. 950

K12 were regarded as safe by experts too. Therefore, the use of these strains to produce medical or edible HA might be more easily accepted by the general public as safe. Bacillus subtilis. B. subtilis had a strong ability to synthesize and secrete extracellular products. B. subtilis could be easily cultured with low cost broth and did not produce endotoxins and exotoxins, and had no hyaluronidase. In addition, B. subtilis genome sequencing had been completed, and the gene manipulation tools were relatively abundant. These advantages made B. subtilis to be an ideal HA exogenous expression system. [10, 12] B. subtilis lacked only HA synthase, so theoretically B. subtilis could synthesize HA with just streptococcal hyaluronan synthase gene imported. However, Widner et al. [12] showed that the synthesis of UDP-glucuronic acid limited the synthesis of HA in B. subtilis, and therefore it was needed that UDP-glucose dehydrogenase gene hasB or endogenous tauD should be incorporated in the same operon. Fermented with the genetically modified B. subtilis, the HA yield could reach the level of a few grams per liter, with the molecular weight between 1.1 ~ 1.2MDa, polydispersity factor about 1.5. Chien et al. reported that the Vitreoscilla hemoglobin gene (VHb) could be introduced into B. subtilis to improve its oxygen transportation and the ATP production. With VHb, hasA and tauD imported, cell density of B. subtilis increased 25% and the HA yield doubled [11]. Furthermore, HA secreted by B. subtilis did not tightly adhere to the cells and thus simplified the downstream purification process [12]. Lactococcus lactis. L. lactis was evolutionary closely related to S. zooepidemicus and its genetic backgrounds were clear from a safety aspect. Furthermore, some mature and efficient inducible expression systems, such as NICE expression system (Nisin-controlled expression system) were available for L. lactis. Chien reported that with NICE Systems, the HA synthase gene hasA and UDP-glucose dehydrogenase gene hasB were imported into L. lactis. Addition of nisin could induce the HA synthesis and the HA concentration was up to 0.65 g/L. [13]. Prasad et al. [14] found that when hasA, hasB and UDP-glucose pyrophosphorylase gene hasC were jointly introduced into L. lactis, the HA yield could be further improved to 1.8 g/L. With NICE inducible expression system, the regulation mechanism of HA could be studied. Sheng et al. [15] investigated the relations among the expression of HA synthase, HA yield and HA molecular weight. By adjusting the concentration of nisin, HA with molecular weight of 550 ~ 850 kDa could be obtained, suggesting a controlled fermentation model to produce targeted molecular weight [15]. Streptococcus thermophiles. Izawa et al. [19] studied extracellular polysaccharide produced by S. thermophilus in dairy foods and found a strain of S. thermophilus YIT 2084 could synthesize HA (about 8 mg/L). The high molecular weight portion (approximately 2,000 kDa) of its extracellular polysaccharide showed similar composition to the commercial HA, confirmed by HPLC and NMR analysis. Due to the endogenous synthesis of HA and itself as a GRAS strain, S. thermophilus YIT 2084 showed potential applications in the medical and food grade HA production and its fermentation parameters needed further optimization. Agrobacterium sp. Agrobacterium sp. ATCC 31749 was commonly used in industrial fermentation of a food polymer, curdlan. Agrobacterium sp. was Gram-negative, so Mao et al. [16] studied transgenetic expression of pmHAS in it. The UDP-glucose dehydrogenase gene kfiD from E. coli K5 and pmHAS gene from P. multocida were transferred into Agrobacterium sp. In shaking flask cultures, the HA yield could accumulate to 0.3 g/L, with the molecular weight between 0.7 ~ 2 MDa. Furthermore, the versatile Agrobacterium genetic tools made it easier for further genetic modification. [16] Escherichia coli. The most abundant genetic tools of E. coli made it an ideal host bacteria for the study of HA biosynthetic pathway. Yu et al. [18] studied the relations among the expression of streptococcal hyaluronan synthase gene sphasA, E. coli gene ugd (hasB), galF (hasC), glmU (hasD) and HA synthesis. They found that sphasA, ugd, and galF were essential for the HA synthesis. However, the HA yield was not high (160 ~ 190 mg/L) due to the differences between Gram-negative and Gram-positive bacteria. The molecular weight of HA obtained was 3.5 x 105 ~ 1.9 x 106 Da. HA synthesis also inhibited E. coli cell growth. Mao et al. [17] adopted the opposite strategy, they

Materials, Mechatronics and Automation IV

introduced Gram-negative P. multocida pmHAS gene into E. coli, together with UDP-glucose dehydrogenase gene from E. coli K5. When using a fed-batch fermentation model, the HA production could reach 2.0 ~ 3.8 g/L. Conclusion HA fermentation with S. zooepidemicus had risks of toxins and other cellular protein contaminants. Furthermore, HA fermentation with S. zooepidemicus had disadvantages such as low fermentation ability and high cost broth. Meanwhile, with the public's increasing concern of the safety of medical or food materials, HA fermentation with S. zooepidemicus might be restricted in future. HA fermentation with GRAS bacteria instead would be preferred. Studies on GRAS strains expressing HA had facilitated the understanding of the structure of HA synthase, initiating, extension and termination of HA chains. Fermentation with genetically modified B. subtilis had similar yields compared to the traditional fermentation and even the costs were lower [12]. Differences among various GRAS bacterial HA expression systems were summarized in Table 1. Table 1 Comparison of different GRAS bacterial HA expression system. Structure of operon

Gram stain

HA yield [g/L]

HA Mw [Da]

B. subtilis

Vhb+hasA+tauD(hasB)

1.8 ~ 2.1

1.1~1.2 M

L. lactis

hasA+hasB+hasC

0.46 ~ 1.8

550~850 k

S. thermophilus

8 x 10-3

Agrobacterium sp.

pmHAS+kfiD

0.3

0.7~2 M

hasA+ugd+galF 0.19 350 ~1,900 k or pmHAS+kfiD 2.0 ~ 3.8 All the genetically modified GRAS strains to produce HA were based on either Streptococcal HA synthase HASs or P. multocida hyaluronan synthase pmHAS. Further studies on the delicate control of HA biosynthetic pathway are needed, especially the balance of UDP-N-acetylglucosamine and UDP-glucuronic acid. With delicate control, HA with a specific molecular weight can be expected eventually. E. coli

References [1] B.F. Chong, L.M. Blank, R. Mclaughlin and L.K. Nielsen: Appl. Microbiol. Biotechnol., Vol. 66 (2005) No.4, p.341. [2] J.H. Kim, S.J. Yoo, D.K. Oh, Y.G. Kweon, D.W Park, C.H. Lee and G.H Gil: Enzyme Microb. Technol., Vol. 19 (1996) No.6, p.440. [3] W.Y. Chen, E. Marcellin, J. Hung and L.K. Nielsen: J. Biol. Chem., Vol. 284 (2009) No.27, p. 18007. [4] L. Liu, G. Du, J. Chen, Y. Zhu, M. Wang and J. Sun: Bioresour. Technol., Vol. 100 (2009) No.1, p.362. [5] L.M. Blank, R.L. Mclaughlin and L.K. Nielsen: Biotechnol. Bioeng., Vol. 90 (2005) No.6, p.685. [6] X.J. Duan, L. Yang, X. Zhang and W.S. Tan: J. Microbiol. Biotechnol., Vol. 18 (2008) No.4, p.718. [7] L. Liu, M. Wang, G. Du and J. Chen: Lett. Appl. Microbiol., Vol. 46 (2008) No.3, p.383.

Advanced Materials Research Vol. 950

[8] L. Liu, G. Du, J. Chen, M. Wang and J. Sun: Bioprocess Biosyst. Eng., Vol. 32 (2009) No.6, p.755. [9] P.H. Weigel and P.L. Deangelis: J. Biol. Chem., Vol. 282 (2007) No.51, p.36777. [10] S.H. Brown and P.E. Pummill: Curr. Pharm. Biotechnol., Vol. 9 (2008) No.4, p.239. [11] L.J. Chien and C.K. Lee: Biotechnol. Prog., Vol. 23 (2007) No.5, p.1017. [12] B. Widner, R. Behr, S. Von Dollen, M. Tang, T. Heu, A. Sloma, D. Sternberg, P.L. DeAngelis, P.H. Weigel and S. Brown: Appl. Environ. Microbiol., Vol. 71 (2005) No.7, p.3747. [13] L.J. Chien and C.K. Lee: Appl. Microbiol. Biotechnol., Vol. 77 (2007) No.2, p.339. [14]S.B. Prasad, G. Jayaraman and K.B. Ramachandran: Appl. Microbiol. Biotechnol., Vol. 86 (2010) No.1, p.273. [15] J.Z. Sheng, P.X. Ling, X.Q. Zhu, X.P. Guo, T.M. Zhang, Y.L. He and F.S.Wang: J. Appl. Microbiol., Vol. 107 (2009) No.1, p.136. [16] Z. Mao and R.R. Chen: Biotechnol. Prog., Vol. 23 (2007) No.5, p.1038. [17] Z. Mao, H.D. Shin and R. Chen: Appl. Microbiol. Biotechnol., Vol. 84 (2009) No.1, p.63. [18] H. Yu and G. Stephanopoulos: Metab. Eng., Vol. 10 (2008) No.1, p.24. [19] N. Izawa, T. Hanamizu, R. Iizuka, T. Sone, H. Mizukoshi, K. Kimura and K. Chiba: J. Biosci. Bioeng., Vol. 107 (2009) No.2, p.119.

Advanced Materials Research Vol. 950 (2014) pp 18-23 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.950.18

Improvement of Inflammability and Biodegradability of Bio-composites Using Recycled Polypropylene with Kenaf Fiber Containing Mixture Fire Retardant Neng Sri Suharty1*, Hanafi Ismail2, Kuncoro Dihardjo3, Muhammad Nizam3, Maulidan Firdaus1 1

Chemistry Department, University Sebelas Maret, Jl. Ir Sutami 36A Surakarta-Indonesia 57126

School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Tebal Nibong, Penang-Malaysia 3

Mechanical Engineering, University Sebelas Maret, Jl. Ir Sutami No 36A Surakarta–Indonesia 57126 *

Corresponding Author’s E-mail: nsuharty@yahoo.com

Keywords: Bio-composites; Flammability; Burning rate

Recycled

polypropylene;

Biodegradability;

Weight

lost,

Abstract. Have been reactively synthesized bio-composites material that has a good in mechanical strength and fuel resistance. The starting material for the manufacture of bio-composite was recycled PP (rPP) modified AA, reinforcement kenaf fiber (KF), the mixture of magnesium hydroxide (MH) and aluminum hydroxide (ATH) without or with boric acid (BA) as a fire retardant. The burning rate (BR) and tensile strength (TS) test were used ASTM D635 and D638, respectively. The presence of mixture fire retardant [MH/ATH] with ratio of 15/5 in the biocomposites can effectively reduce their burning rate (BR). Biodegradability of the bio-composites, which is reflected by weight loss (WL) is achieved arise after burying the bio-composites in garbage soil for four months. However, the presence of mixture fire retardant could marginally decrease the TS of the bio-composites. Introduction Chemical products that are based on renewable resources are important issue to sustainable development [1]. The utilization of renewable resources such as KF filler into PP matrix is being actively pursued due to improvement in material properties as well as biodegradability [2,3,4]. Plastics, especially PP which is widely used in automotive, house hold, and any other industrial applications such as in mineral water packaging [5] contributes a large percentage to household waste and polluting the environment. This is because PP is non-degradable. However, PP waste can be transformed to other useful product such as bio-composite by adding natural fiber, which have higher economic value and saving the environment from pollution. PP waste (referred as recycled PP, rPP), which has non-polar reactive methine functional group, is capable to react with cellulose of KF by using coupling agent acrylic acid (AA). To improve binding efficiency, divinyl benzene (DVB) was used as compatibilizer [6,7]. In this work, KF was used either as filler or enforcement in rPP/DVB/AA/KF bio-composites. The demand for composites in various applications such as components of building materials, and automotive industry is increasing due to the environmental and economical matter. As a function of its purpose to an automotive components in addition to having high mechanical properties also must have a fuel endurance. So the flame retardant of the bio-composite materials has become more important in order to comply with the safety requirements of products [8]. Composite is a lightweight material. The automotive which uses composite components have lightweight mass. The automotive lightweight mass requires relatively less fuel. Therefore the use of composites as automotive components will save on fuel usage. Burning process is depended on 3 conditions, such as: oxygen, fuel and heat. Flame retardancy can be achieved by the disruption of the burning process at any of these stages that can be lead to

Advanced Materials Research Vol. 950

the termination of the process before actual ignition occurs. The most expeditious method used to acquire flame retardancy is the incorporation of flame-retardants that can interfere with the combustion during a particular stage of the process so that the resulting system shows satisfactory flame retardancy [9]. Fire retardant for polymer widely used as metal hydroxide are magnesium hydroxide (MH) and aluminum hydroxide (ATH). MH has its decomposition temperature at 320°C, and ATH at 200°C [8,10,11]. It has been reported that by adding any of these compounds i.e. boric acid (BA), ammonium phosphates or zinc borate to matrix polymer can act as flame retardant additives [8,12]. Depending on the nature of the additives, they can be active chemically or physically in the solid, liquid or gas phase. The objective of this paper is to study the effect of KF, mixture fire retardant [MH+ATH+BA] on the inflammability, biodegradability and mechanical properties of rPP/DVB/AA/KF bio-composites as an automotive component materials with the lightweight mass. Experimental General information. All chemicals as starting compounds are in pro-analysis grade except mentioned, and used as such without any further purification. The rPP was obtained from waste drinking water cup. The rPP samples were prepared by washing the waste cups with ethanol, and chopped in 2x2 mm. The KF used after delignification with 4% NaOH solution, to be followed by blushing with water, drying in oven at 40oC and grinding into 100 mesh particle size. Characterization of starting materials as well as new material produced were performed using: 1) Atlas Melt Flow Indexer (MFI) in order to determine the melt flow index of bio-composite in accordance with ASTM 1238; 2) Paul Weber Machinen-u-Aparatebau D-7064 RhemshaldenBrunbach hot press was utilized to prepare specimens; 3) Tensometry (MPG SC-2 DE) was used to determine tensile strength, TS, in accordance with ASTM D638; 4) Shimadzu FTIR-8201 PC was used to determine functional group; 5) XRD Philips type X’pert in order to determine crystalline peaks at 2θ with their crystal fields; and 6) Horizontal burning method to perform flammability test in accordance with ASTM D635; and 7) Burial method in cellulolytic bacteria enriched garbage soil for four months to perform biodegradability test. Synthesis, characterization and examination of rPP bio-composite using KF reinforcement filler. The synthesis of rPP/DVB/AA/KF/[MH+ATH+BA] bio-composite was reactively done in xylene medium using starting materials: rPP, KF, AA, DVB containing fire retardant mixture of MH and ATH with and without BA additive. The formulation of bio-composites synthesis can be seen in Table 1. Table 1 Formulation of rPP/DVB/AA/KF bio-composites with and without fire retardant Ingredients Composites (phr) rPP F1 F2 F3 F4 F5 rPP 100 80 65 65 65 65 KF 20 15 15 15 15 AA 2 2 2 2 2 DVB 0,1 0,1 0,1 0,1 0,1 Al(OH)3=ATH 15 10 5 15 Mg(OH)2=MH 5 10 15 5 2 H3BO3=BA

F6 65 15 2 0,1 10 10 2

F7 65 15 2 0,1 5 15 2

The flammability of the bio-composites produced by formula F1-F7 was tested in accordance to ASTM D635 in order to determine their Time To Ignition (TTI), and Burning Rate (BR). The highest TTI and the lowest BR show that the material has better inflammability. Biodegradation tests were conducted by burying bio-composites in garbage soil for four months, and then measured the weight loss (WL) of the composites after bio-degradation process.

Materials, Mechatronics and Automation IV

Results and Discussion Structure Interaction Studies of Composites. Composite structure of formed rPP/DVB/AA/KF/[MH+ATH+BA] can be studied using FTIR spectra for its specific functional groups, and the uptake diffractogram which has specific crystal peaks of XRD at 2θ with specific crystal field as shown in Fig 1 and Fig 2.

Fig 1 FTIR spectra of ATH, MDH and rPP/DVB/AA/KF/[MH+ATH+BA] bio-composites

Fig 2 Diffractogram XRD of MDH, ATH and rPP/DVB/AA/KF/[MH+ATH+BA] bio-composites

Based on the FTIR spectra as shown in Fig 1, each functional group starting materials and composites rPP/DVB/AA/KF/[MH+ATH+BA] can be analyzed. Absorption peaks at: 3695 and 3618 cm-1 shown the free hydroxyl groups of MH and ATH respectively. Broad absorption at 3525 cm-1 represents a hydrogen bonded of hydroxyl groups of cellulose KF, MH and ATH. Absorption at 2800-3000 cm-1 was >CH- stretching of methyl and methylene (>CH2) groups. PP has specific absorption peaks at 2723 (>CH- typical PP), 1458 cm-1 of methylene (-CH2-), and 1373 cm-1 methyl (-CH3). The absorption peak of carbonyl have shifted from 1728 cm-1 of acrylic acid [6] to 1732 cm1 new bio-composites. This shifting is related to the formation of carbonyl ester which were produced between hydroxyl cellulose of KF and carboxylic groups of AA [6]. The formation peak at 1165 cm-1 of >C-O-C< are also supporting the presence of ester groups. Absorption at 913-1002 cm-1 shown the Al-O and Mg-O groups [13,14]. Based on the FTIR analyses, it can be concluded that the reaction had taken place to form the new bio-composite. Bio-composites spectra of rPP/DVB/AA/KF/ [MH+ATH+BA] as a whole shows the characteristic peaks of its constituent compounds. XRD diffractogram presented in Fig 2 shows: • rPP has crystalline peaks at 2θ with their respective crystal fields: 14.2(111), 17.0(008), 18.4 (202), 21.4(026) and 21.9(012). • ATH has crystalline peaks at 2θ with their respective crystal fields: 18.3(002), 20.3(110), 37.1(004), 37.7(302), and 45.4(022). • MH has crystalline peaks at 2θ with their respective crystal fields: 18.3(001), 20.3(110), 37.1(004), 37.7(302), and 45.4(022). In rPP/DVB/AA/KF/[MH+ATH+BA] composite, the crystalline peak of its constituent compounds remained seen although their positions are slightly shifted. Diffractogram composite rPP/DVB/AA/KF/[MH+ATH+BA] has crystalline peaks at 2θ: rPP shifted from 14.2 to 14.1 and 17.0 to 16.9; ATH and MH are shifted from 3.18 to 5.18; ATH has another crystalline peak at 37.7 whereas MH is also shifted from 38.0 to 38.1; ATH and MH have other shift in their crystalline peak from 50.5 to 50.8; MH shifted from 58.6 to 58.7 and 62.1 to 62.2. The shifts that occurred above prove there have been interaction between its constituents compounds in the formation of new bio-composites.

Advanced Materials Research Vol. 950

Flammability characterizations. The results of bio-composites (F1-F7) flammability tests can be seen in fig 3. The TTI of starting materials rPP and F1 bio-composites are 1.02 and 2.16 seconds, respectively. The bio-composites rPP/DVB/AA/KF containing 20 phr mixture of fire retardant [MH+ATH] with ratio of 15/5 (F4) inhibited TTI to 84% of bio-composite without fire retardant (F1). When 2 phr BA is added to (F4) that equals to (F7), TTI slows down by 111% longer than F1. The burning rate (BR) of rPP and F1 are 18.99 and 15.69 mm/mins, respectively. The BR of F4 and F7 decrease to 43% and 55% respectively compared to that of F1. In addition, 2 phr BA without reducing fire retardant concentration can decrease the BR up to 12% (Fig 4).

Fig. 3 Results of Time to Ignition, TTI

Fig. 4 Result of Burning Rate (BR)

This indicates that [MH+ATH] can be used as fire retardant mixture for rPP/KF composites at lower fiber loading (15 phr). Mg(OH)2 and Al(OH)3 in burning process will undergo: 2A1(OH)3 Al2O3 + 3H2O; and Mg(OH)2 MgO + H2O. Thus, Mg(OH)2 has the advantage that its decomposition into magnesium oxide, MgO, and water starts at temperature 300 to 320°C, allowing it to be processed in plastics such as PP. However, decomposition temperature of Al(OH)3 is at 200°C [8,10,11]. Decomposition of metal hydroxides in burning process can decrease the amount of heat of the flame. The burning also forms some water in gas, which can decrease the oxygen percentage for combustion. It had been reported in previous work [9] that Mg(OH)2 and Al(OH)3 can act as flame retardant to plastics at a higher loading. Boric acid (H3BO3) when heated produce B2O3 gas which restrict the entry of oxygen into combustion process. This synergetic effect of metal hydroxide when used in conjunction with boric acid or zinc borate has been reported in the previous work [15]. Biodegradation and mechanical characterizations. Results of biodegradability examination can be seen in Figure 5. Water Absorption (WA) of rPP and F1 are 0 and 1.65 respectively. The WA of bio-composites F4 and F7 can increase up to 0.27% and 0.34%, respectively compared to F1. The WL of rPP and F1 are 0 and 5.75% respectively. The WL of bio-composites F7 is higher by approximately 1.2% of F1. This occurs because the cellulose of KF inside composite rPP/DVB/AA/KF in the moist waste ground containing cellulolytic bacteria performed selfbiodegradation. This result is supported by the previous work that plastic composites containing natural fiber can absorb water and thus will degrade after being buried in soil [6,3].

Fig. 5 Results of (WA) and (WL) percentages

Fig. 6 Results of MFI and TS

Materials, Mechatronics and Automation IV

Mechanical properties examination results of bio-composites as presented in Figure 6. are as follows: The MFI of rPP and F1 are 15.6 and 10.6 g/10 minutes respectively. The MFI of F4 and F7 decrease up to 70 and 71% respectively compared to F1. The Tensile Strength (TS) of rPP and F1 are 24.8 and 32.4 MPa respectively. The TS of F4 and F7 were lower by 13% and 15%, respectively compared to F1. The presence of fire retardant [MH+ATH] in the composites resulting the decrease in TS due to reduction of its elasticity. Similar results have been reported in previous work [9] that in the presence of 20% Mg(OH)2, mechanical properties of composite rPP/wood or rice husk fiber were decreased. Conclusion Bio-composites rPP/DVB/AA/KF containing fire retardant mixtures of [MH+ATH] with and without addition BA were studied for their structure interactions, flammability, biodegradability and mechanical properties. Bio-composite rPP/DVB/AA/KF/ [MH+ATH+BA] containing 20 phr of mixture [MH/ATH] with ratio of 15/5 and 2 phr BA can effectively increase TTI to 111% and in the same time reduce burning rate to 55% compared to bio-composites without any addition of fire retardant. The biodegradability, measured through WL of the bio-composite after being buried in garbage soil for four months, was 1.2%. However, TS of bio-composites in the presence of fire retardant mixture was slightly decreased. At the same time, better properties than rPP was obtained. Acknowledgement The authors would like to acknowledge to Indonesian Directorate General of Higher Education for financial support from International Collaboration Research and International Publication Grant. References [1] J.O. Metzger, M. Eissen: Concepts on the contribution of chemistry to a sustainable development. Renewable raw materials, Comptes Rendus Chimie, 7: 1–13 (2004) [2] H.G.B. Premalal, H. Ismail, A. Baharin: Comparison of the mechanical properties of rice husk powder filled polypropylene composites with talc filled polypropylene composites, Polymer Testing 21: 833–839 (2002) [3] H.S. Kim, H.S. Yang, H.J. Kim: Biodegradability and mechanical properties of agro-flourfilled polibutylene succinate biocomposites, J Appl. Poly. Sci, 97: 1513-1521 (2005) [4] N.S. Suharty, and M. Firdaus: Synthesis of degradable bio-composites polystyrene recycle modified in reactively process using natural fibre filler, Proceeding of 12th Asian Chemical Congress, Kuala Lumpur, Malaysia (2006) [5] M. Sain, J. Balatinecz, S. Law: Creep fatigue in engineered wood fibres and plastic compositions. J Appl. Poly. Sci., 77:260 (2000) [6] N.S. Suharty, B. Wirjosentono, M. Firdaus, D.S. Handayani, J .Sholikhah, Y.A. Maharani: Synthesis of degradable bio-composites based on recycle polypropylene filled with bamboo powder using a reactive process, J. Phys. Sci., 19: 105–115 (2008) [7] H. Ismail, M.R. Edyham and B. Wirjosentono, Bamboo Fiber Filled Natural Rubber Composites: The Effects of Filler Loading and Bonding Agent, Polymer Testing, 21:139-144 (2002) [8] Bourbigot Serge, Duquesne Sophie: Fire Retardant Polymer: Recent Developments and Opportunities, J. Mater. Chem., 17:2283-2300 (2007) [9] M. Sain, S.H. Park, F. Suhara, S. Law: Flame retardant and mechanical properties of natural fiber–PP composites containing magnesium hydroxide, Poly. Deg. and Stab.83: 363–367 (2004)

Advanced Materials Research Vol. 950

[10] A.A. Aziz Ahmad, S.M. Alauddin, R.M. Saleh, Sabet Maziyar: Influence of Magnesium Hydroxide/Aluminum Tri-hydroxide Particel Size on Polymer Flame Retardancy: An Overview. Int of Chem Eng Appl.,Vol 3 No 6 (2012) [11] Hao Tang, Xiao-Bai Zhou, Xiao-Lu Liu: Effect of Magnesium Hydroxide on the Flame Retardant Properties of Unsaturated Polyester Resin. ProcediaEngeenering., 52: 336-341 (2012) [12] N.S. Suharty, I.P. Almanar, Sudirman, K. Dihardjo, N. Astasari: Flammability, Biodegradability dan Mechanical Properties of Bio-Composites Waste Polypropilene/Kenaf Fiber Containing Nano CaCO3 with Diammonium Phosphate, Procedia Chemistry, vol.4:282287 (2012) [13] B.R. Ilic, A.A. Mitrovic, and L.R. Ljiljana: Thermal Treatment of Kaolin Clay to Obtain Metakaolin.Hem. Ind 64(4): 351-356 (2010) [14] A. Nagieb Zenat, A. Nassar Mona, G. El-Meligy Magda: Effect of Addition of Boric Acid and Borax on Fire-Retardant and Mechanical Properties of Urea Formaldehyde Saw Dust Composites. International Journal of Carbohydrat Chemistry (2011) [15] J. Jang, and E. Lee: Improvement of flame retardancy of paper sludge/polypropylene composite, Polymer Testing, 20:7 (2001)

Advanced Materials Research Vol. 950 (2014) pp 24-28 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.950.24

Morphological Study of Bacterial Cellulose (BC) /Polyvinil Alcohol (PVA) Nanocomposite as Bone Scaffold A.Z. Abidina, H.P.R. Grahab Department of Chemical Engineering, Faculty of Industrial Technology, InstitutTeknologi Bandung, Jl Ganesa 10 Bandung 40132, Indonesia a

zainal@che.itb.ac.id, bhafis@students.itb.ac.id

Keywords: Bacterial cellulose; Polyvinil alcohol; Nanocomposite; Scaffold; Morphology

Abstract. This research describes morphological aspect of BC-PVA nanocomposite asscaffold for bone tissue that was synthesized by adding PVA to Gluconacetobacterxylinus fermentation medium. PVA concentrationswere varied as 0,3,6,9, and 12 % (w/v) of the medium. The culture was agitated with magnetic stirrer for 28 days. Freeze drying was then conducted to obtain dry BC/PVA nanocomposite. Some nanocomposite samples subjected to sonication treatments. The morphology of BC-PVA nanocomposite was examined by Scanning Electron Microscope (SEM) whileits surface area and pore characteristic were determined by nitrogen adsorption of BJH method (BET device). SEM images showed the smallest fiber diameter of approximately 35 nm andnanocomposite surface that was smoother with higher PVA content in the fermentation medium. The sonicationtreatmentcould enhance nanocomposite surface area from 17,2 m2/g to 72,7 m2/g for pure BC sample and from 9,9 m2/g to 14,3 m2/g for 12% PVA sample. BC/PVA nanocompisite had smaller pore diameter than pure BC and its size increased with more PVA content in the fermentation medium.PVA could modify BC morphology bymakinga hindrance on cellulose nanofiber sothat fiber agglomeration could be avoided andthe sonicationtreatmentshowedto enhance this phenomena. Introduction Bone is a composite material consisting of collagen matrix reinforced with crystalline hydroxyapatite (HAp) [1]. The process of bone formation (ossification) consists of two main stages, namely primary and secondary ossification. Bone secondary structure consisting of collagen and HAp is more complex than the primary structure. Gap caused by a fault could block the transport of nutrients thatwould inhibitthe process of ossificationandslow the bone healing [2]. To overcome these problems a porous scaffold that can be mounted on the broken bone (fracture) is required to allow the transport of nutrients and the bio-mineralization so bone fracture will heal quickly. Bacterial cellulose isan attractivematerial to studyfor application in bone tissue engineering scaffold. It issimpletomodifyits properties by combining with other materials and cheap in the manufacturing costs. In this study bacterial cellulose was blended with polyvinyl alcohol (PVA) by the method of biosynthesis. These composites are expected to mimic the properties of collagen fibres so Hydroxyapatite (HAp) can be formed. The presence of HAp is necessary to initiate the formation of bone in the fracture gap and can eventually fill completely thegap [1] Experiment Nanocomposite Biosynthesis. Bacterial cellulose-PVA nanocomposite was synthesized by biosynthesis method. Fermentation medium was modified byPVAaddition. The nanocompositewas expected toform when PVA was co-crystallized with bacterial cellulose produced by microbes. The tools used for the synthesis was 500 mL erlenmeyer flask with a volume of 250 mL of medium solution. Culture medium used was Hestrin-Scramms Medium (HS medium) [3] with slight modifications to the original glucose concentration, ie 2% to 8%, and the addition of urea as much as 0.5%. PVA was added to the medium with concentration variations of 3, 6, 9, and 12%. Medium with 0%PVA was used as a refference.Sterilization process wasappliedtothe medium and then a solution of nata de coco seed containing theGluconacetobacter xylinussuspension was added to the medium as

Advanced Materials Research Vol. 950

much as 50 mL. Erlenmeyer was equiped with magnetic stirrer and the stirringwas done for 28 days with a speed scale of 1 (Figure 1). Synthesis of nanocompositein static culture was also performed for comparison.

Fig. 1 Fermentation Scheme Nanocomposite Purification and Drying. Nanocomposite formed in the medium was separated by filtration. The filtered solid was washed several times using distilled wate and then dried by freeze drying method and stored in a desiccator until the characterization was conducted. Sonication. Ultrasonic waves was applied to nanocomposite samples of 0% and 12%PVA usinga methodproposed by [4]. About 0.1g of the dried samplewas put into 200 mL of distilled water in an erlenmeyer and stirred for 15 minutes. The ultrasonic waves produced by sonochemical reactor set Transonic Elma with a frequency of 40 kHzwas used to treat the sample for 30 minutes at 60% power. The sample was re-dried by freeze drying and then characterized. PoreCharacterization of Nanocomposite. This test used a Nova ® Surface Area Analyser 3200 series andanalysis method of BJH isothermal adsorption with nitrogen gas. Applied outgassing time was four hours at 150oC. The data generated from the testing were pore diameter and surface area per mass unit for samples of 0%, 6%, and 12% PVA in the medium. Hydroxyapatite Coating. This was to determine whether bacterial cellulose-PVA nanocomposite can be coated with a Hydroxyapatite (HAp) to form a composite bio-ceramics. Nanocomposite samples was immersed in aproximately 10 ml of Simulated Body Fluid (SBF) in a test tubefor 1 week. SBF was replaced with a fresh one in every 24 hours. Composite bioceramics will provide bioactivity to stimulate growth and differentiation potential of bone cells into bone cells [3]. The formation of composite bio-ceramicin the sample provides a great expectation of the nanocomposite for further development as a scaffold material in bone tissue. X-Ray Diffraction (XRD). This test was done to ensure that the formed layer on the nanocomposite was Hap. The test used scan range of 10o-60o, scan speed of 6o/min, and scan angle of 2θ. Hap would be characterized as a peak at angle of 31.7 o and 45.5 o. Scanning Electron Microscopy (SEM). Nanocomposite surface was viewed using SEM to observe the size of the fibre diameter in the material. Forsamples of the nanocompositesoaked in SBF of 1 week, this characterization had specific aim to determineif a deposit of Hap formed in the composite matrix. Result Nanocomposite Yield Table 1 Mass of Nanocomposite Product PVA (%mass) in medium 0 0 3 6 9 12

Stirring no yes yes yes yes yes

Nanocomposite dry weight (g) 7,760 0,680 0,151 0,300 1,020 1,210

Glucose Conversion 9,700 % 3,400 % 0,755 % 1,500 % 5,100 % 6,050 %

Materials, Mechatronics and Automation IV

Pore and Surface Area Characterization Table 2 Surface Area and Pore Diameter Sample (%mass PVA in medium) 0% 0% 6% 12% 12%

Sonication

Surface Area (m2/g)

Average Pore Diameter (nm)

no yes no no yes

17,2 72,7 6,9 9,9 4,3

29,8 19.2 19,2 20,8 24,0

XRD Spectra

Fig. 2 XRD Spectra of the sample of 0% PVA Red line: without HApdeposistion; Blue line: with HAp deposition SEM Photograph a

Fig. 3 SEM image of nanocomposite (a) PVA 0%; (b)PVA 3%; (c)PVA 6%; (d)PVA 9%; (e)PVA12% ; (f) deposisiHAp

Advanced Materials Research Vol. 950

Discussion Data in Table 1shows that synthesis of the cellulose in a static culture gives higher glucose than in agitated culture. For almost all strains of G. Xylinus, the rate of formation of cellulose layer in static culture is higher than in agitated or submergedcultures, in which oxygen was supplied by forced aeration (due to stirring) in order to make bacteriahaving better respiration [5]. For the agitated culture, the samples of 9 and 12% PVAyield higher nanocomposite products than other samples. The mediumbecame very viscous with the addition of 9 and 12% PVA. When stirred, the surface of the liquid medium in the sample of 12% PVAwas smoother than those of other samples. This is due to the liquid staying calm and forming no vortex. Contact of bacteria with air in the erlenmeyer flaskwasnot affected by the agitation so the production of cellulose could be optimized. The agitation would make submerged fermentation condition so supply of oxygen to the bacteria will be inhibited by the presence of medium solution. Looking todata in Table 2 of surface area and average pore diameter of the 0% PVA sample, sonication technique seems to causethe breaking down of fiber cellulose into sub fiber with a smaller diameter. As results, nanocomposite surface area increases and the average pore diameter decreases. The addition of PVA may close the pores between the cellulose fiber. For sample of 12% PVA, the sonication increases the materialsurface areaalthough not as high as the sample of 0% PVA. This may be aresult of cellulose fibers covered by PVA so the cellulose fibersare bonded by PVA andfibers are not broken into sub fibers. There is a possibility that sonication causes the cavity formationin nanocomposite and make larger pores. This is supported by the fact that with sonication process, the average pore diameter in the nanocomposite material increases. Fig 3shows that the smallest diameter of a single fiber that can be observed is about 30 nm. This resultis larger than previous results, ie17 nm [6] and 4 nm [7]. The difference ispossibly due to a process of aggregation offiberstoformlarger diameter as an effect of longersynthesis time. Observation [8] made after 5 days of culture age while [7] made after 10 days culture age. The longer fermentation time maypromotean aggregationto producelarger fiber diameter. The success of HAp coating can be observed from the SEM image in Figure 3fthat has been confirmed by XRD test results.Figure 2 shows that the samples soaked in SBF have distinctive peaks compared with samples that are not soaked in SBF. Two strongest peaksare at 2θ 31.82 and 45.58. According to [8] a crystal with typical peak close to the observations is deficient Calcium Hydroxyapatite crystal crystal (cdHAp) that has a typical peak at 31.7 and 45.5. Formation of cdHAp on bacterial cellulose-PVA nanocomposite is an advantage. In the bone, thermodynamically cdHAp is easier to form than usual HApdue to the presence of hydroxyapatite ions in the body [1]. This nanocomposite is expected to give a good performance in the regenerating bone in the body. Conclusion Application of ultrasonic waves in the nanocomposite can increase the surface area per unit mass and increase the amount of pore with bigger size.Scanning Electron Microscopy and Analysis qualitatively using X-Ray Diffraction showed that Hydroxy Apatite successfully deposited in bacterial cellulose-PVA nanocomposite. Hence the nanocomposite has the potential to be a bone scaffold. References [1] Hutchens, S.A.; Benson, R.S.; Evans, B.R.; O’Neill, H.M.; Rawn, C.J., “Biomimetic synthesis of calcium-deficient hydroxyapatite in a natural hydrogel”, Biomaterials (27)2006, 4661–5670. [2] Olszta,Matthew. J.; et al, "Bone structure and formation: A new perspective", Materials Science and Engineering: R: Reports (58) Issues 3–5, 28 November 2007,77–116. [3] Hestrin, S.; Schramm, M., “Synthesis of cellulose by Acetobacterxylinum. II. Preparation of freeze-dried cells capable of polymerizing glucose to cellulose”, Biochem J, 58(2), 1954, 345–352.

Materials, Mechatronics and Automation IV

[4] Tischer, etal., “Nanostructural Reorganization of Bacterial Cellulose by Ultrasonic Treatment”,Biomacromolekul 11, 2010, 1217-1224. [5] Chawla, P.R.; et al., “Fermentative Production of Microbial Cellulose”, Food Technol. Biotechnol. 47 (2), 2009, 107–124. [6] Brown, Elvie.E., “Bacterial Cellulose /Thermoplastic Polymers Nanocomposites”, Thesis, Washington State University.2007 [7] Zaar, K., “The biogenesis of cellulose by AcetobacterXylinum”. Cytobiologie European Journal Of Cell Biology (16) 1977, 1-15. [8] Zimmermann, K.A.; LeBlanc, J.M.; Sheets, K.T.; Fox, R.W.; Gatenholm, Paul., “Biomimetic design of a bacterial cellulose/hydroxyapatite nanocomposite for bone healing applications”, Material Science and Engineering C 31, 2011, 43-49.

Advanced Materials Research Vol. 950 (2014) pp 29-32 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.950.29

Extraction of Di-Methyl Phthalate Using Smarta Nanoscavengers Nezar H. Khdary King Abdulaziz City for Science and Technology (KACST), P.O. Box 6086 Riyadh 11442, Kingdom of Saudi Arabia nkhdary@kacst.edu.sa Keywords: Di-methyl phthalate, Extraction, C18, Nanoscavenger

Abstract. A base-catalyzed process was applied to the synthesis C18-silicananoparticles.The basecatalyzed process led to the rearrangement of spherical particles to form a flower-like aggregation of 300-nm silica particles. IR and TGA supported the success of the modification. The extraction of di-methyl phthalate(DMP) was successfully achieved (Fig. 1) in the ngrange.

Fig. 1 Extraction of DMP silica nanoparticles Introduction Phthalates are frequently used as plasticizers, solvents, and additives in a number of products, such as polyvinylchloride (PVC) plastics and cosmetic products. A number of phthalates, such as di(2ethylhexyl)phthalate, are known to be carcinogenic.[1] Other phthalates, such as dibutyl phthalate, can also cause health problems, particularly at high levels of exposure.[2] Kelly and Larroque[3] foundtrace levels of diethyl phthalate in water using a solid-phase microextraction preconcentration step followed by high-performance liquid chromatography (HPLC). Automated online, in-tube solid-phase microextraction, coupled with HPLC, was developed by Kataoka et al.[4] The pre-concentration was carried out in a capillary column (60cm × 4.0mm ID, 12-µm film thickness), then placed between the injection loop and injection needle of the autosampler. Recoveries of phthalates varied from 63%–106%. Seven phthalate esters were determined in water samples by GC-MS.[5] The procedure employed solid-phase microextraction, with 5-µm Carbowax templated resin giving a recovery of around 60%, with a detection limit of 1µg L-1. Gas chromatography with an attached electron capture detector was employed for the determination of six types of phthalates in water, and the sample was concentrated by solid-phase microextraction. The study demonstrated that fibers coated with polyacrylate were suitable for the analysis of phthalates, with recoveries varying between 0% for dimethyl phthalate to 116% for butylbenzyl phthalate.[6] Phthalate was successfully pre-concentrated using silica gel modified with the Saccharomyces cerevisiae microorganism;[7] a recovery of over 95% was obtained. A styrenedivinylbenzenecopolymer used for the pre-concentration of di-n-butyl phthalate and benzylbutyl phthalate gave recoveries of 62% and 56%, respectively.[8] In this work, modified silica nanoparticles were for the first time utilized for the extraction and pre-concentration of phthalate. The surface was modified using an amine catalyst. Tripp and Hair[9] developed an amine-catalyzed method for the attachment of chlorosilanes to the silica surface at room temperature. The authors extended their work[10] and found that, whilst in the absence of moisture, the reaction between

Materials, Mechatronics and Automation IV

chlorosilane and silica does not occur at temperatures below 300°C in carbon tetrachloride, and that the reaction can occur at room temperature in the presence of triethylamine. Recent work hasbeen published, utilizing modified silica nanoparticles for scavenging heavy metals and drugs.[11–13] In this work, the ability of C18-Silica toextract DMP is assessed; measurements were carried out using HPLC. Experiments Chemicals. All glassware was washed with detergent and water, rinsed with deionized water, and dried in an oven. Before using the glassware, it was rinsed with acetone and finally with hexane, and left to dry at room temperature. Triethylamineand Di-n-butyl phthalate (DnBP) were obtained from Aldrich.Acetonitrile, n-hexane,carbon tetrachloride, chloroform, and ethanol were supplied by Rathburn (Walkerburn, UK). Modification of Silica Nanoparticles. The modification of silica surface using a base catalyst was carried out by adding a small volume of the base catalyst triethylamine.[8] Carbon tetrachloride (30mL, 99.5%) was transferred into a 250-mL round-bottomed flask and connected to a condenser. Silica particles (500mg), dried at 150°C for 4 hours, were added to the flask. The contents were agitated using a magnetic stirrer, the temperature being kept constant at 29±3°C. Triethylamine (1mL, 99%) was added to the flask, and octadecyltrichlorosilane (1mL, 95%) was introduced to the reaction flask after 15 minutes; the mixture was left for 2 hours under nitrogen. The white suspension was centrifuged, the solid product was rinsed thoroughly with chloroform and finally with ethanol, and both were dried overnight in an evacuated desiccator. Results and Discussion Alkytrichlorosilane monolayers were successfully covalently attached tosilica nanoparticles. The mechanisminvolveda penta-coordinate intermediate, as illustrated in Fig.2(Unger and Kinkel.[14]

Fig. 2 Base catalyzed for silica modification[14] Infrared Spectroscopy. The spectra of the modified silica showed bands at 1794 and 1104cm–1, respectively associated with Si-O-Si symmetric and asymmetric vibrations, and two peaks at 2916 and 2854cm–1 attributed to C-H stretching.[8] A band located at 1462cm–1was attributed to C-H bending. The strong bands from2800–2960cm–1are evidence of the modification of the silica surface.[10]The results strongly support the modification of silica nanoparticles with C18 groups. Thermo gravimetric Analysis. Thermo gravimetric analysis (TGA) was carried out from 50°C to 750°C;theheating rate was 10°C min-1. Three areas of weight loss were evaluated for modified silica

Advanced Materials Research Vol. 950

particles. The initial weight loss from 50°C to around 120°C of 2.3% is believed to be due to the evaporation of residual solvent and water (physically adsorbed), while the second weight loss of about 1.6% over the temperature region 200°C–450°C was due to the elimination of chemicallybound water. The third weight loss from450°C–800°C of 1.3% may be due to the condensation of the silanol groups to siloxane bonds through water elimination.[12] The total loss from plain silica nanoparticles was 5.2%;the loss was7.1% from modified silica. The higher organic loading on the commercial 5-µ C18hypersil ODS, which reached around 28%, could be due to the forming of multilayer C18. Scanning Electron Microscope. Scanning electron microscope (SEM) imaging of unmodified silica showed a spherical shape of around 300nm in diameter(Fig 3(a)). However, the silica modified using a catalyzed base show a flower-like rearrangement of the spherical particles (Fig 3(b)), which means that the base-catalyzation process could lead to the rearrangement of the particles to form a hexagonal flower-like arrangement, which means that the aggregation of particles was increased, producing large particles, as shown in Fig 3(b).

Fig. 3 SEM images of (a) unmodified silica and (b) silica modified with C18 Phthalate Uptake of C18 Scavengers. In order to assess the quantity of analyte that could be extracted by the C18scavenger, di-n-butyl phthalate capacity was evaluated.Accurately weighed portions (ca. 50mg) of purified C18scavengers were transferred into 10mL volumetric flasks;10mL of a 10µgmL–1DnBP solution in deionized water was added to each flask and left overnight. The solutions were filtered through cellulose nitrate membrane filters (47mm diameter,0.1µm pore size), and the membrane filters were carefully transferred to specimen vials and dried under reduced pressure. Acetonitrile (3mL) was added to each specimen vial to release the DnBP and then shaken for 1hour. Each solution was transferred to a 5mL volumetric flask and made up to the mark with acetonitrile;20µL from each solution was then injected to HPLC. Table 1 shows that the C18 scavenger has 38 times higher uptake than unmodified silica. Table 1 Uptake of DnBP for silica batches Sample Unmodified silica C18-silica 5µmHypersil ODS C18-scavenger

Capacity µ molDnBP/g silica 0.014 0.79 0.54

Pre-concentration and Extraction of DMP For three 100mLvolumetric flasks 10mL (80ngmL-1, DMP) was transferred to each flask and50mL of deionized water was added; 100mg of C18-NS was added to each flask and then checked well. The flasks were made up to 100mLwith deionized water and checked. The solutions were filtered by a 0.1µm cellulose nitrate membrane filter, the membrane filters were gently removed to 25mLvials, and hexane was added to each glass vial to release the DMP from C18-NS. The hexane extract was the transferred into 5mLvolumetric flasks and made up to with hexane. An appropriate volume was injected to HPLC.

Materials, Mechatronics and Automation IV

Fig. 4 DMP calibration curve Table 2 Recovery of DMP extracted using a C18 scavenger Method of extraction Extraction OF DMP using a C18 scavenger Solvent extraction with n-hexane

DMP Recovery % 82%±7 90±4

Conclusion DMP was successfully extracted from water using a nanoscavenger. The recovery was over 80%. Using a solvent extraction technique showed a bit of increase in recovery, while large volumes of harmful organic solvents have been involved. The nanoscavnger technique is a green chemistry technique in whicha small volume of organic solvent was used. References [1] W.W. Huber, B.G. Kraupp, R.S. Hermann, Critical Reviews in Toxicology 1996, 26, 365. [2] E. Mylchreest, R.C.Cattley, P.M. Foster, Toxicology Science 1998, 43, 47. [3] M.T. Kelly, M. Larroque, Journal of Chromatography A 1999, 841, 177. [4] H. Kataoka, M. Ise, S. Narimatsu, Journal of Separation Science 2002, 25, 77. [5] B.K. Luks, P. Popp, B. Janoszka, H. Paschke, Journal of Chromatography A 2001, 938, 93. [6] G. Prokupkova, K. Holadova, J. Poustka, J. Hajslova, AnalyticaChimicaActa 2002, 457, 211. [7] H. Katsumata, A. Begum, S. Kaneco, T. Suzuki, K. Ohta, Analytica Chimica Acta 2004, 502, 167. [8] L. Brossa, R.M. Marce, F. Borrull, E. Pocurull, Journal of Chromatography A 2002, 963, 287. [9] C.P. Tripp, M.L. Hair, Journal of Physical Chemistry 1993, 97, 5693. [10] M.L. Hair, C.P. Tripp, Colloids and Surfaces a-Physicochemical and Engineering Aspects 1995, 105,95. [11] N.H. Khdary, Advanced Materials Research2013 699, 144. [12] N.H. Khdary, A.E. Gassim, A.G. Howard, Analytical Methods 2012, 4, 2900–2907. [13] N.H. Khdary, A.G. Howard,Analyst 2011,136, 3004–3009. [14] J.N. Kinkel, K.K. Unger, Journal of Chromatographic Science 1984, 316, 193.

Advanced Materials Research Vol. 950 (2014) pp 33-37 © (2014) Trans Tech Publications, Switzerland doi:10.4028/www.scientific.net/AMR.950.33

Preparation and Characterization of Al2O3/PVDF-HFP Based Polymer Electrolyte Hong Shi 1, Qing Zhu 2 1

School of Chemical and Environmental Engineering, Jianghan University, Wuhan 430056, China 2

Dongfeng Motor Corporation, Shiyan, Hubei, 442000, China

Keywords: PVDF-HFP; Al2O3; Polymer electrolyte; Conductivity; Lithium batteries

Abstract. Al2O3/PVDF-HFP based polymer electrolyte was prepared by the phase transfer method with different mass ratios of organic solvent and non-organic solvent. The solid polymer electrolyte was characterized by means of SEM, FTIR and AC impedance methods. The results show that the optimum mass ratio of organic solvent to non-organic solvent is 1:0.3 and the optimum mass ratio of Al2O3 is 7%. The liquid absorption rate of the polymer electrolyte is 225%. The lithium ionic conductivity of the polymer electrolyte at room temperature is about 1.75×10−3 S·cm-1, and the LiCoO2/Al2O3/PVDF-HFP/Li cell has good cycle performance. Introduction Olid polymer electrolytes (SPE) have been studied extensively in recent years for application in many electrochemical devices, such as cellular phones, smart credit cards, and laptop computer [1-3]. Compared with other types of electrolytes, solid polymer electrolytes have amounts of advantages such as good mechanical properties, light quantity, easy processing [4-6]. Solid polymer electrolyte has great potential applications in electrochemical devices: high energy batteries, electro chromic display devices, chemical sensors and polymer electrolyte fuel cells. Solid state polymer lithium ion batteries which use polymer material as electrolyte were consider to over safer and more reliable batteries for electric vehicles and domestic applications then other lithium ion batteries. But there are remaining some problems need resolved like low ion conductivity, poor interfacial properties, etc. PVDF and its copolymers used as matrix for solid polymer electrolyte had been extensively studied because of its high solubility, lower crystalline and lower glass transition temperature, which had high ion conductivity and low interfacial resistor [7-10]. In this study, a kind of porous solid polymer electrolyte was prepared by inversion method. The preparation processes of the classification of solution and the effect of temperature have been investigated. The influence of Al2O3 incorporated in porous solid polymer on the structure and properties have been examined. Moreover, a kind of polymer lithium ion battery which used this PVDF-HFP-based polymer electrolyte has been studied. Experiment Materials preparation. The PVDF-HFP (Aldrich，90%) was dissolved in a mixture solvent which mixed by organic solvent and non-organic solvent (the ratio of organic solvent to non-organic solvent was between 1:0.2—1:0.5). The solution was under continuous stirring about 4h with the rate at 200 rpm and kept the temperature at 60℃. The organic solvent was acetone and the non-organic solvent was water. A transparent and colloidal solution which containing about 7% PVDF-HFP was obtained. For preparing the composite porous solid polymer electrolyte, an appropriate amount of Al2O3 micron particles (D50 = 1.5 µm, A.R., Shanghai) was dispersed in the PVDF-HFP solution with help of an ultrasonic dispersed. The solution was then injected into a glass template and scratched by a doctor blade. A white porous solid polymer electrolyte was obtained after exposed to the ultraviolet light about 8 hours for volatile organic solvent and non-organic solvent at room temperature. Generally,