international conference on computer, communication...

International Conference on Computer,Communication, Chemical, Materials&Electronic Engineering

Faculty of EngineeringUniversity of Rajshahi, Bangladesh

24~25 March 2016

IC4ME2

Proceedings

ISBN: 978-984-34-0889-1

Proceedings

ISBN: 978-984-34-0889-1

ISBN:

978-984-34-0889-1

mailto:[email protected]

http://www.ru.ac.bd/icmeie2015/[email protected]

Foreword On behalf of the IC

4ME

2-2016, I warmly invite you to the International Conference on Computer,

Communication, Chemical, Materials and Electronic Engineering, IC4ME

2-2016, at the green premise

of the University of Rajshahi during 24~25 March, 2016.

The IC4ME

2-2016 is the second of its kind hosted by the Faculty of Engineering of University of

Rajshahi. The IC4ME

2-2016 continues the successful format from previous years ICMEIE-2015.

While having the same overarching goal of presenting cutting-edge results, ideas, techniques, and

theoretical advances in the mentioned theme, the IC4ME

2-2016 is separately tasked by focusing on

emerging topics that complement the areas covered by the main technical program.

The objective of organizing this conference is to bring together leading scientists, researchers and

scholars to exchange and share their experiences and research results about all aspects of Electrical,

Electronics, Communication, Chemical Engineering and IT, and discusses the practical challenges

encountered and the solutions adopted.

The international character of this meeting is illustrated by the participation of researchers from Fiji,

Germany, India, Japan, Malaysia, Nepal, and Sri Lanka. Among the huge number of submissions only

56% have been accepted for publication. The conference includes 6 keynote speeches, 2 invited

papers and 89 contributed papers distributed in 1 plenary session and 15 oral sessions.

The information presented herein should help open up new avenues for research and provide

researchers of the mentioned themes with new ideas to help them improve their production efficiency.

We thank the reviewers from various countries who did this thankless job even in their busy schedule.

The editorial team of this book deserves special thanks for their outstanding efforts in reviewing and

preparing the abstracts for publication. Sponsorship for this meeting is an important feature of its

success. On behalf of the organizing committee of IC4ME

2-2016, we thank the University Grants

Commission of Bangladesh for their support to promote the meeting.

Finally, we would like to thank the presenters for their willingness to share their latest research and

ideas. Without their efforts, this conference would not be possible. We hope you will enjoy your

staying at very beautiful campus of the University of Rajshahi.

Abu Bakar Md. Ismail, PhD

Chair

International Conference on Computer, Communication, Chemical,

Materials and Electronic Engineering, IC4ME

2-2016

Faculty of Engineering, University of Rajshahi

Rajshahi 6205, Bangladesh

International Conference on Computer, Communication, Chemical, Materials and Electronic Engineering

IC4ME

2-2016, 24~25 March, 2016

Contents

Program Schedule 08

Organizing Committee 10

International Advisory Committee 10

Technical Program Committee 12

Reception Committee 14

Budget, Finance and Sponsor Committee 14

Registration Committee 15

Publication Committee 15

Decoration and Discipline Committee 16

Accommodation Committee 16

Social Event and Tour Committee 17

Food and Refreshment Committee 17

Paper ID Title

Keynote Simulation of Normal Incidence Sound Absorption Coefficients of Perforated Panels

with/without Glass Wool by Transmission Line Parameters in a two-port Network

18

Takayoshi Nakai

Keynote Settlement of Crystalline Structure of Group II-VI Semiconductor Nanoparticles by

Profile Refinement Technique and Size Determination by Tight Binding Model

18

Surendra K. Gautam

Keynote Readerless RFID Transponder: A Concept 19

Mamun Bin Ibne Reaz

Keynote Science, Technology and Innovation: For Engineering Our Future 19

Aravind Chinchure

Keynote Progress of Low-Temperature Fabrication Technologies of Thin Film Transistors for

Preservation of Global Environment

20

Susumu Horita

Keynote Factors that Facilitate and Impede Hitherto Untried R&D in Engineering 20

Sisil Kumarawadu

Invited Water-in-oil Microemulsions as Nanoreactors to Prepare Nanoparticles with Tunable

Electrical, Optical, and Antibacterial Properties

21

Md. Abu Bin Hasan Susan, M. Muhibur Rahman and M. Yousuf A Mollah

Invited Physics and Technology in Radiation Oncology and Imaging 21

Golam Abu Zakaria

5 Fabrication of Cardiac Biomarker Immunosensor based on Three Different Electrode

Surfaces and Contrasting Their Efficiencies

23

Payal Gulati, Prabhash Mishra and Safiul Islam

9 Simulation of the Electrical Activity of Cardiac Tissue by Finite Element Method 27

Tanzina Rahman and Md. Rezaul Islam

10 Baking of Ilmenite on Moistening with Sulfuric Acid followed by Leaching with Dilute

Sulfuric Acid Solution

31

Ranjit K. Biswas, Aneek K.Karmakar, Jinnatul Ara and Muhammad A. Gafur

11 Thermal Treatment of Ilmenite on Moistening with Concentrated HF followed by

Leaching with Dilute Sulfuric Acid Solution

35

Ranjit K. Biswas, Mohammad A. Habib, Aneek K. Karmakar and Mohammad J. Alam


IC4ME

2-2016, 24~25 March, 2016

Paper ID Title

12 Solvent Extraction of V(V) from Nitrate Medium by Tri-n-Octylamine Dissolved in

Kerosene

39

Ranjit K. Biswas, Aneek K. Karmakar and Mottakin

13 Kinetics of Extraction of Ti(IV) from SO42-

Medium by Cyanex 301 Dissolved in

Kerosene

43

Ranjit K. Biswas and Aneek K. Karmakar

16 Production and Improvement of Waste Tire Pyrolysis Oil to be Utilized as Biofuel in

Diesel Engine

47

Md. Nurul Islam and Md. Rafsan Nahian

24 Biological Evaluation of Radiotherapy Treatment Plan for Different Field Techniques in

3-Dimensional Conformal Radiotherapy (3DCRT).

51

Kausar A, Azhari H A and Zakaria G A

25 Design of a Linearly Polarized Multi-Band Transmission Line Feed Microstrip Patch

Antenna for Wireless Communications

55

Sheikh Dobir Hossain, Md. Khalid Hossain and Rebeka Sultana

26 Design and Fabrication of an Unmanned Video Transmitting Tele-Bot using 3G GSM

Network

59

Md. Mamunoor Islam and Mehdi Hasan Chowdhury

29 Effect of Sintering Temperature on Nb+Nd Doped Bismuth Ferrite 63

Sadia Tasnim Mowri, M A Gafur, Quazi Delwar Hossain, Aninda Nafis Ahmed and

Muhammad Shahriar Bashar

30 Silicon Nanocrystals Rich Lanthanum Fluoride Films for Future Electronic Devices 67

Ferdous Rahman, Sk. Rashel Al Ahmed, Md. Golam Saklayen and Abu Bakar Md. Ismail

41 Study on the Displacement Effect at Cylindrical Ionization Chamber with different Radii

in High Energy Photon of Flat Beam and True Beams

71

Kumaresh Chandra Paul, Guenther H Hartmann, Enamul Hoque and Golam Abu Zakaria

42 Electrical and Optical Properties of Cu-Nanoparticles- Doped α-Fe2O3 Thin Film Spin-

Coated on Glass Substrate

75

Sanjida Ferdous, Afroza Yasmin, Jinia Sultana and Abu Bakar Md. Ismail

43 Study on Morphological Properties of Cu-NPs Doped α-Fe2O3 Thin Film deposited on

Glass Substrate

78

Jinia Sultana, Afroza Yasmin, Sanjida Ferdous and Abu Bakar Md. Ismail

47 MRI Segmentation using Fuzzy C-Means Clustering and Bidimensional Empirical Mode

Decomposition

82

Gulam Sarwar Chuwdhury, Md. Khaliluzzaman and Md. Rashed-Al-Mahfuz

48 Wear and Morphological Behavior of Electron Beam Dose Irradiated Polyoxymethylene

Copolymer (POM-C)

86

Md. Shahinur Rahman, Heon-Ju Lee, Muhammad Sifatul Alam Chowdhury and

Konstantin Lyakhov

49 Study of Structural and Optical Properties of Pyrolised CuO Films 90

M. Majhar, S. Ahmed, M. Mozibur Rahman and M. K. R. Khan

52 Algorithm for Performance Appraisal using CAW Method 94

M. Z. Ahsan and Md. Mamun-Ur-Rashid Khandker

56 Friction and Morphological Properties of Ion Implanted Polyoxymethylene Copolymer

(POM-C)

99

Md. Shahinur Rahman, Md. Mehedi Hasan, Muhammad Sifatul Alam Chowdhury and

Konstantin Lyakhov


IC4ME

2-2016, 24~25 March, 2016

Paper ID Title

57 Fabrication and Mechanical Characterization of Aluminium- Rice Husk Ash Composite

by Stir Casting Method

103

Adnan Adib Ahamed, Rashed Ahmed, Md. Benzir Hossain, Masum Billah

58 Analysis of Annual and Seasonal Precipitation Concentration Index (PCI) of North-

Western Region of Bangladesh

107

Ahsan Habib Rasel, Md Monirul Islam and Mumnunul Keramat

62 Bitwise Template Fusion of Noisy Images for Enhanced IRIS Recognition System 111

Sohel Ahammed and Biprodip Pal

65 Kinetics of Extraction of Ti(IV) from Sulfate Medium by Cyanex 302 115


66 Autonomous Human Face and Tracking System with Variant Poses, Blur and Illumination 120

Md. Zweel Rana, Monimul Islam and Mohiuddin Ahmad

67 Electrochemical Corrosion Characterization of Artificially Aged Al-6Si-0.5Mg (-1Cu)

Alloys in Sodium Chloride Solution

125

Abul Hossain, M. A. Gafur, Fahmida Gulshan and A S W Kurny

69 Effects of Inclusions on the Mechanical Properties of Structural Steel Reinforced Bars 129

Abul Hossain, Fahmida Gulshan and A S W Kurny

72 Utilizing Solar Energy in the Filling Stations of Bangladesh: Technical and Economical

Representation

133

Mohammad Jalal Uddin, Muhammad Sifatul Alam Chowdhury, Md. Ridwanul Karim, Md.

Arman Uddin and Md. Bakiuzzaman

74 Conversion of Prawn Shell Waste into Value Added Products for Textile Finishes 137

Md. Mofakkharul Islam, Firoz Ahmed and Md. Ibrahim H. Mondal

75 Textile Performance of Functionalized Cotton Fibre with Silane Coupling Agents 141

Md. Khademul Islam, Md. Abdul Aziz and Md. Ibrahim H. Mondal

77 Synthesis and Characterization of Hydrogels from Cellulosic Materials for Green

Adsorbent Products

145

Md. Obaidul Haque, Md. Abu Sayeed and Md. Ibrahim H. Mondal

83 Study the Encryption Techniques for Multimedia 149

Md. Martuza Ahamad and Md. Ibrahim Abdullah

84 Influence of Deposition Temperature on the Deposition of SiO2 Films from Reaction of

Silicone Oil Vapor and Ozone Gas

153

Arifuzzaman Rajib, Susumu Horita, Atowar Rahman and Abu Bakar Md. Ismail

85 An Improved Representation of Audio Signal in Time-Frequency Plane 158

Kazi Mahmudul Hassan, Ekramul Hamid and Takayoshi Nakai

86 On the Optimization of Number of Message Copies for Multi-Copy Routing Protocols in

Scalable Delay-Tolerant Networks

163

Md. Sharif Hossen and Muhammad Sajjadur Rahim

90 Emotional Bangla Speech Signals Classification using K-NN 168

Md. Tohidul Islam, Md. Ekramul Hamid and Somlal Das

92 Content Based Image Searching Using Multidimensional MSF 172

Saiful Islam, Ekramul Hamid and Emdadul Haque

93 Silicon Nanocrystals based Schottky Junction Solar Cell Fabrication and Characterization 177

A.T.M. Saiful Islam, Md. Enamul Karim, Arifuzzaman Rajib and Abu Bakar Md. Ismail

95 Fabrication and Characterization of α-Fe2O3 Homo-Junction Photocathode for Efficient

Solar Water Splitting

181

Arifuzzaman Rajib, Atowar Rahman, A.T.M. Saiful Islam and Abu Bakar Md. Ismail


IC4ME

2-2016, 24~25 March, 2016

Paper ID Title

97 A Practical Approach to Spectrum Analyzing Unit using RTL-SDR 185

Md. Habibur Rahman and Md. Mamunoor Islam

101 Fabrication of Bismuth Ferrite Multiferroic Perovskite Nanoparticles Using an Aqueous

Organic Gel Route

189

Mayeesha Haque, M. S. Parvez, M. S. Islam, M.A. Hakim and M. A. Gafur

105 Analysis of GLDAS data for Estimating and Distribution of Evapotranspiration and

Rainfall over Bangladesh

195

Md Ataur Rahman, Md Mainul Islam Mamun and Md Monirul Islam

113 Robustification of Logistic Classifer for Binary Classification in Microarray Gene

Expression Data

199

Md. Shahjaman, Md. Mushfiqur Rahman, Md. Manir Hossain Mollah, Anjuman Ara

Begum, S. M. Shahinul Islam and Md. Nurul Haque Mollah

115 Molecular Evolutionary Analysis of a-Defensin Peptides in Vertebrates 203

Arafat Rahman, M Sahidul Islam, Otun Saha and Titon Chandra Saha

117 Microencapsulated Probiotic Bacteria Protect the Spoilage of Functional Foods 207

Md. Symoom Hossain, Md. Abdul Alim Al-Bari, Mir Imam Ibne Wahed and

Md. Anwar Ul Islam

124 Preparation of Highly Cross-Linked Magnetic Polymer Composite Particles and

Application in the Separation of Arsenic from Water

212

M. K. Sharafat, H. Ahmad, M. A. Alam and M.M. Rahman

125 Preparation of Hydrophobic Poly((lauryl methacrylate)-Coated Magnetic Nano-

Composite Particles and their Application as Adsorbents for Organic Polutants

216

Rukhsana Shabnam and Hasan Ahmad

126 Statistical Methods for Functional Analysis of Metagenomes 219

Zobaer Akond and Md. Nurul Haque Mollah

127 Simulation of Microalgae and CO2 Flow Dynamics in a Tubular Photobioreactor and

Consequent Effects on Microalgae Growth

224

Saumen Barua, Mohammad Morshed Alam and Ujjwal Kumar Deb

137 Evaluation of PCA in spatial, frequency and wavelet domains for face recognition 229

Samsi Ara and M. Babul Islam

139 Time-Frequency Coherence Analysis of Multichannel Electroencephalography Signals

using Synchrosqueezing Transform

233

Md. Sujan Ali, Mst. Jannatul Ferdous, Md. Ekramul Hamid and Md. Khademul Islam

Molla

142 Experimental Study on Optical Characterization of Mono Crystalline Silicon Solar Cell 237

Nusrat Chowdhury, Md. Abdur Rafiq Akand and Zahid Hasan Mahmood

143 Canonical Correlation Analysis for SNP based Genome-Wide Association Studies 241

Atul Chandra Singha, Arafat Rahman, Md. Jahangir Alom and Md. Nurul Haque Mollah

148 Frequency Recognition of SSVEP for BCI Implementation using Canonical Correlation

Analysis with Adaptive Reference Signals

245

Shalauddin Ahamad Shuza, Md. Rabiul Islam, Md. Kislu Noman and Md. Khademul Islam

Molla

151 Expert Reviewer Detection from Online Experiential Product Reviews 249

Atiquer Rahman Sarkar

153 FPGA based Pulse Oximeter using VHDL 253

Farhana Binte Sufi, Md. Fahmidur Rahman and Md. Maruful Islam


IC4ME

2-2016, 24~25 March, 2016

8

Program Schedule

Conference Kit Distribution

23 March, 2016 11:00 am – 02:00 pm

05:00 pm – 08:00 pm

Conference Room

Department of CSE

4th

Science Building

University of Rajshahi

24 March, 2016 08:00 am – 08:50 am Senate Bhaban


Inaugural Session 24 March, 2016 09:00 am – 9:45 am Senate Bhaban


Keynote Session 24 March, 2016 10:00 am – 11:30 am

11:45 am – 01:15 pm

Senate Bhaban


Invited Talk 24 March, 2016 03:00 pm – 04:00 pm Senate Bhaban


Technical Session 24 March, 2016 04:30 pm – 06:00 pm 4

th Science Building

25 March, 2016 09:00 am – 12:30 pm 4th

Science Building

Keynote Session: 24 March, 2016 10:00 am - 1:15 pm Room # Senate Bhaban

Chair: Prof. M. Abdus Sobhan, University of Rajshahi, Bangladesh

Title

Simulation of Normal Incidence Sound Absorption Coefficients of Perforated Panels with/without Glass Wool

by Transmission Line Parameters in a Two-Port Network

Takayoshi Nakai

Settlement of Crystalline Structure of Group II-VI Semiconductor Nanoparticles by Profile Refinement

Technique and Size Determination by Tight Binding Model

Surendra K. Gautam

Readerless RFID Transponder: A Concept

Mamun Bin Ibne Reaz

Science, Technology and Innovation: For Engineering Our Future

Aravind Chinchure

Progress of Low-Temperature Fabrication Technologies of Thin Film Transistors for Preservation of Global

Environment

Susumu Horita

Factors that Facilitate and Impede Hitherto Untried R&D in Engineering

Sisil Kumarawadu


IC4ME

2-2016, 24~25 March, 2016

9

Invited Talk: 24 March, 2016 03:00 pm - 4:00 pm Room # Senate Bhaban

Chair: Prof. Mamun Bin Ibne Riaz, Kebangsaan Universiti, Malaysia

Title

Water-in-oil Microemulsions as Nanoreactors to Prepare Nanoparticles with Tunable Electrical, Optical, and

Antibacterial Properties

Md. Abu Bin Hasan Susan, M. Muhibur Rahman and M. Yousuf A Mollah

Physics and Technology in Radiation Oncology and Imaging

Golam Abu Zakaria

Technical Session

Session Chair Date & Time Paper ID Venue

1A Prof. Khademul Islam Molla


24 March, 2016

04:30 pm – 6:00 pm

62, 85, 90, 92, 137,

148

Room # 219

4th

Science Building

1B Dr. Surendra Kumar Gautam

Tribhuvan University, Nepal

10, 11, 16, 65, 74,

75

Room # 223

4th

Science Building

1C Dr. Susumu Horita

JAIST, Japan 3, 14, 23, 29, 30, 42

Room # 122

4th

Science Building

1D Prof. Abdur Razzak

RUET

25, 26, 83, 97, 151,

153

Room # 120

4th

Science Building

2A Prof. Md. Rabiul Islam

RUET

25 March, 2016

09:00 am – 10:30 am

45, 47, 52, 53, 66,

96

Room # 120

4th

Science Building

2B Prof. C. M. Mostofa


12, 13, 67, 76, 77,

101

Room # 219

4th

Science Building

2C Dr. Riazul Islam

University of Dhaka

43, 48, 49, 56, 69,

84

Room # 223

4th

Science Building

2D Prof. Abu Reza

University of Rajshahi 113, 126, 129, 143

Room # 122

4th

Science Building

3A

Prof. Golam Abu Zakaria

Anhalt University of Applied

Sciences, Germany

25 March, 2016

11:00 am – 12:30 pm

5, 9, 24, 41, 60, 139 Room # 120

4th

Science Building

3B Prof. Ranjit K Biswas


102, 115, 117, 125,

127, 157

Room # 219

4th

Science Building

3C Prof. Md. Abu Bin Hasan Susan

University of Dhaka

93, 95, 124, 156,

158, 159

Room # 223

4th

Science Building

3D Prof. Mamnunul Keramat


58, 72, 86, 105, 142,

152

Room # 122

4th

Science Building


IC4ME

2-2016, 24~25 March, 2016

10

Organizing Committee

Chair : Abu Bakar Md. Ismail, Ph.D

Dean, Faculty of Engineering & Professor

Dept. of Applied Physics & Electronic Engineering

University of Rajshahi, Bangladesh

Co-Chair : Professor Dr. Ranjit Kumar Biswas

Dept. of Applied Chemistry & Chemical Engineering


Secretary : Professor Mamun Ur Rashid Khandker



Treasurer : Professor Dr. Dipankar Das

Dept. of Information & Communication Engineering


Members:

Chairman, Dept. of Applied Physics & Electronic Engineering, University of Rajshahi

Chairman, Dept. of Applied Chemistry & Chemical Engineering, University of Rajshahi

Chairman, Dept. of Computer Science & Engineering, University of Rajshahi

Chairman, Dept. of Information & Communication Engineering, University of Rajshahi

Chairman, Dept. of Materials Science & Electronic Engineering, University of Rajshahi

Professor Dr. M. Mozaffor Hossain,

Dept. of Applied Physics & Electronic Engineering, University of Rajshahi

Professor Dr. M. Abdus Sobhan


Professor Dr. Mumnunul Keramat


Professor Dr. M. Rostom Ali

Dept. of Applied Chemistry & Chemical Engineering, University of Rajshahi

Professor Dr. M. Mamunur Rashid Talukder


Professor Dr. M. Khademul Islam Molla

Dept. of Computer Science & Engineering, University of Rajshahi

Engr. S. M. Rezaul Kabir

Principal, BCMC College of Engineering & Technology, Jessore

International Advisory Committee

Professor Dr. Surendra K. Gautam

Tri-Chandra Campus


Professor Dr. Sisil Kumarawadu

Dept. of Electrical Engineering

University of Moratuwa, Sri Lanka

Dr. D.M.G. Preethichandra

Discipline Leader – Electrical Engineering

School of Engineering and Technology

Central Queensland University, Australia


IC4ME

2-2016, 24~25 March, 2016

11

Professor Dr. Keikichi Hirose

Dept. of Information and Communication Engineering

The University of Tokyo, Japan

Dr. Keiji Nagai

Associate Professor

Chemical Resource Laboratory

Tokyo Institute of Technology, Japan

Dr. Wu Ping

Associate Professor

Division of Engineering Product Development

Singapore University of Technology and Design, Singapore

Professor Dr. Md. Mamun Bin Ibne Reaz

Dept. of Electrical, Electronic and Systems Engineering

University Kebangsaan Malaysia, Malaysia

Professor Dr. Hartmut Baerwolff

Dept. of Analog & Optoelectronics

Cologne University of Applied Sciences, Germany

Professor Dr. Tomokazu Iyoda

Chemical Resource Laboratory

Tokyo Institute of Technology, Japan

Professor Dr. Norihiko Kamata

Dept. of Functional Materials Science

Graduate School of Science and Engineering

Saitama University, Japan

Professor Yousuke Nakashima

Plasma Research Center

University of Tsukuba, Japan

Dr. Susumu Horita

School of Materials Science

Japan Advanced Institute of Science & Technology, Japan

Professor A B M Shawkat Ali

Department of Computer Science and Information Technology

Dean, School of Science and Technology

The University of Fiji, Fiji

Dr. Golam Zakaria

Dept. of Medical Radiation Physics

University of Cologne, Germany

Anis Haque, Ph.D, P.Eng.

Senior Instructor

Fellow, Institute for Sustainable Energy, Environment and Economy (ISEEE)

Associate Director of Students

Dept. of Electrical and Computer Engineering

University of Calgary, Canada

Dr. Mohammad Abdul Fazal

Senior Lecturer

University of Malaya, Malaysia


IC4ME

2-2016, 24~25 March, 2016

12

Technical Program Committee

Co-Chair : Professor Dr. C. M. Mostofa

Dept. of Applied Chemistry & Chemical Engineering


Secretary : Professor Dr. Shamim Ahmad

Dept. of Computer Science & Engineering


Members:

Professor Dr. Md. Ariful Islam Nahid


Professor Dr. M. Shameem Ahsan


Professor Dr. M. Taufiq Alam


Professor Dr. Ekramul Hamid


Professor Dr. A. K. M. Akhter Hossain


Professor Dr. Md. Nurul Haque Mollah

Dept. of Statistics, University of Rajshahi

Professor Dr. Md. Ziaur Rahman Khan

Dept. of Electrical & Electronic Engineering, BUET

Professor Dr. Zahid Hasan Mahmood

Dept. of Electrical & Electronic Engineering, Dhaka University

Professor Dr. M. M. A. Hashem

Dept. of Computer Science & Engineering, KUET

Professor Dr. Mohammad Abdul Goffar Khan

Dept. of Electrical & Electronic Engineering, RUET

Professor Dr. Md. Rafiqul Islam

Dept. of Electrical & Electronic Engineering, KUET

Professor Dr. Shahid Uz Zaman

Dept. of Computer Science & Engineering, RUET

Professor Dr. S. M. Abdur Razzak

Dept. of Electrical & Electronic Engineering, RUET

Professor Dr. Md. Anisur Rahman

Dept. of Computer Science & Engineering, Khulna University

Professor Dr. Mohammad Shahidur Rahman

Dept. of Computer Science & Engineering, Shahjalal University of Science & Technology

Professor Dr. Mohammad Iqbal

Dept. of Industrial & Production Engineering, Shahjalal University of Science & Technology

Professor Dr. Md. Mahbubur Rahman

Dept. of Computer Science & Engineering, MIST

Professor Dr. Mortuza Ali

Dept. of Electrical & Electronic Engineering, Eastern University, Dhaka

Professor Rezaul Karim Mazumder

Dept. of Electronics & Telecommunication Engineering, ULAB, Dhaka


IC4ME

2-2016, 24~25 March, 2016

13

Professor Dr. Jugal Krishna Das

Dept. of Computer Science & Engineering, Jahangirnagar University

Professor Dr. Farid Ahmed

Dept. of Physics, Jahangirnagar University

Professor Dr. Md. Shahjahan

Dept. of Applied Physics, Electronics & Communication Engineering, BSMRSTU

Professor Dr. M. Mahbubur Rahman

Dept. of Information & Communication Engineering, Islamic University

Professor Dr. M. Maniruzzaman

Dept. Applied Chemistry & Chemical Engineering, Islamic University

Professor Dr. Momtazul Islam

Dept. Applied Physics, Electronics & Communication Engineering, Islamic University

Dr. Bilkis Ara Begum

Head, Chemistry Division, BAEC, Dhaka

Dr. Shamshad Begum Quraishi

Chief Scientific Officer, Chemistry Division, BAEC, Dhaka

Dr. Samia Tabassum

Senior Scientific Officer, BCSIR, Dhaka

Dr. M. Babul Islam

Associate Professor, Dept. of Applied Physics & Electronic Engg., University of Rajshahi

Dr. Md. Shafiqul Islam

Associate Professor, Dept. of Nuclear Engineering, Dhaka University

Dr. Md. Atowar Rahman

Associate Professor, Dept. of Applied Physics & Electronic Engg., University of Rajshahi

Dr. Md. Nur-Al-Safa Bhuiyan

Associate Professor, Dept. of Information & Communication Engg., University of Rajshahi

Dr. Sabbir Ahmed


Dr. Md. Emdadul Haque


Dr. Asadul Hoque

Associate Professor, Dept. of Materials Science & Engineering, University of Rajshahi

Dr. M. Anwarul Kabir Bhuiya


Dr. G. M. Shafiur Rahman


Mr. Subrata Pramanik

Associate Professor, Dept. of Computer Science & Engineering, University of Rajshahi

Mr. Muhammad Sajjadur Rahim


Dr. N. A. Ruhul Azad

Lecturer & Programme Leader for Engineering Foundation, LBIC, Brunel University, UK

Dr. Md. Iqbal Aziz Khan

Assistant Professor, Dept. of Computer Science & Engineering, University of Rajshahi

Mr. Mahboob Qaosar


Mr. A. F. M. Mahbubur Rahman


Mr. M. Rashed Al Mahfuz


IC4ME

2-2016, 24~25 March, 2016

14


Reception Committee

Convener : Professor Rostom Ali

Dept. of Applied Chemistry& Chemical Engineering


Members:

Chairman


Chairman


Chairman


Chairman

Dept. of Information & Communication Engineering, University of Rajshahi

Chairman

Dept. of Materials Science & Engineering, University of Rajshahi

Chairman

Dept. of Electrical & Electronic Engineering, University of Rajshahi

Professor M. Mozaffor Hossain


Professor Dr. M. Abdus Sobhan


Professor Dr. Mumnunul Keramat


Budget, Finance and Sponsor Committee

Convener : Professor Abu Bakar Md. Ismail

Dean, Faculty of Engineering, University of Rajshahi

Members:

Professor Md. Ekramul Hamid


Professor M. Ahsan Habib


Dr. G. M. Shafiur Rahman


Dr. Nur Al Safa Bhuyan



IC4ME

2-2016, 24~25 March, 2016

15

Registration Committee

Convener : Professor Mamun Ur Rashid Khandker

Dept. Applied Physics & Electronic Engineering, University of Rajshahi

Members:

Professor Shameem Ahsan


Dr. M. Babul Islam


Muhammad Sajjadur Rahim


Dr. Sabbir Ahmed


Dr. Anwarul Kabir Bhuiya


Dr. M. Iqbal Aziz Khan


Mahboob Qaosar


Publication Committee

Convener : Professor Shamim Ahmad


Members:

Dr. M. Babul Islam


Muhammad Sajjadur Rahim


Dr. Md. Emdadul Haque


Dr. Sabbir Ahmed


Dr. M. Asadul Hoque


Dr. Anik K Karmakar


Foez Ahmed


A.F.M. Mahbubur Rahman


Farhana Binte Sufi


Sangeeta Biswas



IC4ME

2-2016, 24~25 March, 2016

16

Decoration and Discipline Committee

Convener : Professor Md. Ekramul Hamid


Members:

Professor Rubaiyat Yasmin


Dr. M. Abdul Matin


Dr. Halida Homyara


Dr. Sinthia Shabnam Mou


Mahboob Qaosar


Sanjoy Kumar Chakravarty


Sangeeta Biswas


Shammi Farhana Islam


Saiful Islam


Mousumi Haque


Accommodation Committee

Convener : Dr. M. Babul Islam


Members:

Professor Shamim Ahmad


Professor Md. Ekramul Hamid


Mirza A. F. M. Rashidul Hasan


Dr. Md. Asadul Haque


Dr. Sabbir Ahmed


Md. Morshedul Arefin


Khairul Islam


Sajjadul Kabir



IC4ME

2-2016, 24~25 March, 2016

17

Social Event and Tour Committee

Convener : Professor Shaikh Enayet Ullah


Members:

Professor Syed Mustafizur Rahman


Dr. M. Atowar Rahman




Utpalananda Chowdhury


Sajjadul Kabir


Food and Refreshment Committee

Convener: Professor Md. Rezaul Islam

Dept. Applied Physics & Electronic Engineering, University of Rajshahi

Members:

Professor Dr. M. Mamunur Rashid Talukder


Professor Abu Zafor Muhammad Touhidul Islam


Dr. Aurangzib Md. Abdur Rahman



Dept. of Materials Science & Electronic Engineering, University of Rajshahi

Dr. M. Hasnat Kabir


Md. Rokonuzzaman


Abu Mohammad

Dept. of Materials Science & Electronic Engineering, University of Rajshahi

Dilip Kumar Sarker



IC4ME

2-2016, 24~25 March, 2016

18

Simulation of Normal Incidence Sound Absorption Coefficients of

Perforated Panels with/without Glass Wool by Transmission Line

Parameters in a two-port Network

Takayoshi Nakai

Professor

Department of Electrical and Electronic Engineering

Shizuoka University, Japan

ABSTRACT

This paper describes simulation of normal incidence sound absorption coefficients of

perforated panels by transmission line parameters in a two-port network. Maa and

Sakagami have investigated micro perforated panels, MPP. But their theories can treat

only near 1% perforation rates of perforated panels with back cavities. If sound

propagates as a plane wave, sound propagation can be represented as transmission line

parameters in a two-port network. Perforated panels, back cavities, and glass wool

absorption materials are represented as matrix of transmission line parameters,

respectively. Transmission line parameters of a perforated panel with a back cavity are

calculated as multiplication of their matrices. An input impedance can be calculated from

the transmission line parameters. A normal incident absorption coefficient is calculated

from the input impedance. Holes of the perforated panels have losses of viscous friction

and thermal conduction at their walls. Simulations are done in the condition of 0.25 mm

to 5 mm diameters of holes, 0.25 % to 25 % perforation rates, 0.5 mm to 5 mm thickness

of the perforated panels with back cavities in which there are or are not glass wool

absorption materials. The results of these simulations are good agreements with the

results of our measurements by transfer function method except in the condition of more

than 1 mm diameter of holes.

Settlement of Crystalline Structure of Group II-VI Semiconductor

Nanoparticles by Profile Refinement Technique and Size

Determination by Tight Binding Model

Dr. Surendra Kumar Gautam

Department of Chemistry


ABSTRACT

Group II-VI semiconductor nanoparticles have gained huge interest both in fundamental

research and technical applications due to their unique optical and electrical properties.

They have extensive range of applications in the field of opto-electronic devices such as

light emitting diodes (LEDs), bio-sensors, photo-detectors, solar cells etc. The properties

of such semiconductor nanoparticles are dependent on their crystal structure and size.

The settlement of crystalline structure of those nanoparticles is done by profile

refinement of X-ray diffraction (XRD) pattern. The size quantization effect and blue-

shift resulting in the change of band gap with crystalline size are studied from optical

absorption spectra. Particle sizes are calculated by Tight Binding (TB) model. The

verification of particle size and the crystalline structure of as-synthesized nanocrystals

are further carried out from Transmission Electron Microscopy (TEM) images and

Selected Area Electron Diffraction (SAED) patterns.

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

19

Readerless RFID Transponder: A Concept

Mamun Bin Ibne Reaz

Professor

Department of Electrical Electronic and Systems Engineering

Universiti Kebangsaan Malaysia

Bangi, 43600 Selangor

Malaysia

ABSTRACT

RFID is a technology that enables the non-contact, automatic and unique identification of

objects using radio waves. It is projected that the RFID market will be worth more than

US $25 billion in 2018. However, RFID system suffers from limited address space, local

mobility, security and privacy. Above all, it is a monopoly business with few vendors,

which are trying to dominate the market with proprietary standard of RFID reader. In

order to overcome this major issue, we are proposing an RFID tag communicating with

the existing wireless network interface card (WNIC) instead of the reader. In this novel

RFID transponder, IPv6 address will be used to provide a universal identification number

to the objects with seamless address space, global mobility and data security. The

existing EPC (Electronic Product Code) of RFID will now directly map into IPv6

address by using auto configuration method. This talk will mainly focus on different key

issues related to this readerless RFID system and suggests the mechanism of reducing

significant cost, physical location detection and usage of global unique address.

Science, Technology and Innovation: For Engineering Our Future

Aravind Chinchure

Chair Professor

Centre for Enterpreneurship & Innovation Symbiosis International University

Pune, India

ABSTRACT

Every third person in this world today subsists with income less than 2 dollars a day.

Majority of these people live in Asian countries. The rising socio-economic inequality

and climate change are posing biggest risk to the world. The world is also moving

towards knowledge-based competencies and industries where the emphasis is not on

tangible assets, but on intangible knowledge assets, which is good news for the

developing countries. Today, world’s major knowledge industries are based on

telecommunication, microelectronics, new materials, and information technology. This

offers a great opportunity to researchers from academia and industry from Asian

countries to appropriately engineer the future of the nation and society by developing

innovative solutions to cater to the needs of the people for the sustainable and inclusive

development. To reap the full benefit of the emergence of knowledge-based industry

requires building a new culture in academia and industry that seamlessly connects

science, technology and innovation with relevance. This talk provides several examples

of academic institutions, professors, researchers who have been able to successfully

leverage science, technology and innovations for national and social good. I will also

present new ideas that are emerging and debated in the world on the cost-conscious

frugal science and technology.

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

20

Progress of Low-Temperature Fabrication Technologies of Thin Film

Transistors for Preservation of Global Environment

Dr. Susumu Horita

Associate Professor

School of Materials Science

Japan Advanced Institute of Science and Technology, Japan

ABSTRACT

Low-temperature fabrication technology can contribute enhancement of preservation of

global environment due to reduction of not only power or natural source consumption

but also greenhouse effect. So, as an example, we have been studying on low-

temperature fabrication of poly-or microcrystalline silicon (poly-Si) films on

temperature-sensitive and cheap substrates. The appropriate applications of poly Si are

thin-film transistor (TFT) in an active matrix flat panel display, solar cells, and so on

because of its higher reliability and higher mobility. For future application, industry

requires shorter annealing time, lower annealing temperature, more uniform electrical

property such as mobility, threshold voltage, and so on in a whole substrate area. For

meeting these requirements, we have been investing solid-phase crystallization of Si film

on a glass by using pulsed laser annealing(PLA) with crystallization-induction (CI) layer

of yttria-stabilized zirconia [(ZrO2)1-x(Y2O3)x :YSZ]. PLA method can crystallize Si films

effectively at room temperature because of its short pulse duration time less than 10 ns.

The YSZ CI layer can transfer its crystalline information to crystallized Si on a glass so

that we can obtain higher and more uniform crystalline quality of Si films.

As another important technology for TFT, we have low-temperature fabrication of

insulator, e.g, oxide film, in particular, for gate layer. Our group uses atmospheric

pressure CVD (AP-CVD) with silicone oil and ozone gas to obtain Si oxide. As you

know, silicone oil is a safety material for human body, chemically stable, and cheap, and

ozone is an indispensable substance for global environment. By using this technology,

we can produce a SiO2 film at 200 to 300 0C.

In this conference, our previous and current research results on the above low

temperature technologies are presented, including new two-step method in PLA for

much improving film quality and characteristics of Si TFTs fabricated by the above

techniques.

Factors that Facilitate and Impede Hitherto Untried R&D in

Engineering

Dr. Sisil Kumarawadu

Professor

Department of Electrical Engineering

University of Moratuwa, Sri Lanka

ABSTRACT

Completing a research & development (R&D) or postgraduate research project requires

stamina, determination, and willingness to stretch your intellectual and emotional

capabilities. An unmistakable initial momentum is vital to avoid stall out at some point

when working on a research project as it may lead to feel as if there is no light at the end

of the tunnel, or encounter disappointments or unexpected setbacks, or even

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

21

embarrassments. Not to be confused with procrastination or self-doubt, which is a mental

road-block, second-guessing at the conception of the R&D project is to guess, predict or

anticipate what you will encounter during the project duration and what you will finally

end up with. This is quite challenging as the research project opportunities that come

along the way of a researcher are rarely repetitions of previous experiences (hitherto

untried). Right second-guessing requires some quality time for an effective literature

review process, peer consultation, reflection, mulling things over and sitting with your

thoughts. The speaker intends to use his close to two decades long experience in

academic and industrial research projects as well as at postgraduate and undergraduate

levels to discuss, with some real world examples, the factors that facilitate and impede

hitherto untried R&D efforts in engineering & technology.

Water-in-oil Microemulsions as Nanoreactors to Prepare

Nanoparticles with Tunable Electrical, Optical, and Antibacterial

Properties

Md. Abu Bin Hasan Susan

Professor

Department of Chemistry, University of Dhaka

Dhaka 1000, Bangladesh

ABSTRACT

Nanomaterials with tunable electrical, optical and antibacterial properties have been a

fascinating domain of current research for their promising application in diverse areas. In

this work, we report preparation, characterization and applications of metal and metallic

oxide nanoparticles, core@shell nanoparticles and polymer-nanocomposites from water-

in oil (w/o) microemulsions as nanoreactors. Attempts have been made to tune electrical,

optical and antibacterial properties of the nanoparticles and nanocomposites by

controlling parameters for preparation of w/o microemulsions.

Physics and Technology in Radiation Oncology and Imaging

Golam Abu Zakaria

Professor

Department of Electrical, Mechanical and Industrial Engineering

Anhalt University of Applied Sciences, Koethen, Germany

ABSTRACT

Medical Physics is the application of physics concepts, theories and methods to medicine

or healthcare. On the other hand, biomedical engineering is the application of

engineering principles and design concepts to medicine and biology for healthcare.

Medical physicists and biomedical engineers play a vital and often leading role for any

medical research team. Their activities cover some key areas such as cancer, heart

diseases and mental illnesses. In cancer treatment, they primarily work together on issues

involving imaging and the radiation oncology. Thus the medical physicist/biomedical

engineer plays a mandatory role in every radiation oncology team.

The capability of controlling the growth of any cancer with radiation dose is always

associated with the unavoidable normal tissue damage. Accordingly, many physical-

technical developments in radiotherapy facilities are aimed to give a maximum radiation

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

22

dose to tumour cells and – at the same time - minimize the dose to the surrounding

normal tissue.

For that reason, 60-Co irradiation units were developed in the 50ties and medical linear

accelerators in the following decades. Last but not least, neutrons, protons and even

heavier ions have also been applied. At the same time, treatment calculation and delivery

methods have continuously been improved from conventional multi-beam techniques to

tumour shape conformal methods such as radio surgery, Intensity Modulated

Radiotherapy (IMRT), Image Guided Radiotherapy (IGRT), Stereotactic Body Radiation

Therapy (SBRT) tomotherapy and brachytherapy (BT).

The concentration of dose to tumour requires precise information of the shape and the

anatomical geometry of the tumour within the body. The techniques providing such

pieces of Information in a visible form is summarized by the term “Imaging”. X-ray has

played a dominant role almost from the time of its discovery in 1895. Up to now, the use

of x-rays has been extended to tomographic imaging with Computer Tomography (CT)

and other imaging modalities like Ultrasound (US), Magnetic Resonance Imaging (MRI)

or Positron Emission Tomography (PET) which have been developed over the last

decades. By their combined use, the required information level on the clinical tumour

target volume for radiotherapy has been tremendously raised.

The physical and technical development of radiation oncology and imaging are discussed

in this talk covering aspects of biology as well.

ISBN: 978-984-34-0889-1

International Conference on Computer, Communication, Chemical, Materials and Electronic Engineering IC4

ME2-2016, 24~25 March, 2016

23

Fabrication of cardiac biomarker Immunosensor based on

three different electrode surfaces and contrasting their

efficiencies

Payal Gulati, Prabhash Mishra, S.S.Islam*

Centre for Nanoscience and Nanotechnology

Jamia Millia Islamia,

New Delhi-110025, India

* [email protected]

Abstract— Myoglobin is important biomarker for

the detection of cardiac abnormalities like acute

myocardial infarction because it is the first to release

after the damage. Accordingly, a peculiar label-free

electrochemical immunosensor is fabricated to detect

myoglobin based on three different electrodes like

glassy carbon, Indium tin oxide glass and porous silicon.

All the electrodes were functionalized with GPMS

resulting in highly reactive epoxy groups on their

surface which covalently binds with the amino group of

Monoclonal Anti-Myoglobin Human antibody. Finally,

sensing of the electrodes was done with Ag-Mb in a

linear range from 0.01 to 1.00µg/ml in PBS buffer (pH

7.4) by using cyclic voltammetry technique. All the

electrodes responded to the stepwise changes done on

their surface but out of these, glassy carbon electrode

was found to be highly sensitive as it showed more

current change with respect to small change in the

antigen concentration.

Keywords—Electrochemical immunosensing, cyclic

voltammetry, GC, PS and ITO.

I. INTRODUCTION

Cardiovascular disease (CVD) [1] is a life threatening disorder that affects heart and blood vessels. Coronary heart disease is a most common form of CVD, associated with two major clinical form that is heart attack (often known as Acute Myocardial Infarction) and angima. An Acute Myocardial Infarction (AMI) occurs when heart blood vessel is suddenly blocked, damaging the heart muscle and its function causing cell death. To predict CVD risk, cardiac biomarkers can be identified in the bloodstream which provides therapeutic value in medical applications. An ideal biomarker should have high sensitivity and specificity whereas on the other hand it should be quickly released in blood enabling early diagnosis.

Myoglobin [2] (17.8KDa) is an iron- and oxygen- binding protein found in the skeletal muscles and heart of vertebrates. Levels of myoglobin start to rise within 2-3 hours of heart attack or other muscle injury reach their highest level within 8-12 hours and generally fall back to normal within one day. Normal level of myoglobin in serum is 10-65ng/ml and elevates to 200ng/ml after onset of AMI.

Electrochemical biosensors [3] based detection offer sensitivity, selectivity and reliability, making

them very attractive tools for biomarker protein detection. Due to their low cost, low power and ease of miniaturization, electrochemical biosensors hold great promise for sensing applications as compared to those tedious, time consuming multi-stage process used in hospitals like ELISA (Enzyme linked immuno sorbent assay), fluorescence, Radioimmunoassay.

ITO (Indium Tin Oxide) glass provides certain attractive properties like excellent adhesion properties to the substrate, surface stability under harsh condition and it has good conductivity. GC is used for electrochemical sensing purpose because of its low electrochemical resistivity, high chemical resistance, good electrical conductivity and it is biocompatibility. PS is the etched form of silicon wafer, which has high surface area to volume ratio in order to increase adherence to the large molecules about micrometer range and it also exhibits high biocompatibility. For immobilization of Antibodies, Enzymes or DNA on the electrode surface requires functional interlayer of organic SAM (Self- assembled monolayer) like GPMS (3-Glycidoxypropyl trimethoxy Silane) [4].

In this work, we report a planar ITO, Glassy Carbon and Porous Silicon based immunosensor functionalized with GPMS silane whose exposed epoxy groups readily reacts with amino groups of the antibody. Finally sensing of myoglobin was done by cyclic voltammetry in a range from 0.01µg/ml to 1µg/ml. In order to compare the sensitivity of all the electrode surfaces, Anodic peak Current v/s Myoglobin Conc. plot was made.

II. EXPERIMENTAL PROCEDURE

A. Conditioning & development of electrode

The selected electrodes were conditioned for the immunosensor fabrication. Due to highly conductive nature of Indium- tin oxide coated glass electrode, it was taken as a planar surface for the bio-electrode formation. It is a high quality glass because it is not affected by moisture. The ITO coated glass was cut into (5cm × 0.8cm). Then electrodes were cleaned ultrasonically with acetone, ethanol and water for 10 min each respectively and dried. Further, they were immersed into 1M HCl for 10 min. Then wash with De-ionised water. Then immersed in solution (1:1:5) v/v H2O2 (30%) / NH4OH (30%) /H2O (Pirhana

ISBN: 978-984-34-0889-1

mailto:[email protected]


IC4ME

2-2016, 24~25 March, 2016

24

solution). Finally, rinse with DI water and Dried under the steam of N2.

Similarly, glassy carbon having high conductivity

was also used as planar surface for the bio-electrode

formation. The glassy carbon electrode (5mm in

diameter), was cut into 1cm length pieces. Then

electrodes were polished with rough and smooth

sandpaper. Further, they were boiled in HNO3 for 1

hour. Then wash with DI-water and air dried. In the same way, the p-Si wafer [5,6] (100) with a

resistivity: 1-10Ωcm, thickness: 356-406 µm was anodized in Teflon cell using HF: DMF (1:3) electrolyte with current density: 30mA/cm

2 for 40 min

etching time6 to obtain porous silicon of high surface

to volume ratio.

B. Fabrication of immunosensor

These activated electrodes were silanized with 10 ml of 5% (3-Glycidoxypropyl) trimethoxysilane (GPMS) in toluene for 18hr at room temperature to form self-assembled monolayer of it, acting as necessary linker molecules to immobilize biomolecules on solid electrode surface. After this treatment, electrode surface contains an active epoxy group which reacts with amino groups present on the antibody molecules. Further these functionalized electrodes were then immobilized with 100µg/ml monoclonal anti-myoglobin human antibody (produced in mouse, Sigma Aldrich) in PBS buffer pH=7.4 for 24 hours at 4°C. Wash these electrodes with PBS buffer to remove physically adsorbed antibodies and then incubate in a 1% Bovine serum albumin (BSA) in PBS (pH=7.4) for 1 hour at 37

ᵒ C to

block the non-binding sites present on the electrode surface. Again rinse the electrodes with PBS buffer. Finally, sensing of these bio-electrodes was done after they were incubated with different Myoglobin (from equine heart) concentration varying in a linear range: 0.01µg/ml, 0.05µg/ml, 0.10µg/ml, 0.05µg/ml, and 1.00µg/ml in PBS buffer (pH=7.4) for 1 hour at room temperature.

C. Characterization

Scanning Electron Microscopy (SEM) was used to study the surface morphology of the porous silicon i.e. porosity of the porous silicon using NOVA NANOSEM 450 model.

Cyclic Voltammetry is a potentio-dynamic electrochemical method which is used to study the resulting current change of the modified electrode surface in an electrochemical cell. Cyclic voltammetry was conducted on Solatron 1280 C Potentiostat/Galvenostat with conventional three electrode system in which Ag/AgCl was used as a reference electrode, Platinum as counter electrode and ITO, Glassy Carbon, Porous Silicon as a working electrode. The alterations in the cathodic- anodic peak current and peak potentials of working electrode were studied using 5mM concentration of redox mediators K3Fe(CN)

-36/ K4Fe (CN)

-46 in PBS buffer (pH-7.4)

with potential range from -0.9 to +0.9V at the scan rate of 50mV/s.

III. RESULT & DISCUSSIONS

Fig1 shows the formation of porous silicon having a pore size in a range of 4-5µm making it suitable for the immunosensor fabrication. The purpose to obtain highly porous sample is for the proper attachment of antibody on the electrode surface, resulting in uniform immobilization of antibody.

Fig. 1: SEM image of PS

Cyclic voltammetry measures the resulting current in

an electrochemical cell by cycling the potential of the

working electrode. As we can see in the fig1, 2, 3;

(step a) well defined cathodic and anodic peaks (Epc

& Epa) was obtained because activated electrode

surface contains –OH groups. After silanization i.e.

treating the electrode with GPMS (in step b), we

found that there was significant decrease in current

level indicating the SAM formation on the electrode

surface rendering it insulating property.

Fig. 2: CV spectra of Cleaned ITO (a), GPMS treated

(b), monoclonal anti-myoglobin human antibody (c),

BSA treated (d).

Fig. 3: CV spectra of bare PS (a), GPMS treated (b),

monoclonal anti-myoglobin human antibody (c), BSA

treated (d).

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

25

Fig. 4: CV spectra of cleaned GC (a), GPMS treated

(b), monoclonal anti-myoglobin human antibody (c),

BSA treated (d).

Further (in step c) immobilization of monoclonal

anti-myoglobin human antibody whose amine groups

were linked to the epoxy groups of GPMS; there was

very slight increase in cathodic and anodic peak

current (ipc & ipa) due to presence of non-binding sites

present on the electrode surface which allows

electron to flow through the surface. Eventually,

when non-binding sites present on the electrode

surface was blocked by treating electrode with BSA

solution (in step d), it was found that there was

significant decrease in the cathodic current (ipc) and

peak–to-peak separation was increased. This shows

that remnant surface of electrode for electron transfer

was occupied by the protein i.e. BSA.

Fig. 5: ITO electrode based CV spectra of different

myoglobin concentration with myoglobin antibody:

monoclonal anti-myoglobin human antibody (a), 0.01

µg/ml (b), 0.05 µg/ml (c), 0.10 µg/ml (d), 0.50 µg/ml

(e), 1.00 µg/ml (f).

Fig. 6: PS electrode based CV spectra of different




(e), 1.00 µg/ml (f).

Fig. 7: GC electrode based CV spectra of different




(e), 1.00 µg/ml (f).

It is observed from C-V studies that same pattern of

result was observed on all substrates while studying

different antigen (Myoglobin) concentration anodic

peak current was different of every electrode with

respect to different concentration. A comparison plot

of efficiencies among all the three electrodes is made

to determine the most sensitive material where

sensitivity is calculated from the slope of the figs.

It is also observed that as the concentration of antigen

increases the current level decreases because of the

immune-complex formation between antigen-

antibody. This spectra indicates as the concentration

of antigen goes up, electron transfer is blocked on the

surface.

Fig. 8: Current v/s Myoglobin Conc. plot achieved

from cyclic voltammetry studies

Fig.8 shows that GCE is highly sensitive in

comparison to those materials as it is a stable,

unreactive material and forms strong covalent binding

upon functionalization. Being a carbon form it is

highly conductive to electrons and has great

electrochemical conductivity exhibiting good

repeatability, reproducibility and fast electron transfer

kinetics. The reason for PS being not as sensitive as

GC is due to surface instability because of the

presence of highly reactive Silicon Hydride species

that are very reactive both in air and water. Thus PS

substrate must be made stabilize by certain

modification to use for biosensing purpose. Similarly,

ITO glass being not as sensitive as GC because of the

inhomogeneous deposition of In & Sn on the glass

surface resulting in surface instability.

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

26

IV. CONCLUSION

All the bio-electrodes developed are sensitive for the

lowest antigen detection limit upto 10ng/ml. But

glassy carbon electrode surface is highly sensitive in

comparison to other two materials as it showed large

change in current response with respect to small

change in the myoglobin concentration. The

advantage of these immunosensor is that they are

very cheap and highly sensitive for abnormal

myoglobin level detection in patient’s serum with

cardiac problems. Another advantage is that an

untrained person can also use it.

REFERENCES

[1] Barry McDonnell, Stephen Hearty, Paul Leonard, Richard O'Kennedy Clinical Biochemistry 42 (2009) 549–561.

[2] Anjum Qureshi, Yasar Gurbuz, Javed H. Niazi Sensors and Actuators B 171– 172 (2012) 62– 76.

[3] DorotheeGrieshaber, Robert MacKenzie, Janos Voros and Erik Reimhult Sensors 2008, 8, 1400-1458.

[4] Mamas I. Prodromidis Electrochimica Acta xxx (2009) xxx–xxx.

[5] Werner Kern J. Electrochem. Soc., Vol. 137, No. 6, June 1990.

[6] Kumari, Vinita; Gulati, Payal; Mishra, Prabhash; Islam, S.S. Advanced Science Letters, Volume 20, Numbers 7-9, pp.1574-1577(4).

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

27

Simulation of the Electrical Activity of Cardiac Tissue by

Finite Element Method

Tanzina Rahman

Dept. of Applied Physics and Electronic

Engineering


Rajshahi, Bangladesh

e-mail:[email protected]

Md.Rezaul Islam

Dept. of Applied Physics and Electronic

Engineering


Rajshahi, Bangladesh

e-mail: [email protected]

Abstract—The electrical activity is responsible for

the periodic contraction and relaxation cycle of the

human heart. Significant implications of simulating

electrical activities are helpful to understand cardiac

abnormalities like cardiac arrhythmias. Mathematical

modeling of heart provides a better understanding for

the complex biophysical phenomena related to electrical

activity in the heart. Various reaction-diffusion models

have been developed to study the proper function of

human heart at different conditions. In this research

work monodomain model which is coupled with the

single cell FitzHugh-Nagumo model is used to

simulation the electrical activities. Two dimensional

monodomain model equations on a general domain with

equal isotropy and no fiber orientation are considered.

Finite element method which has been widely used as an

analysis and design tool is used to deal with the complex

monodomain model equations. For35×35 nodal elements

current above the threshold values is applied to the

middle node and less than threshold to the others. The

outcome of the simulation shows variations of excitation

propagation for uniform time steps.

Keywords—Electrical Activity of the Heart, Bidomain

and Monodomain model, Finite lement method.

I. INTRODUCTION

Electrical activity of cardiac tissue is an important part of bio-medical science. Computer simulation is becoming an important tool in cardiovascular research. We are on the brink of a revolution in cardiac research, one in which computational modeling of proteins, cells, tissues, and the organ permit linking genomic and proteomic information to the integrated organ behavior, in the quest for a quantitative understanding of the functioning of the heart in health and diseases [1]. Mathematical model of cardiac electrical activity has been recognized as one of the significant approaches capable of revealing diagnostic information about the heart. The electrical activity of the heart is an important tool for the primary diagnosis of the heart diseases; it shows the electrophysiology of the heart and the ischemic changes may cause myocardial infection, conduction defects and arrhythmia [1]. The electrical activity of the cardiac as a whole is thus characterized by a complex multi scale structure, ranging from the microscopic activity of ion channels in the cellular membrane to the macroscopic properties of the anisotropic propagation of the excitation and recovery fronts in the whole cardiac. Mathematically, reaction–diffusion systems take the form of semi-linear

parabolic partial differential equations. In order to describe electrical activity in the whole heart, a single cell model with the Partial differential equations model that describes how electricity flows across a network of cells [2]. The most complete model of such a complex setting is the anisotropic bidomain model that consists of a system of two degenerate parabolic reaction diffusion equations describing the intracellular and extracellular potentials in the cardiac muscle, coupled with a system of ordinary deferential equations describing the ionic currents flowing through the cellular membrane [3]. But this model requires a long simulation time, large computer memory. So in this research monodomain model is used. The technique of finite element method has been used to build a computer program to solving the phenomena propagation of excitations. The finite element method (FEM) has been widely used as an analysis and design tool in many engineering disciplines like structures and computational fluid mechanics. The FEM method is a powerful tool for solving differential equations. The method can easily deal with complex geometries and higher-order approximations of the solution [4]. A domain of interest is represented as an assembly of finite elements.

II. BIDOMAIN MODEL

Bidomain is a structure defining a model of heart tissue consisting of two interpenetrating domains representing cardiac cells and the surrounding space. It is one of the two differential equation based models for cardiac electrical activity [5]. The model is considered as the mathematical equations that have been used for simulating cardiac electrophysiological waves for years taking into account the non-linear dynamic nature of the cardiac signal and giving realistic simulation. This model gives the representation of the cardiac tissue at a macroscopic scale by relating the transmembrane potential, the extracellular potential and the ionic currents. Heart tissue can be classified into two groups: intracellular and extracellular as shown in fig. 1. It consists of a system of two non-linear partial differential equations coupled to a system of ordinary differential equations [6]. The set of bidomain equations is currently the most complete mathematical models for describing the spread of cardiac electrical activity, especially for simulating activity on the organ level. Conductivity is

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

28

usually greater along the fibers rather than across them [5, 6].

Fig. 1. Bidomain model

The bidomain model of cardiac tissue is based on current flow, distribution of electrical potential, and the conservation of charge and current [6]. The description of each domain is based on a generalized version of Ohms law defining the relationship between the electric field E, derived from the potential

(V), the current density J and the conductivity tensor D. So we have

E (1)

DDEJ

(2)

Now in case of the intracellular and extracellular

spaces we have

iii DJ

eee DJ

Where Ji and Je are the intracellular and extracellular current densities, Di and De are the corresponding

conductivity of the tensors, respectively i and e are the electrical potential in the intracellular and extracellular spaces.

In this paper we are considering the heart in isolation. Hence, a change in current density will be of equal magnitude in both domains but will have the opposite sign:

ei JJ (3)

0)( ei JJ (4)

Now

mi IJ

me IJ

where Im is transmembrane current per unit volume which is composed of a capacitive component and an ionic component Iion. So we have

applion

mmm II

t

VCI

)( (5)

Here Cm is the specified cell membrane capacitance, Iappl is the stimulus current and Vm is the transmembrane voltage which is given by

eimV (6)

Combing (4) and (5) we have

applion

mmemi II

t

VCVD

)()(.

(7)

( ).()).(( mieie VDDD

(8)

Equation (7) is the parabolic equation and (8) is the

elliptic equation [61, 62]. Those are known as the

governing equations of the biodomain model of

cardiac tissue.

III. MONODOMAIN MODEL

The monodomain model is a simplification of the bidomain model that is easier to analyze. It is also notable that computational cost of using the monodomain model is about one-half to one-tenth the cost of using the bidomain model, depending on the complexity of the cell model used [7].

This model helps to understand the patterns of electrical conduction and propagation from the scale of a single tissue to whole heart. In this physical model the cell membrane is viewed as an electrical network with the fibers of myocardial cells constituting a cable [7]. In this analysis, it is assumed that the anisotropy of the intracellular and extracellular spaces is the same, i.e. that the conductivity in the extracellular space is proportional to the intracellular conductivity.

ie DD (9)

Here is a scalar, which representing the ratio between the conductivity of the intercellular and

extracellular spaces. The choice of the value of can determines physiological accuracy, but it is important to select a suitable value that gives the satisfactory results [1, 7].

Substituting (9) into (8) we get

).()).(( mieie VDDD (10)

).()1

1().( miei VDD

(11)

Substituting (11) into (7) we have

applionm

mmi IIt

VCVD

)().()

1

1(

(12)

Since an effective conductivity = ⁄ then

by the monodomain model for cardiac tissue is given by

applion

mmm II

t

VCVD

)().( (13)

The conductivity of the tensor D, in the above equation is defined largely by the orientation of the tissue. Cardiac cells are grouped into muscle fibers,

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

29

and the muscle fibers are grouped into sheets of fibers. The structure of the heart influences the flow of electricity. Conductivity is usually greater along the fibers rather than across them [1, 7].

IV. SOLUTION OF MONODOMAIN MODEL BY

FEM

In this research work the FEM is used to solve the monodomain model. FEM has been widely used as an analysis and design tool in many engineering disciplines. The method can easily deal with complex geometries and higher-order approximations of the solution. Galerkin method is used to discretize the monodomian model. Galerkin methods are a class of methods for converting a continuous operator problem (such as a differential equation) to a discrete problem [4]. In principle, it is the equivalent of applying the method of variation of parameters to a function space, by converting the equation to a weak formulation. Typically one then applies some constraints on the function space to characterize the space with a finite set of basis functions.

Finite Element Equations

The monodomain equation which is coupled the

modified FitzHugh-Nagumo model is given below

applionm

m IIt

VC

mV

iDD

)()(. (14)

From the above equation we can write

)2

2

()2

2

y

mV

yD

x

mV

(x

Dappl

Iion

I)t

mV

(m

C

We can apply the Euler method in the above equation for time derivative and the application of Galerkin method to the diffusion term only over the entire domain of equation. Now we can write

dy

mV

yD

x

mV

xDWd

applI

ionIWd

t

mV

Wm

C )]2

2

()2

2

([)(

where, W is the weighting function. Now applying the

Euler method for time derivative the resulting

algebraic equation in matrix form is following

equation

applionnnnm MIMIMv

t

CvkM

t

C

1)(

Here M is the FEM lumped mass matrix and K is

stiffens matrix.

V. SIMULATION RESULT AND DISCUSSION

The simulation result is obtained by the MATLAB code to generate the uniform mesh for the heart tissue as a triangular element. The first step in the finite element method is to divide the structure or solution region into subdivisions or elements. Hence, the structure is to be modeled with suitable finite elements. The number, type, size, and arrangement of the elements are to be decided.

Although the implementation supports both two dimensional and three-dimensional problems, for the simplicity only two dimensional equations are used. The Intel dual core processor computer with 4GB RAM also used for simulation. Table 1 shows the parameters are used for simulation purpose and corresponding values.

TABLE I. TABLE MONODOAMIN MODEL SIMUATION

PARAMETERS.

Parameters Description Value Unit

Iappl Applied current 0.255 mA

dy Diffusion co-

efficient in the horizontal axis

2.6000e-004 cm

dx Diffusion co-

efficient in the vertical axis

0.0012 cm

Cm Capacitance 1 μF/cm2

dt Time 0.001 ms

A. Applied current at the middle node for35×35

nodal elements

In simulation purpose cardiac tissue is considered as a uniform mesh for triangle elements. For this condition a MATLAB code is built for 1225 nodes

and 2312 elements. The diffusion co-efficient dx along

the fibers while the diffusion dy perpendicular to the

fibers not in the plane. We can observe the propagation of excitations in the heart tissue by the Fig. 2.

(a)

(b)

(c)

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

30

(d)

(e)

Fig. 2. Surface plot for the propagation of excitations in the heart tissue at a uniform time step for 35×35 nodal element

The surface plots show the propagation of excitations for 35×35 nodal numbers. The current above the threshold value is applied to the middle node of the square mesh grid less than threshold value to other nodes. The diffusion coefficient dx along the fibers and dy perpendicular to the fibers but not in the plane. The value of dx is more than dy. The excitations from the middle nodes propagated to the nearby horizontal and vertical nodes. The propagation of excitations along the horizontal axis is more than the vertical. It is because value of dx is more than dy. The potential of those nodes changes consequently. After a uniform time interval the excitations reached at the end of the nodes. Then the process started from the initial condition. Fig. 2 consequently shows the process.

VI. CONCLUSION

In this research work propagation of excitation in the cardiac tissues is simulated, based on reaction-diffusion monodomain model. This work has been able to create some insights about the electrical behavior of human heart, revealing the nature of the excitation, propagation pattern in the cardiac tissue. The electro-physical mathematical models are based on ordinary differential equations and partial differential that describe the behavior of this electrical activity. Generating an efficient numerical solution of these models is a challenging task, and in fact the physiological accuracy of tissue-scale models is often limited by the efficiency of the numerical solution process.

The two dimensional monodomain equations solved to study the behavior of excitation propagation. The surface plots showed how excitation propagated in the cardiac tissue. For 35×35 nodal elements current above the threshold is applied to the middle node and less than threshold to the others. Excitation propagated from the middle nodes to

nearby horizontal and vertical nodes of the rectangular mesh grid. Then the nearby nodes also excited. In this way excitation propagated to the corner nodes. The propagation rate in the horizontal axis is more than vertical axis. The simulation worked is done in a small portion of the SA node. The model is solved for two dimensional equations for less complicity. If we want to increase more elements and nodes number then the simulation process becomes difficult. Because the simulation process need more time, computer memory and computational power. In future the models can be updated with patient-specific geometry and body surface potentials. At the same time more detailed cell models can be used and eventually the model can be improved by coupling with other electro-mechanical and blood flow models.

ACKNOWLEDGMENT

The authors are thankful to department of Applied Physics and Electronic Engineering, University of Rajshahi, Rajshahi-6205, Bangladesh.

REFERENCES

[1] J. Sundnes, G. T. Lines, X. Cai, B. F. Nielsen, K.-A.

Mardal, and A. Tveito, “Computing the electrical

activity in the heart”,Springer-Verlag, Berlin, 2006.

[2] A. J. Pullan, M. L. Buist, and L. K. Cheng,

“Mathematically modelling the electrical activity of the

heart: from cell to body surface and back again”, World

Scientific, New Jersey, 2005.

[3] C. S. Henriquez, “Simulating the electrical behavior of

cardiac tissue using the bidomain model”,Crit. Rev.

Biomed. Eng. ,vol. 21, pp. 1–77, 1993.

[4] S. C. Brenner and L. R. Scott, “The mathematical theory

of finite element methods”,Springer,Berlin, 1994.

[5] Jairo Villegas G and Andrus Giraldo M, “The electrical

activity of cardiac tissue via finite element method”,

Adv. Studies Theor.

Phys., vol. 6, PP.995 – 1003, 2012.

[6] J.M .Rogers and A.D. McCulloch, “A collacation-

Galerkin finite element model of cardiac action

potential propagation”, IEEE Trans. Biomedical

Engineering.41, PP.743-757, 1994.

[7] Shuaiby M. Shuaiby, M. A. Hassan, Abdel-Badie

Sharkawy and Abdel-Rasoul M.M.Gad, “A finite

Element Model for the electrical activity in human

cardiac tissues”, J. Eco. Heal. Env.vol. 1, PP.25-33,

2013.

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

31

Baking of Ilmenite on Koistening with Sulfuric Acid followed

by Leaching with Dilute Sulfuric Acid Solution

Ranjit K. Biswas, Aneek K. Karmakar and

Jinnatul Ara

Dept. of Applied Chemistry and Chemical

Engineering

Rajshahi University

Rajshahi-6205, Bangladesh

[email protected]

Muhammad A. Gafur

Pilot Plant and Project Development(PPPD) Division

BCSIR Laboratories, Dr. Kudrat-E-Khuda Road,

Dhanmondi

Dhaka-1205, Bangladesh

[email protected]

Abstract— It is very difficult to dissolve ilmenite quantitatively; and as a result, hundreds of papers and patents are available on its dissolution using various ways and techniques. But none of these claims for cent percent dissolution. The objective of ilmenite dissolution is to prepare pigment grade TiO2, or at least, the Chloride feed grade TiO2. A new, easy and attractive technique for ilmenite dissolution is described in this work. In this work, ilmenite has been moistened with conc. H2SO4, baked (heated) at a temperature near the boiling point of H2SO4 and then leached with very dilute solution of H2SO4. The optimized baking temperature and time are found to be 300o C and 30 min (for ilmenite to H2SO4 wt. ratio of 1), respectively. The single stage baked mass can be leached by 0.10 mol/L H2SO4 solution at its boiling temperature under reflux and at ilmenite to liquid ratio of 0.01 g/mL for 20 min to extract ~86% Fe and only 1.1% Ti from ilmenite. On the other hand, the 3-stage baking and 1-stage leaching remove as much as 97% Fe and only 2.4% Ti. The residue left after 3-stage baking and 1-stage leaching is almost white and identified as rutile, which can be regarded as a very good quality Chloride feed for manufacture of pigment grade TO2. Reasonable low temperature and time required in baking, together with the requirements of very low concentration of H2SO4 and time in leaching will attract technologists of this field to adopt this technique for almost complete removal of Fe from ilmenite to produce Chloride feed grade TiO2.

Index Terms— Ilmenite, H2SO4, Baking, Leaching, Chloride feed

INTRODUCTION

Pure TiO2 is widely used in paint, plastic, paper, textile, rubber and ceramic industries. Its sources are rutile (natural occurring TiO2) and ilmenite (TiFeO3). Rutile is generally used to prepare pigment grade TiO2 using the well-known Chloride process. But the reserve of rutile in nature is almost exhausted by this time. Consequently, the TiO2 – industry now depends solely on ilmenite (mixed oxides of ferrous and titanium). Ilmenite can be processed either for synthetic rutile by eliminating Fe from it, or for pigment grade TiO2 on its complete dissolution (Sulfate) method.

A considerable amount of heavy mineral deposits containing ilmenite, rutile, magnetite, zircon, monazite, garnet, leucoxene, kyanite, epidot, amphobiles, biotite, apatite etc. have been discovered in the Sitakundu-Chittagong-Banskhali-Cox’s Bazar-Inani-Teknuf beach and off-shore islands of Moheshkhali, Matabari, Kutubdia, Nijhum Dwip etc.

in Bangladesh. This (sp. gr.>2.88 g/cc) accounts for 10% of the total sand and contains about 27% ilmenite on average [1, 2]. In processing ilmenite to pigment grade TiO2, it is necessary to dissolve either both Fe and Ti or at least one component from ilmenite completely. This step still remains unsolved [1, 3 - 8] causing low recovery percentage in the existing manufacturing technologies of TiO2. However, methods have been developed for separating Fe(II)/Fe(III) from Ti(IV) existing in the leach solution obtained by partial leaching of both Ti and Fe from ilmenite [9 - 13].

As Bangladesh has considerable reserve of ilmenite, it is very important to work on processing of ilmenite to get either pigment grade TiO2, or at least, rutile enriched feed for the Chloride process. Previously [14], it was observed that copper dust on baking with 98% H2SO4 followed by leaching with 0.05 mol/L H2SO4 resulted in preferential leaching of copper leaving almost all iron in the residue. Being inspired with this result and as the mineral acid baking of ilmenite is not yet reported, the present study has been carried out with an aim to its complete dissolution, or at least, preferential leaching of either Fe or Ti from it.

EXPEIMENTAL

A. Materials

Ilmenite was collected in a single lot from the

Pilot Plant of Beach Sand Exploitation Centre at

Kalatali (Cox’s Bazar) of Bangladesh. Collected

ilmenite was dry-ground and sieved to collect <53

µm sized particles to use in the most baking studies.

Reagent grade chemicals of either Merck, BDH or

Loba chemie were used in this study without further

purification.

B. Analytical

The XRD patterns of powdered samples were

taken from the PPPD Center of the BCSIR

Laboratories, Dhaka. The SEM images were taken

from the Glass and Ceramics Engineering

Department, BUET, Dhaka. Routine analyses of

Ti(IV) and Fe(III) in aqueous solutions were carried

out by the H2SO4 – H2O2 method at 410 nm and

HNO3 – NH4SCN method at 480 nm, respectively,

using a visible spectrophotometer (SP 1105, China).

The HNO3 – NH4SCN method estimated the amount

of Fe(III) present in a solution; whereas, prior

oxidation of the solution by boiling for 5 min with 2

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

32

mL conc. HNO3 followed by the application of the

HNO3 – NH4SCN method yielded the amount of

Fe(II) plus Fe(III) in the solution. The difference gave

the amount of Fe(II).

C. Work Plan

The plan of work is schematically depicted below

(Fig. 1) which is self-explanatory:

Fig. 1. Flow sheet of the work plan

D. Procedure for baking

An aliquot of 1 g sized ilmenite was taken on a

quartz boat and moistened with 1 mL conc. H2SO4

and left overnight. With the aid of a wire attached at

one end of the boat, the container was then placed in a

tubular furnace (Carbolite CTF 12/65/550 type, UK)

at a certain thermostated temperature (100 – 800 oC).

The system was closed. Using a small air pump, air

was passed through the furnace and allowed to flow

from the other end via a plastic tube. Exit air carried

the acid vapor for condensation in the tube and

allowed to vent. After baking, the material with the

container was taken out from the furnace and put on a

flat ceramic sheet for cooling. It was then

quantitatively scratched over to a glossy paper for

leaching.

E. Procedure for leaching

An aliquot of 100 mL of 0.10 mol/L H2SO4

solution was taken in a 500 mL quick-fit conical flask

fitted with a 1 m long glass tube acting as a condenser.

The flask was set on a magnetic hot plate for heating

as well as for pulp agitation using a magnetic capsule

of 2 cm in length. When the boiling of the leaching

agent started, the baked mass was added and switched

on for time counting. When the ambient temperature

was greater than 25oC, the glass tube acting as

condenser, was wrapped with moist cloth or cotton to

facilitate condensation. After being leached for a

specific time, the leached slurry was filtered and the

filtrate was analyzed for its Ti(IV), Fe(II) and Fe(III)

contents.

RESULTS AND DISCUSSION

A. Characterization of Ilmenite Used in This Study

The collected ilmenite fraction of size <53 µm was used for powder XRD, SEM-XRF, chemical analyses and baking studies. The XRD pattern as taken by Cu Kα radiation (40 kV, 30 mA, scan speed 0.02

o/s and

step time 0.8 s) is depicted in Fig. 2, in order to identify the main phases existing in the sample. Main identical phases are: FeTiO3 and Fe9TiO15 (TiO2. 4Fe2O3.FeO). Other minor phases detected are SiO2, Fe2O3, TiO2, (Fe, Mg) Ti2O5 and FeCr2O4.

Fig. 2. X-ray diffraction pattern

Fig. 3. SEM image of Ilmenite

The SEM image of the sample as shown in Fig. 3, shows the crystallinity of different phases in the sample. The almost complete dissolution of the sample in molten KHSO4 for about 6 h, subsequent solublization in 15% H2SO4 solution and the colorimetric analysis of the resultant solution indicates that it contains 32.4% Fe (in both -ous and -ic states) and 27.8% Ti(IV). In the dissolution process, ~5% material remains undissolved. The other minor ingredients such as Si, Mn, Cr, Mg etc. are not quantified. On considering that the insoluble part does not contain any Fe and Ti, the extent of leaching (thermal treatment as well) has been monitored on the basis of 32.4% total Fe and 27.8% Ti existing in the sample.

B. Optimization of Baking Temperature The progress in baking is monitored by the extents (%s) of titanium and iron dissolved in succeeding leaching experiments conducted using 0.10 mol/L H2SO4 solution at its boiling temperature under reflux. The effect of baking temperature is investigated for a constant baking time of 30 min. The effect of baking temperature on dissolution of ilmenite, within 100 -800

o C, is provided in Fig. 4, as

the weight percentages of Ti(IV), Fe(II), Fe(III) and total Fe dissolved on subsequent leaching versus baking temperature plots. It is seen from this figure that the % dissolution of Ti(IV) is very low (< 4%), irrespective of baking temperature. On the other hand, Fe(II) and Fe(III) – dissolutions under identical conditions are notable. A 33.1% Fe(II) – dissolution at 100

o C is increased to 36.2% at 200

o C; and then

continuously decreased with the rise of baking temperature. At about 600

o C, it becomes negligible.

On the other hand, 29.5% Fe(III) – dissolution is increased to 44% at 400

o C and then, gradually

decreased to 41.3% at 500o C followed by rapid fall

within 500o C to 600

o C. At 800

o C, Fe(III) –

dissolution is only 0.6%. Total weight percentage of Fe – dissolved from the baked mass at 300

o C is the

maximum (73.6%) At both lower and higher temperatures, total Fe – dissolutions are lower, but considerable within baking temperatures of 100

o C -

500o C. Over 500

o C, total Fe – dissolution is sharply

decreased to only ~1% at 800o C. The combined

baking and leaching results indicate that near the boiling point of H2SO4 (316

o C), ilmenite sample

Quartz boat/Platinum Crusible

Left overnightand placed in

furnace

Furnace

Ilmenite (1g)

Conc. acid

Small air pump

Coiled plastic tubefor acid

condensationTo vent

Baked mass Leaching assemble FilterFiltrate

Analysis for metal ions

Residue

(), 01-070-6267: ilmenite (), 00-054-1267: Fe9TiO15

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

33

used in this study is principally broken down to TiO2 and mixture of FeSO4 and Fe2(SO4)3, during baking, according to the following reactions:

TiFeO3 + H2SO4 TiO2 + FeSO4 + H2O (1)

Fe9TiO15 + 13H2SO4 TiO2 + FeSO4 + 4Fe2(SO4)3 + 13H2O (2)

followed by dissolutions of only FeSO4 and Fe2(SO4)3 in very dilute sulfuric acid solution, leaving intact TiO2 as a solid phase.

One more point is notable here. With the increase of baking temperature, the reason for the decreased Fe(II) – dissolution and increased Fe(III) dissolution at higher temperature regions (up to ~ 500

o C) is the

enhanced oxidation of Fe(II) to Fe(III), in air atmosphere as per the following reaction:

4FeSO4 + 2H2SO4 + O2 2Fe2(SO4)3 + 2H2O (3)

At temperature above ~ 500o C, the decomposition of

Fe2(SO4)3 starts possibly according to following reaction:

Fe2(SO4)3 Fe2O3 + 3SO3 (4)

followed by decomposition of SO3 in the atmosphere of low partial pressure of O2 as shown below:

2SO3 2SO2 + O2 (5)

Ferric oxide, formed in this way, is not possibly leached out by dilute sulfuric acid solution used in this study. This result opens a way for selective leaching out of iron from ilmenite using conc. H2SO4 in baking and dil. H2SO4 solution in leaching. Fig. 4: Effect of baking temperature. Baking time = 30 min, leaching time = 1 h. (), Ti4+; (), Fe3+; (), Fe2+; (), Total Fe (Fe3+ + Fe2+).

C. Optimization of Baking Time

At a constant baking temperature of 300o C, the

effect of baking time (5 min interval within 50 min) is

investigated keeping other conditions stated

unchanged. Results are presented in Fig. 5, as plots of

wt.% metal ions dissolved versus baking time (min).

The figure indicates that the baking for 30 min gives

the best dissolution of Fe from ilmenite. For Ti(IV) –

dissolution, the percentage is gradually decreased with

time of baking (3.8% at 5 min to 0.9% at 50 min). The

decreased Fe – dissolution for baked masses over 30

min may be due Eqs. (3) and (4) occurring for longer

time in a high temperature of 300o C. It is concluded

that the best partial leaching of Fe from ilmenite can

be achieved at a baking temperature of 300o C for 30

min.

D. Optimization of Leaching Time

The baked mass of H2SO4 – moistened ilmenite (wt.

ratio of ilmenite/conc. acid = 1, baking temperature =

300o C and baking time = 30 min) is leached with 100

mL of 0.10 mol/L H2SO4 at boiling temperature under

reflux for variable leaching time ranging from 2 – 60

min to examine the effect of leaching time in the

system. Results are given in Fig. 6. It is seen that the

Ti – dissolution is limited within less than 1.7% up to

leaching time of 40 min which increased to ~3.7% at

60 min. The Fe(III) – dissolution percentage of 44.1%

at 2 min is increased to ~ 61.5% at 20 min followed

by a decrease to 43.6% at 60 min. On the other hand,

the dissolution percentage of Fe(II) is gradually

increased from 13.2% at 2 min to 30% at 60 min. The

maximum total iron dissolution of ~ 86% is obtained

at leaching time of 20 min. The reason for decrease in

dissolution percentage with increasing leaching time is

not known.

E. Stage-wise Baking The results of stage –wise baking (the mass

obtained in the 1st stage of baking is re-baked on

addition of 1 mL conc. H2SO4 and so on) but single

stage leaching is provided in Fig. 7. The stagewise baking is carried out at baking temperatures of 200

o C

and 300o C.

Figure 7 shows that increase in baking - stage number, operated at 200

o C, has little influence on

Ti(IV) dissolution. In contrast, 36% Fe(II) dissolution from single - stage baked mass is decreased to ~ 26% from three - stage baked mass. On the other hand, ~

35.5% Fe(III) dissolution from singlestage baked mass is increased, extensively, to ~ 70.8% from

threestage baked mass. Eventually, total

Fedissolution is increased if stagebaking is

0 100 200 300 400 500 600 700 800 9000

20

40

60

80

100

Wt%

of

met

als

dis

solv

ed (

bas

ed o

n

amoun

ts p

rese

nt

in i

lmen

ite)

Baking temperature, C

0 10 20 30 40 50 600

20

40

60

80

Wt.

% o

f m

etal

s dis

solv

ed

Baking time, min

Fig. 5. Effect of baking time on dissolution. Baking temperature = 300o C and leaching time = 1 h. (), Ti4+; (), Fe3+; (), Fe2+;

(), Total Fe (Fe3+ + Fe2+).

Fig. 6. Effect of leaching time, following baking, on dissolution. Baking time = 30 min and baking temperature = 300o C. (), Ti4+;

(), Fe3+; (), Fe2+; (), Total Fe (Fe3+ + Fe2+).

0 10 20 30 40 50 60 700

20

40

60

80

100

Wt.

% o

f m

etal

s dis

solv

ed

Leaching time, min

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

34

practiced. Total iron dissolution of ~ 71.7% from single - stage baked mass is increased to 90% from two – stage baked mass and to 96.8% from the

threestage baked mass. Almost similar results are obtained for baking at

300o C. In these cases, Ti(IV)dissolution is more

decreased. About 3.75% Ti(IV)dissolution obtained from single - stage baked mass is decreased to ~ 1.8% Ti(IV) - dissolution from three - stage baked mass.

Although Fe(II)dissolution curve shows a maximum,

Fe(III)- and total Fe dissolution percentages are increased with increase in stage number. ~ 86% total

Fedissolution from single - stage baked mass is increased to 98.4% from two - stage baked mass and to 98.7% from three - stage baked mass.

F. Characterization of baked mass and leached

residue The X-ray diffraction pattern (not shown) of three

stage baked mass (at 300C for 30 min) indicates that it is semi-crystalline. Comparison of this pattern with that in Fig. 2, clearly indicates that the crystal lattices of components present in ilmenite are completely destroyed on baking. The very weak new peaks appeared are probably due to the presence of Fe(II) and Fe(III) compounds of sulfate (however, not assigned) which could be leached out by dilute sulfuric acid solution and even mostly by water. Probably, the baked products do not get enough time during baking for large crystal growths. On the other hand, XRD pattern of baked (3-stages) – leached residue at optimized conditions (not shown) differ from those of ilmenite and baked ilmenite. It is seen that the peaks of ilmenite (Fig. 2) and of baked mass are not present in the XRD pattern of residue. The residual product appears almost as amorphous; but some diffraction peaks for rutile is obtained. The SEM images of baked (3-stages) mass and baked – leached residue are depicted in Figs. 8. The comparison of these images with that given in Fig. 3 demonstrates the changes occurring in baking and leaching.

It can be demonstrated that, from 3-staged baked

mass at optimized condition, 36.8% total Fe (32%

Fe(III) and 4.8% Fe(II)) can be dissolved by even

distilled water; while, 96.8% total Fe can be dissolved

by 0.10 mol/L H2SO4 solution. This supports the

formations of FeSO4 and Fe2(SO4)3 during baking.

CONCLUSION

Ilmenite, available in Bangladesh, containing TiFeO3 and Fe9TiO15 as main phases, can be baked

with conc. H2SO4 (1:1 by wt.) at 300 C for 30 min to produce a mass from which only iron can be leached out efficiently. A two – stage baking at optimized condition (300

oC, 30 min, ilmenite / conc. H2SO4 wt.

ratio of 1) followed by single – stage leaching by 0.10 mol/L H2SO4 solution at boiling temperature under reflux for 20 min can extract more than 98% Fe from ilmenite. On the other hand, for baking at 200

oC, 90%

iron is dissolved from a two – stage baked mass; whereas, ~97% iron is dissolved from a three – stage baked mass on leaching under identical condition. The changes during baking and leaching are demonstrated by XRD and SEM. The technique can be considered as a break through phenomena in titanium technology; as the method uses smaller amount of acid, comparatively lower temperature and comparatively little times in baking and leaching. The ultimate residue can be regarded as a rich Chloride feed for pigment grade TiO2.

REFERENCES

[1] R. K. Biswas and M. G. K. Mondal, “A study on the dissolution of ilmenite sand,” Hydrometallurgy, vol. 17, pp. 385-390, 1987.

[2] M. A. B. Biswas, “Lithology of recent titanium-zirconium places in the Bay of Bengal beach sands in the region of Cox’s Bazar (Bangladesh): Dissertation for the degree of Doctor of Philosophy, Voronezh State University, Voronezh, USSR, pp. 125-170, 1976.

[3] R. K. Biswas, M. F. Islam and M. A. Habib, “Dissolution of Ilmenite by roasting with LPG-pyrolysed products and subsequent leaching,” Ind. J. Eng. Mat. Sci., vol. 1, pp. 267-272, 1994.

[4] C. Sasikumar, D. S. Rao, S. Srikant, B. Ravikumar, N. K. Mukhopadhyay and S. P. Melhotra, “Effect of mechanical activation on the kinetics of sulfuric acid leaching of beach sand ilmenite from Orissa, India,” Hydrometallurgy, vol. 75, pp. 189-204, 2004.

[5] F. Islam, R. K. Biswas and C. M. Mustafa, “Solvent extraction of Ti(IV), Fe(III) and Fe(II) from acidic sulphate media with HDTP–benzene–hexan–1–ol system: A separation and mechanism study,” Hydrometallurgy, vol. 13, pp. 365-376, 1985.

[6] R. K. Biswas, M. A. Habib and N. C. Dafadar, “A study on the recovery of titanium from hydrofluoric acid leach solution of ilmenite,” Hydrometallurgy, vol. 28, pp. 119-126, 1992.

[7] R. K. Biswas and R. K. Jana, “Crude electrorefining electrolyte obtained from ICC(Ghatsila, India) copper dust,” Min. Proc. Extr. Metall, vol. 113, pp. C45-C52, 2004.

Fig. 8. SEM images of (a) H2SO4 - baked mass and (b) residue

obtained on leaching of H2SO4 - baked mass.

(a) (b)

Fig. 7. Effect of stage-wise baking. Wt. of H2SO4 added in each stage = 1 g, baking time =30 min, baking temperature = 200o C

(open symbols) and 300o C (closed symbols), leaching time = 20 min. (,), Ti4+; (,), Fe3+; (,), Fe2+; (,), Total Fe (Fe3+

+ Fe2+).

0 1 2 3 40

20

40

60

80

100

Number of baking stage

Wt.

% o

f m

etal

s dis

solv

ed

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

35

Thermal Treatment of Ilmenite on Moistening with

Concentrated HF followed by Leaching with Dilute Sulfuric

Acid Solution Ranjit K. Biswas, Mohammad A. Habib,

Aneek K. Karmakar and Mohammad J. Alam Dept. of Applied Chemistry and Chemical Engineering

Rajshahi University


[email protected]

Abstract— As it is very difficult to dissolve ilmenite

(FeTiO3) quantitatively, enormous studies on ilmenite

dissolution have been patented and published. The

objective of this dissolution is to prepare pigment grade

TiO2, or at least, the chloride feed grade TiO2. A new

technique for Fe dissolution from ilmenite is described

in this work.

Ilmenite has been moistened with conc. HF, heated

(baked) at a higher temperature and leached with dilute

H2SO4 solution. The optimized baking temperature and

time are found to be >170 C and 20 min for ilmenite to

HF wt. ratio of 1, respectively. The baked mass can be

leached by 0.5 mol/L H2SO4 solution at its boiling

temperature under reflux and at ilmenite to liquid ratio

of 0.01 g/mL for 1 h to extract ~37% Fe (total) and 7%

Ti from ilmenite sample. About 37% Fe-dissolution

from the 1st stage baked mass is increased to ~96% Fe-

dissolution from the 6th stage baked mass. Comparisons

of the XRD pattern and SEM image of mother ilmenite

with those of the residue obtained on 96% Fe removal

indicates that ilmenite crystal is completely destroyed to

form an amorphous-almost white product containing

most of titanium present in ilmenite. As the residue

contains ~4% Fe only, it can be regarded as a feed

material for the chloride process of pigment grade TiO2

manufacture.

Keywords— Ilmenite, HF, H2SO4, Baking, Leaching,

Chloride feed

I. INTRODUCTION

Titanium, being light and possessing high strength,

is used in aircrafts and its oxide is extensively used in

paint, plastic, paper, textile, rubber and ceramic

industries. Their source materials are rutile and

ilmenite. Previously, rutile was used to prepare

pigment grade TiO2 using the well-known chloride

process in which TiO2-graphite mixture was heated in

presence of Cl2 gas to distill out TiCl4 with other

chlorides. Then TiCl4 was decomposed by air to form

TiO2 and to regenerate Cl2. But as the reserve of rutile

in nature is depleted off, the TiO2-industry now

depends solely on ilmenite. It can be processed either

for synthetic rutile by eliminating Fe from it, or, for

the pigment grade TiO2 on its complete dissolution,

solution purification by crystallization and solvent

extraction, thermo-hydrolytic precipitation and

ignition.

There is a considerable of reserve of ilmenite in the

beach sand of Bangladesh. The pilot plant beach sand

exploitation centre of BAEC at Kalatali, Cox’s Bazar

has successfully fractionated beach sand into

ilmenite, rutile, zircon, monazite, garnet etc. In

processing ilmenite for production of pigment grade

TiO2, it is necessary to dissolve it completely, or at

least one component (Fe or Ti) preferentially. This

step still remains unsolved [1-7] resulting in low yield

in the existing manufacturing technologies of TiO2.

However, methods have been developed for

separating Fe(II)/Fe(III) from Ti(IV) existing in the

leach solution obtained by partial leaching of both Ti

and Fe from ilmenite [8-12].

Sulfuric and hydrochloric acid have been widely

used for dissolving ilmenite [13-18]. But no method

demands complete dissolution of ilmenite or of one

component from ilmenite. There are a few reports on

partial dissolution of ilmenite by HF [19-21].

As Bangladesh possesses a considerable reserve of

ilmenite, it is worthy to work on processing of

ilmenite to get either pigment grade TiO2, or at least,

rutile enriched feed for the chloride process.

Previously [22], it was observed that copper dust on

baking with 98% H2SO4, followed by leaching with

0.05 mol/L H2SO4, resulted in preferential leaching of

Cu leaving almost all iron in the residue. Being

inspired by this work and as the mineral acid baking

of ilmenite is not yet reported, the present study on

baking of ilmenite after moistening with conc. HF,

followed by H2SO4 leaching has been undertaken with

an aim to its complete dissolution, or at least,

preferential leaching of either Fe or Ti from it.

II. EXPEIMENTAL

A. Materials

Ilmenite was collected from BAEC’s Pilot Plant

of Beach Sand Exploitation Centre at Kalatali (Cox’s

Bazar). The sample was found to contain 27.8% Ti

and 32.4% Fe (both in Fe2+

and Fe3+

states). It was

dry-ground and sieved to collect < 53 m sized

particles to use in the most baking studies. The

chemicals were A. R. grade E. Merck – BDH

products and used without further purification.

B. Analytical

The XRD patterns were taken from the PPPD

center of BCSIR laboratories, Dhaka. The SEM

images were taken from the Glass and Ceramic

Engineering Department of BUET, Dhaka. Routine

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

36

analyses of Ti(IV) and Fe(III) in aqueous solutions

were carried out by the H2SO4-H2O2 method at 420

nm and HNO3-NH4SCN method at 480 nm,

respectively, using a visible spectrophotometer (SP

1105, China). The HNO3-NH4SCN method estimated

the amount of Fe(III) present in a solution; whereas,

prior oxidation by boiling for 5 min with 2 mL conc.

HNO3 followed by the application of the HNO3-

NH4SCN method yielded the amount of Fe(II) +

Fe(III) in the solution. The difference gave the amount

of Fe(II).

C. Work Plan

The plan of work is schematically depicted below

(Fig. 1) which is self-explanatory:

Fig. 1. Flow sheet of the work plan

D. Procedure for baking

An aliquot of 1 g ilmenite (< 53 m size) was taken

in a Pt-crucible and moistened with 1 g conc. HF and

left overnight. With the help of a wire, tightened

cross-sectionally at the middle, the container was

placed in a tubular furnace (Carbolite CTF 12/65/550

type, UK) at a certain thermostated temperature (150 –

225 C). The system was closed. Using a small air

pump, air was passed through the furnace and allowed

to flow from the other end via a plastic tube. Exit air

carried the acid vapor for condensation in the tube and

allowed to vent. After baking, the material with the

container was taken out from the furnace, cooled and

then quantitatively scratched over to a glossy paper for

leaching.

E. Procedure for leaching

An aliquot of 100 mL of 0.50 mol/L H2SO4

solution was taken in a 500 mL quick-fit conical flask

fitted with a 1 m long glass tube acting as a condenser.

The flask was set on a magnetic hot plate for heating

as well as for pulp agitation using a magnetic capsule

of 2 cm in length. When the boiling of the leaching

agent started, the baked mass was added and switched

on for time counting. When the ambient temperature

was greater than 25oC, the glass tube acting as

condenser, was wrapped with moist cloth or cotton to

facilitate condensation. After being leached for a

specific time, the leached slurry was filtered and the

filtrate was analyzed for metal ions contents.

III. RESULTS AND DISCUSSION

A. Characterization of Ilmenite Used in This Study

The collected sized (<53 µm) ilmenite has been

used for powder XRD, SEM, chemical analyses and

baking studies. The XRD pattern as taken by Cu Kα

radiation (40 kV, 30 mA, scan speed 0.02o/s and step

time 0.8 s) in Fig. 5 (i) indicates the presence of

FeTiO3 and Fe9TiO15 along with some un-identified

phases. However, a Japanese analysis indicates the

presence of SiO2, Fe2O3, TiO2, (Fe, Mg) Ti2O5 and

FeCr2O4 as minor phases. The SEM image shows the

crystallinity of different phases in the sample. The

almost complete dissolution of the sample in molten

KHSO4 for about 6 h, subsequent solublization in 15%

H2SO4 solution and the colorimetric analysis of the

resultant solution indicates that it contains 32.4% Fe

(in both -ous and -ic states) and 27.8% Ti(IV). In the

dissolution process, ~5% material remains

undissolved. The other minor ingredients such as Si,

Mn, Cr, Mg etc. are not quantified. On considering

that the insoluble part does not contain any Fe and Ti,

the extent of leaching (thermal treatment as well) has

been monitored on the basis of 32.4% total Fe and

27.8% Ti existing in the sample.

B. Optimization of Baking Temperature

The progress in baking is monitored by the extents

(%s) of Ti and Fe dissolved in succeeding leaching

experiments conducted using 0.50 mol/L H2SO4

solution at its boiling temperature under reflux. The

effect of baking temperature is investigated for a

constant baking time of 20 min. The effect of baking

temperature on dissolution of ilmenite, within 150 -

225 C, is given in Fig. 2, as weight %s of metal ions

dissolved on subsequent leaching versus baking

temperature plots.

It is seen from this figure that the dissolution

percentages of Ti(IV) and Fe(II) are little varied, but

those of Fe(III) and total Fe are increased

considerably, within 150-200 C. The Ti(IV)

dissolution percentage from baked mass up to 200oC

is within (7 )% and this is decreased to ~ 4.3% for

baked mass at 225 oC. Although Fe(II)-dissolution

percentages lie within (18.5 1.5) C for baking

temperature variation of 150-225oC, the Fe(III)-

dissolution percentage is increased from ~ 11% for

baked mass at 150 C to ~ 21% for baked mass at 225

C. Total Fe-dissolution percentage of 28 % for baked

mass at 150 C is increased to 39% for baked mass at

175oC and this value is little varied within 175 – 220

C. This result predicts the preferential leaching of Fe

over Ti(IV) from ilmenite. Ilmenite matrix is broken

down at least partially by the treatment with HF at a

temperature of ~ 170 C within only 20 min.

C. Optimization of Baking Time

The effect of baking time on subsequent leaching

has been investigated. The HF moistened ilmenite has

been baked at 200oC for either 10, 20 or 30 min and

the resultant masses are subjected to H2SO4 acid

solution leaching under identical condition to find out

the leaching percentages of metal ions.

The results from the above experiments are given as

wt. % of metals dissolved versus time in min plots in

Fig. 3. All metal ion dissolution %s show maxima at

baking time of 20 min. From a baked mass at 200oC

for 20 min, a total Fe dissolution of 37% with < 7%

dissolution of Ti(IV) are achieved.

Quartz boat/Platinum Crusible

Left overnightand placed in

furnace

Furnace

Ilmenite (1g)

Conc. acid

Small air pump

Coiled plastic tubefor acid

condensationTo vent

Baked mass Leaching assemble FilterFiltrate

Analysis for metal ions

Residue

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

37

Fig. 2. Effect of baking temperature of concentrated HF moistened ilmenite. Wt. of ilmenite sample = 1 g, particle size = < 53 µm,

amount of concentrated HF added to moisten ilmenite = 1 g,

baking time = 20 min, leaching agent = 100 mL 0.5 M H2SO4, leaching temperature = boiling temperature, leaching time = 1

hour.

At around 150 C and above, ilmenite sample used in this study is principally broken down to TiO2, TiOF2, FeF2, FeF3 etc. during baking, according to the following reactions: TiFeO3 + 2 HF = TiO2 + FeF2 + H2O (1) TiO2 + 2 HF = TiOF2 + H2O (2) Fe9TiO15 + 26HF = TiO2 + FeF2 + 8FeF3 + 13H2O (3) followed by dissolutions of FeF2, FeF3 and TiOF2 in dilute H2SO4 solution, leaving intact TiO2 as a solid phase. The presence of rutile (TiO2) and titanium oxide fluoride (TiOF2) in the baked mass has been identified by XRD (see later). D. Stage – wise baking

Interesting result is obtained from the stage-wise baking study. An aliquot of 1 g ilmenite is just moistened with conc. HF (left over-night) and baked at optimized baking temperature of 200

oC for 20 min.

The leaching of this baked mass was carried out as usual to calculate dissolution %s of metal ions for gathering single- stage baking results. To obtain the second stage baking result, the baked mass obtainable from the first stage was again moistened with conc. HF, baked and leached as usual. In the similar way, for six - stage leaching, addition of HF to ilmenite and baking was continued for 6 times. The results obtained on stage-wise baking followed by leaching at identical conditions are shown as the dissolution wt. % of metal ions versus baking stage number plots in Fig. 4. The Ti(IV)-dissolution of ~7% from single-stage baked mass is gradually decreased to only 1% dissolution from the sixth - stage baked mass. On the other hand, though Fe(III) dissolution percentage is decreased to some extent with the increase in baking stage number, Fe(II) and total Fe-dissolutions are remarkably increased with the increase in baking stage number. The Fe(II)-dissolution of 16% from the single - stage baked mass is increased to 82% from the sixth - stage baked mass. Likewise, total iron-dissolution of 37% from the single - stage baked mass is increased to 96% from the sixth - stage baked mass. Therefore, a procedure involving six-stage baking followed by single-stage leaching with 0.50 mol/L sulphuric acid solution produces a mass from which 96% iron can be leached out leaving 99% titanium in the solid state. The residual product is almost white and can be used as a raw material for

chlorination process in order to obtain pigment grade TiO2.

Fig. 3. Effect of baking time of concentrated HF moistened

ilmenite. Wt. of ilmenit sample = 1 g, particle size = < 53 µm, amount of concentrated HF added to moisten ilmenite = 1 g, baking

temperature = 200oC, leaching agent = 100 mL 0.5 M H2SO4,

leaching temperature = boiling temperature, leaching time = 1 hour.

Fig. 4. Effect of stage-wise baking on metals dissolution from

ilmenite. Wt. of ilmenite sample = 1 g, particle size = < 53 µm, amount of concentrated HF added to moisten ilmenite = 1 g in each

stage, baking temperature = 200oC, leaching agent = 100 mL 0.5

M H2SO4, leaching temperature = boiling temperature, leaching time = 1 hour.

E. XRD patterns and SEM images The XRD patterns of ilmenite sample used in this study and of ilmenite-HF baked mass of sixth stage are shown in Fig. 5, for comparison. It is seen that the diffraction peaks for TiFeO3 and Fe9TiO15 are almost disappeared in the XRD pattern of baked mass with the appearance of diffraction peaks for rutile (TiO2) and titanium oxide fluoride (TiOF2). Therefore, Eqs. (1)-(3) suggested above for baking reactions appear true. The incomplete baking in single stage might be due to the volatility of HF at the baking temperature region and also due to higher stoichiometric HF acid requirement. The XRD pattern of the baked-leached residue appears as of amorphous substance. The SEM images of ilmenite sample used in this study and of baked – leached residue are given in Fig. 6. The crystals of species present in the sample disappear to form amorphous lumps in baked-leached residue.

IV. CONCLUSION

The baking of ilmenite after moistening with conc.

HF at 200 C for 20 min produced a mass from which iron can be leached out efficiently. A six – stage

baking at optimized condition (200 C, 20 min, ilmenite moistened with conc. HF) followed by single – stage leaching by 0.50 mol/L H2SO4 solution at 100

oC under reflux for 1 h can extract ~96% Fe from

140 160 180 200 220 2400

10

20

30

40

50

Baking temperature, oC

Wt.%

of m

eta

ls d

issolv

ed

(based

on a

mou

nts

pre

sen

t in

ilm

enite)

() Total Fe; () Fe3+; () Fe2+; () Ti4+

() Total Fe

() Fe3+

() Fe2+

() Ti4+

5 10 15 20 25 30 350

10

20

30

40

Baking time, min

Wt.%

of m

eta

ls d

issoved

() Total Fe

() Fe3+

() Fe2+

() Ti4+

0 1 2 3 4 5 6 70

20

40

60

80

100

Wt.%

of m

eta

ls d

issolv

ed

Number of baking stage

() Total Fe

() Fe3+

() Fe2+

() Ti4+

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

38

ilmenite. The changes during baking and leaching are demonstrated by XRD and SEM. This technique can be regarded as another break through phenomena in titanium technology; as the method uses smaller amount of acid, comparatively lower temperature and little times in baking and leaching. The ultimate residue can be regarded as a rich chloride feed for pigment grade TiO2.

Fig. 5. X-ray diffraction pattern of (i) ilmenite (ii) ilmenite -

hydrofluric acid baked mass.

Fig. 6. SEM images of (a) Ilmenite sample and (b) residue left after

leaching of HF - baked mass.

REFERENCES

[1] R. K. Biswas and M. G. K. Mondal, “A study on the dissolution of ilmenite sand,” Hydrometallurgy, vol. 17, pp. 385-390, 1987.

[2] M. A. B. Biswas, “Lithology of recent titanium-zirconium places in the Bay of Bengal beach sands in the region of Cox’s Bazar (Bangladesh): Dissertation for the degree of Doctor of Philosophy, Voronezh State University, Voronezh, USSR, pp. 125-170, 1976.

[3] R. K. Biswas, M. F. Islam and M. A. Habib, “Dissolution of Ilmenite by roasting with LPG-pyrolysed products and subsequent leaching,” Ind. J. Eng. Mat. Sci., vol. 1, pp. 267-272, 1994.

[4] R. K. Biswas, M. F. Islam and M. A. Habib, “Processing of ilmenite by roasting with the reformed product of LPG-water mixture in presence of nickel powder and subsequent leaching,” Bang. J. Sci. Ind. Res., vol. 33, pp. 425-433, 1998.

[5] R. K. Biswas, M. F. Islam and M. A. Habib, “Processing of ilmenite through sodium carbonate-water vapor roasting and leaching,” Bang. J. Sci. Ind. Res., vol. 32, pp. 103-110, 1997.

[6] R. K. Biswas, M. F. Islam and M. A. Habib, “Processing of ilmenite through salt-water vapour roasting and leaching,” Hydrometallurgy, vol. 42, pp. 367-375, 1996.

[7] M. A. Habib, R. K. Biswas, P. K. Sarkar and M. Ahmed, “Leaching of ilmenite by mixed solvents and their kinetics,” Bang. J. Sci. Ind. Res., vol. 38, pp. 1-12, 2003.

[8] C. Sasikumar, D. S. Rao, S. Srikant, B. Ravikumar, N. K. Mukhopadhyay and S. P. Melhotra, “Effect of mechanical activation on the kinetics of sulfuric acid leaching of beach sand ilmenite from Orissa, India,” Hydrometallurgy, vol. 75, pp. 189-204, 2004.

[9] F. Islam, M. Ali and S. Akhter, “Separation and recovery of titanium from iron bearing leach liquors by solvent extraction with di-2-ethyl hexyl phosphoric acid-tributyl phosphate-thiocyanate system,” Bang. J. Sci. Ind. Res., vol. 13, pp. 222-230, 1978.

[10] F. Islam and Z. Kawnin, “Separation and recovery of titanium from iron bearing leach liquors by solvent extraction with di-2-ethyl hexyl phosphoric acid,” Bang. J. Sci. Ind. Res., vol. 13, pp. 83-89, 1978.

[11] F. Islam, H. Rahman and M. Ali, “Solvent extraction separation study of Ti(IV) Fe(III) and Fe(II) from aqueous solutions with di-2-ethyl hexyl phosphoric acid in benzene,” J. Inorg. Nucl. Chem., vol. 41, pp. 217-221, 1979.

[12] F. Islam, R. K. Biswas and C. M. Mustafa, “Solvent extraction of Ti(IV), Fe(III) and Fe(II) from acidic sulphate media with HDTP–benzene–hexan–1–ol system: A separation and mechanism study,” Hydrometallurgy, vol. 13, pp. 365-376, 1985.

[13] R. K. Biswas, M. A. Habib and N. C. Dafadar, “A study on the recovery of titanium from hydrofluoric acid leach solution of ilmenite,” Hydrometallurgy, vol. 28, pp. 119-126, 1992.

[14] A. A. Baba, S. Swaroopa, M. K. Ghosh and F. A. Adekola, “Mineralogical characterization and leaching behavior of Nigerian ilmenite ore,” Trans. Nonfer. Met. Soc. China, vol. 23, pp. 2743-2750, 2013.

[15] L. Jia, B. Liang, L. Lu, S. Yuan, L. Zheng, X. Wang and C. Li, “Beneficiation of titania by sulfuric acid pressure leaching of Panzhihua ilmenite,” Hydrometallurgy, vol. 150, pp. 92-98, 2014.

[16] M. H. H. Mahmood, A. A. Afifi and I. A. Ibrahim, “Reductive leaching of ilmenite ore in hydrochloric acid for preparation of synthetic rutile,” Hydrometallurgy, vol. 73, pp. 99-109, 2004.

[17] T. Ogasawara and R. V. Veloso de Araujo, “Hydrochloric acid leaching of a pre-reduced Brazilian ilmenite concentrate in an autoclave,” Hydrometallurgy, vol. 56, pp. 203-216, 2000.

[18] V. S. Gireesh, V. P. Vinod, S. K. Nair and G. Ninan, “Catalytic leaching of ilmenite using hydrochloric acid: A kinetic approach,” Int. J. Miner. Processing, vol. 134, pp. 36-40, 2015.

[19] R. K. Biswas and M. G. K. Mondal, “A study on the dissolution of ilmenite sand,” Hydrometallurgy, vol. 17, pp. 385 – 390, 1987.

[20] K. Nagasubramanian and K. Liu, “Recovery of TiO2 from ilmenite – type ore by a membrane based electrodialysis process,” US Patent No. 4,107,264, 1978.

[21] D. A. Hansen and D. E. Traut, “The kinetics of leaching rock ilmenite with hydrofluoric acid,” J. Metals, vol. 41, pp. 34-36, 1989.

[22] R. K. Biswas and R. K. Jana, “Crude electrorefining electrolyte obtained from ICC(Ghatsila, India) copper dust,” Min. Proc. Extr. Metall, vol. 113C, pp. 45-52, 2004.

(i)

(ii)

(), 01-070-6267: ilmenite; (), 00-054-1267: Fe9TiO15

(), 01-070-7347: Rutile; (), 01-076-7831: Titanium Oxide Fluoride

(a) (b)

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

39

Solvent Extraction of V(V) from Nitrate Medium by Tri-n-

Octylamine Dissolved in Kerosene

Ranjit K. Biswas, Aneek K. Karmakar and Mottakin

Dept. of Applied Chemistry and Chemical Engineering

Rajshahi University


[email protected]

Abstract— The liquid-liquid extraction of V(V) from

nitrate medium by tri-n-octylamine (TOA) dissolved in

distilled colorless kerosene has been investigated as

functions of various experimental parameters.

Equilibration time is less than 10 min. HNO3 is found to

be extracted by TOA (HNO3 + (C8H17)3N →

(C8H17)3NH.NO3). The nature of species extracted into

the organic phase depends on the existing aqueous

species prevailed at a certain pH. At lower pH regions,

the extraction of VO2+ occurs via cation (H+) exchange

of (C8H17)3NH.NO3 as follows: VO2++NO3-H.TOA →

VO2NO3.TOA + H+. On the other hand, at higher pH

region, anionic V(V) species such as V10O26(OH)24-,

V10O27(OH)5-, V10O286- etc. are extracted by solvated

ion-pair formation mechanism (eg. V10O26(OH)24-

+2H++TOA → H2V10O26.TOA + 2H2O). The TOA

concentration dependence depends on pH region of

extraction. It is seen that the extraction ratio increases

with the increase in V(V) concentration in the aqueous

phase which is possibly due to the formation of

extraction favorable V(V) species with increasing its

concentration in the aqueous phase. The extraction is

also found to be favored by the rise of nitrate

concentration in the aqueous phase; and the variation

may be quantitatively expressed by: log D = const. + log

(1+1.82[NO3-]); where, const. depends on pH and [TOA]

used. Temperature has a pronounced effect with H <

55 kJ/mol. The extracted species can be stripped by 0.75

mol/L NH4OH solution to the extent of 71%; but stage-

wise stripping is not so effective. A very high loading of

~2.3 mol V(V) per mol/L TOA is observed.

Keywords— Extraction, stripping, V(V), TOA,

loading, NO3--medium

I. INTRODUCTION

Vanadium is extensively used as an alloying

element for high strength steel used in the

manufacture of pipe lines, rail lines, axles and

crankshafts for motor vehicles, high speed tool steel,

jet engines etc. Its non-steel application fields include

welding, nuclear engineering, superconductor,

catalyst, fuel cell etc. In 2012, 74,000 tons of

vanadium was produced worldwide [1]. However,

there is no rich ore of V; and consequently, it is

manufactured generally from petroleum fly ashes, tar

sand fly ashes, black shape desulphurization waste

catalyst, carnolite etc. using the hydrometallurgical

route involving roasting, leaching, extraction,

stripping and precipitation. On leaching, vanadium

dissolves either as V(IV) or V(V). Vanadium (IV) can

be easily oxidized to V(V) by boiling with HNO3; and

V(V) can be easily reduced by Na2SO3(SO2) solution.

The extraction of both V(IV) and V(V) by various

extractants have been investigated substantially [2-

15]. As species variation of V(IV) is limited,

mechanistic studies on V(IV) extraction are simple in

nature. On the other hand, V(V) exists as VO2+ a pH <

1 and starts to hydrolyze and polymerization with

increasing pH to form species such as VO7(OH)3,

V10O26(OH)24-

, V10O27OH5-

, V10O286-

, V3O93-

, etc.

within acidic pH region. It appears, therefore, that the

extraction of V(V) in pH region 1-6 by various

extractants are little investigated from the mechanistic

point by view, though there are several reports on

separation of V(V) from other metal ions using

various extractants. Consequently, the extraction of

V(V) from nitrate medium by TOA is reported in the

paper from mechanistic point of view.

II. EXPEIMENTAL

A. Materials

Tri-n-octylamine (TOA) was collected from

Tokyo Kaie Ind (90%) and was used without further

purification. It was diluted with distilled colorless

kerosene to constitute the organic phase. All other

chemicals were of reagent grade and used without

further purifications. Kerosene was bought from the

local market and distilled to collect colorless fraction

distilling over 200-260 C. Requisite amount of

NH4VO3 was dissolved in 170 mL 6 mol/L HNO3

solution and diluted to 500 mL to obtain a stock

solution containing 5 g/L V(V) and 1.92 mol/L

HNO3. In most cases, this solution was 10 times

diluted to obtain test solutions containing 0.5 g/L

V(V) and 0.192 mol/L HNO3 or NO3-.

B. Analytical

A double buffer calibrating pH meter (mettle

toledo 220) was used for pH measurement and

adjustment of aqueous phase by the addition of

anhydrous Na2CO3. Aqueous V(V) concentration was

determined by the H2O2 colorimetric method [16] at

450 nm using a visible spectrophotometer ()

C. Procedure for extraction

All studies excepting the temperature dependence

were carried out at (298±1) K using a thermostatic

water bath. Equal volumes (20 mL) of aqueous and

organic phases were taken in a 100 mL reagent bottle,

stoppered and shaken well, in a thermostatic water

bath for predetermined time of 10 min usually for

equilibration. On equilibration, phases were settled

and disengaged. Aqueous phase was analyzed for its

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

40

V(V) content and equilibrium pH. The extraction ratio

D was then calculated using the following relation: D = (CV(V)

O at equilibrium)/(CV(V)

A at equilibrium)

= (CV(V) (ini)A – CV(V) (eq)

A)/(CV(V)

A at equilibrium) (1)

D. Procedure for loading

An aliquot of the organic phase (20 mL 0.10 mol/L

TOA) was repeatedly contacted for 5 min in each

stage with fresh aqueous solution containing 2 g/L

V(V) at pH 1 and 298 K. After each stage extracted

V(V) concentration was estimated to calculate

cumulative concentration of V(V) in the organic

phase.

E. Procedure for stripping

This was virtually similar to the procedure for

extraction. In this case, the organic phase containing

V(V) as solvated ion pair with TOA was equilibrated

with equal volume of NH4OH solution for 10 min. On

equilibration, phases were separated on settling and

the aqueous phase was analyzed for V(V) content.

Then stripping percentage (S, %) was calculated as

follows:

S, % = ((CV(V) (eq)A)×100)/(CV(V) (ini)

O) (2)


Preliminary experiment showed that the extraction

process under consideration, was quite fast (5 min

required for equilibration). However, subsequent

experiments were carried out with equilibration time

of 10 min to ensure the attainment of equilibration at

different conditions. The effect of [V(V)] on

extraction ratio is depicted in Fig. 1 as log D vs. log

[V(V)], mol/L plots for pH(ini) of 1 but at [TOA] of

0.01, 0.05 and 0.10 mol/L. It is found that the

extraction ratio is extensively increased with

increasing [V(V)] in the aqueous phase. The broken

line represents the data at pH(eq) of 2.85 for 0.10 mol/L

TOA system. In this case, also D is increased with

increasing [V(V)] with a slope of ~2.5. In general

D – value should remain unchanged with the

variation of metal ion concentration if extractable

species variation is absent there. The result is the

indicative of species variation with increasing [V(V)].

Not all V(V) – species is extractable by TOA; rather

particular [V(V)]-species is susceptible to be extracted

by TOA and the concentration of this species is

increased with increasing [V(V)] in the aqueous

phase.

The variations of extraction of V(V) with aqueous

pH are displayed in Fig. 2, as log D vs. pH(ini) and in

Fig. 3, as log D vs. pH(eq) plots for [TOA] of 0.03, 0.05

and 0.10 mol/L. Initial pH is varied significantly on

extraction; and so the isotherms given in Fig. 2 are not

representative to actual systems. On the other hand,

the isotherms given in Fig. 3 are the better

representative to the system (some error still exists

owing to [TOA] variation on different extents of

extractions). For cation exchange reactions, the pH-

dependency (slope of log D vs. pH plot) should be

positive due to liberation of H+ by extraction reaction.

The negative pH-dependency (negative slope of log D

vs. pH plot) is indicative of the association of H+ with

existing V(V) species to form the extractable species.

Fig. 1. Effect of [V(V)] on extraction. pH(ini) = 1, [TOA] = 0.01 (),

0.05 () and 0.10 () mol/L, Temp. = 298 K, O/A = 1, time = 10

min. pH(eq) = (), 1.3±0.18; (), 2.3±0.20; (), 2.85±0.6. Dashed line (), pH(eq) = 2.85, [TOA] = 0.10 mol/L.

Fig. 2. Effect of initial pH on extraction. [V(V)](ini) = 0.50 g/L,

temp. = 300 K, O/A = 1, time = 10 min, (), [TOA] = 0.10 mol/L; (), [TOA] = 0.05 mol/L and (), [TOA] = 0.03 mol/L.

Fig. 3. Effect of equilibrium pH on extraction. [V(V)](ini) = 0.50

g/L, temp. = 300 K, O/A = 1, time = 10 min, (), [TOA] = 0.10

mol/L; (), [TOA] = 0.05 mol/L and (), [TOA] = 0.03 mol/L.

According to Zeng and Yong Cheng [17], yellow

colored VO2+ exists within pH 1-2; whereas, within

pH 2-6.5, orange-red V10O28-6

exists. However, it is

also reported [7] that with the gradual of increase of

pH from zero, VO2+ is gradually transformed to

VO(OH)3 (to a small extent), V10O26(OH)24-

,

V10O27(OH)5-

, V10O286-

, V3O93-

, V4O124-

, VO2(OH)2-

etc. V10O26(OH)24-

is virtually doubly protonated

V10O286-

; whereas, V10O27OH5-

is single protonated

V10O286-

. The distribution of these species as function

of pH are also available [7] as shown in Table I.

-3 -2 -1 0-2

-1

0

1

2

3

log

D

log [V(V)], mol/L

1 2 3 4 5-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

log

D

pH(ini)

1 2 3 4 5 6-2

-1

0

1

2

3

log

D

pH(eq)

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

41

Table I. Distribution of V(V)-species at different pH values [7].

pH % (approximate) Theoretical pH dependence

VO2+ VO(OH)3 V10H26(OH)2

4- V10H27OH5- V10O286- V3O9

3- VO2(OH)2- V4O12

4-

1.0 99 1 - - - - - - 0.99

1.5 98 2 - - - - - - 0.98

2.0 65 3 31 - - - - - 0.526

2.5 24 2 74 - - - - - -0.056

3.0 4 1 80 15 - - - - -0.355

3.5 - - 65 35 - - - - -0.435

4.0 - - 35 65 - - - - -0.455

4.5 - - 13 85 1 - - - -0.477

5.0 - - 4 87 6 1 2 - -0.517

5.5 - - 2 81 12 2 3 - -0.535

6.0 - - - 57 32 6 4 1 -0.577

TOA is found to extent HNO3 just by acid-base

reaction as shown below:

(C8H17)3N + HNO3 → (C8H17)3NH.NO3 (3)

triocttylammonium salt of nitrate

The product may extract low pH existing predominant

species (VO2+) according to the following reaction:

VO2+ + (C8H17)3NH.NO3 → (C8H17)3NVO2.NO3 + H

+

(cation exchange) (4)

At higher pH values, extraction occurs via the

following reaction: V10O26(OH)2

4- + 4 H+ + nTOA → 4H2V10O26.nTOA +2H2O (ion pair solvation) (5)

V10O27(OH)5- + 5H+ + nTOA → H4V10O27.nTOA + H2O

(ion pair solvation) (6)

V10O286-

+ 6 H+ + nTOA → H6V10O28.nTOA (7)

(ion pair solvation)

Rer V(V), the extractant dependence for reaction represented by Eqs. (4), (5), (6) and (7) are +1, -0.4, -0.5 and -0.6, respectively. It is, therefore, possible to calculate the theoretical pH dependence at a given equilibrium pH (eg. at pH(eq) = 2.50, pH dependence = 0.24×1+0.74× (-0.4) = -0.056; and at pH(eq) = 3.0, pH dependence = 0.04×1+0.80× (-0.4)+0.15×(-0.5) = -0.355). The theoretical pH dependences at various pH(eq) values are shown in the last column of Table I. Experimental results on pH(eq) dependence are of similar nature; positive sloped to zero sloped to negative sloped curves with increasing pH(eq) value are obtained consequently, above extraction reactions satisfy well the experimental pH-dependence.

The extractant dependence curve is shown in Fig. 4 for four sets of experimental parameters. In all cases, straight lines with positive slopes are obtained. In each case, though initial pH was kept constant, equilibrium pH was varied. No correction is made here. The positive extractant dependence supports the solvation of ion-pair by TOA, but the number of TOA per ion-pair varies with pH(eq).

The effect of NO3- on extraction is presented in

Fig. 5. The log D vs. log [NO3-], mol/L plot is a

curve which can be presented by Eqn: log D = -0.28 + log (1+1.82[NO3

-]). Therefore, the extraction ratio is

independent of [NO3-] in its lower concentration

region, but it is directly proportional to [NO3-] in its

higher concentration region. The results support the extraction of HNO3 by TOA.

Fig. 4. Effect of [TOA] on extraction. [V(V)](ini) = 0.50 g/L, temp. = 298 K, O/A = 1, time = 10 min, (), pH(ini) = 1, pH(eq) = 2.3±1.1;

(), pH(ini) = 2, pH(eq) = 4.1±1.0; (), pH(ini) = 3, pH(eq) = 4.25 ±

0.55; (), pH(ini) = 5, pH(eq) = 4.25±0.55.

Fig. 5. Effect of [NO3-] on extraction. [V(V)](ini) = 0.50 g/L, [TOA]

= 0.01 mol/L, pH(ini) = 1, Temp. = 300 K, Curve is theoretical: log D = -0.28 + log (1+1.82[NO3

-]); whereas, points are experimental.

Fig. 6. Effect of temperature. [V(V)](ini) = 0.5 g/L, O/A = 1, time =

10 min, [NO3-] = 0.192 mol/L, pH(ini) = 1; (), [TOA] = 0.10 mol/L,

pH(eq) = 2.96; (), [TOA] = 0.05 mol/L, pH(eq) = 2.17.

Figure 6 represents the vant Hoff’s plots for the

extraction system. It is seen that with the rise of

-3 -2 -1 0 1-2

-1

0

1

2

3

log D

log [TOA], mol/L

S = 2.6

S = 0.5

S = 1.2

S = 0.8

-1.0 -0.5 0.0 0.5 1.0-0.5

0.0

0.5

1.0

1.5

log

D

log [NO-

3], mol/L

3.1 3.2 3.3 3.4 3.50.5

1.0

1.5

2.0

2.5

S = 2.8 x 103

H = 54 kJ/mol

log D

(1/T)x103, K

-1

S = 3.25 x 103

H = 62 kJ/mol

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

42

temperature, extraction ratio is decreased. The

extraction process is, therefore, exothermic with H

value of about -58 kJ/mol

Loading of TOA by V(V) is shown in Fig. 7. It is

seen that the organic phase is almost saturated with

V(V) at about 12th contact when 0.10 mol/L TOA

solution is repeatedly contacted with 2 g/L V(V)

solution at pH(ini) = 1. The cumulative [V(V)]

increases gradually with contact number and almost

levels off at around 12th contact. At O/A = 1 in each

contact, 0.10 mol/L TOA can extract as much as 11.73

g V(V)/L; consequently, the loading capacity is 117.3

g V(V)/mol TOA. It is exceedingly a very high value

demanding commercialization.

Stripping of the extracted V(V) can be done by

0.75 mol/L NH4OH solution to the extent of 72% in

single stage. Stage-wise stripping is not so impressive.

IV. CONCLUSION

Vanadium (V) can be well extracted by tri-n-

octylamine within 5 min contact. Extraction ratio is

found to increase with increasing – [V(V)], [NO3-] and

[H+] in the aqueous phase and with increasing [TOA]

in the organic phase. More than 90% V(V) can be

extracted at pH(eq) = 2 by 0.10 mol/L TOA solution.

Mechanism of extraction is suggested. Rise of

temperature decreases extraction. 1 mole TOA can

extract as much as 2.3 mol V(V) at saturated loading.

Extracted species can be stripped by 0.75 mol/L

NH4OH solution to the extent of 72% in single stage;

but stage-stripping is not fruitful.

Fig. 7. Loading of V(V) in the organic phase. [V(V)] = 2 g/L, [TOA] = 0.1 mol/L, pH(ini) = 1, Temp. = 298 K.

REFERENCES [1] http://minerals.usgs.gov

[2] F. Islam and R. K. Biswas, “The solvent extraction of

vanadium(IV) from acidic sulhate-acetato solutions

with HDEHP in benzene and kerosene,” J. Inorg.

Nucl. Chem., vol. 42, pp. 415 – 420, 1980.

[3] R. K. Biswas and M. G. K. Mondal, “Kinetics of VO2+

extraction by D2EHPA,” Hydrometallurgy, vol. 69,

pp. 117-133, 2003.

[4] M. A. Hughes and R. K. Biswas, “Kinetics of

vanadium(IV) extraction in acidic sulphate-D2EHPA-

n-hexane system using Rotating Diffusion Cell

Technique,” Hydrometallurgy, vol. 26, pp. 281 – 297,

1991.

[5] K. O. Ipinmoroti and M. A. Hughes, “Mechanism of

V(IV) extraction in a chemical kinetic controlled

regime,” Hydrometallurgy, vol. 24, pp. 255-262, 1990.

[6] P. Nekovar and D. Schrotterova, “Extraction of V(V),

Mo(VI) and W(VI) polynuclear species by primene

JMT,” Chem. Eng. J., vol. 79, pp. 229-233, 2000.

[7] M.A. Olazabal, M. M. Orive, L. A. Fernandez and J.

M. Madariaga, “Selective extraction of V(V) from

solutions containing molybdenum (VI) by ammonium

salts dissolved in toluene,” Solvent Ex. Ion Exch., vol.

10, pp. 623-635, 1992.

[8] P. Zhang, K. Inoue, K. Yoshizuka and H. Tsuyama,

“Extraction and selective stripping of molybdenum

(VI) and vanadium (IV) from sulfuric acid solution

containing aluminum (III), cobalt (II), nickel (II) and

iron (III) by LIX 63 N in Exxsol D80,”

Hydrometallurgy, vol. 41, pp. 45-53, 1996.

[9] S. Jayadas and M. L. Reddy, “Solvent extraction

separation of V(V) from multivalent metal chloride

solutions using 2-ethylhexyl phosphonic acid mono-2-

ethylhexyl ester,” J. Chem. Tech. Biotech., vol. 77, pp.

1149-1156, 2002.

[10] R. K. Biswas and A. K. Karmakar, “Liquid liquid

extraction of V(IV) from sulfate medium by Cyanex

301 dissolved in kerosene,” Int. J. Nonfer. Met., vol. 2,

pp. 21-29, 2013.

[11] T. Sato, S. Ikoma and T. Nakamura, “Solvent

extraction of vanadium (IV) from hydrochloric acid

solutions by neutral organophosphorous compounds,”

Hydrometallurgy, vol. 6, pp. 13-23, 1980.

[12] V. L. Bykhovtsov and G. N. Melixhova, “Extraction

of quinquevalent vanadium with a technical mixture of

trialkylphosphine oxides,” Zh. Prikl. Khim., vol. 43,

pp. 954-959, 1970.

[13] S. Kopacz and L. Paidovski, “Extraction of vanadium

(V) from sulphuric acid solutions by aliphatic

alcohols,” Russ. J. Inorg. Chem., vol. 16, pp. 236-239,

1971.

[14] Y. Anjaneyulu, B. S. R. Sarma and V. P. R. Rao,

“Studies on the influence of some inorganic amines on

the extraction of vanadium (V)-oxine complex,” Ind.

Chem. Soc., vol. 4, pp. 596-598, 1977.

[15] A. Saily and S. N. Tandon, “Liquid-liquid extraction

behavior of V(IV) using phosphinic acids as

extractants,” Fresenius J. Anal. Chem., vol. 360, pp.

266-270, 1998.

[16] J. Bassette, R. C. Denny, G. H. Jeffery and J.

Mendham, “Vogel’s Textbook of Quantitative

Inorganic Analysis,” 4th Edn., ELBS, London., p. 752,

1979.

[17] L. Zeng and C. Y. Cheng, “A literature review of

recovery of molybdenum and vanadium from spent

hydrodemlphusisation catalysts; Part I and II,”

Hydrometallurgy, vol. 98, pp. 1-20,

2009.

0 2 4 6 8 10 12 140

2

4

6

8

10

12

14

Cu

mm

ula

tive

[V

(V)]

(org

), g

/L

Contact number

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

43

Kinetics of Extraction of Ti(IV) from SO42- Medium by

Cyanex 301 Dissolved in Kerosene


Dept. of Applied Chemistry and Chemical Engineering

Rajshahi University


[email protected]

Abstract— The kinetics of Ti(IV)-extraction by

Cyanex 301 (HA) have been investigated by measuring

initial flux of Ti(IV)-transfer using a Lewis cell operated

at 3 Hz. The empirical flux eqation at 298 K is found to

be: F (kmol/m2 s) = 10-4.288 [Ti(IV)](1+447[H+])-

1[HA](o)(1+1.18[SO42-])-1. The activation energy, Ea has

been measured to be 37-60 kJ/mol depending on

experimental parameters and temperature region. The

S± value is always highly negative. Analysis of the flux

equation has been done, at various parametric

conditions, to elucidate the mechanism of extraction.

The rate determining chemical reaction step, at all

parametric conditions appears as: TiO2+ A- → TiOA+;

and this step occurs via and SN2 mechanism.

Keywords— Kinetics, extraction, Ti(IV), Cyanex 301,

Lewis cell

I. INTRODUCTION

Bangladesh has a considerable reserve of ilmenite

in the beach sand, which is now considered as the

principal raw material for Ti-technology. Ilmenite can

be dissolved in sulfuric acid using various techniques

to yield solution containing Ti(IV), Fe(II) and Fe(III),

principally [1-4]. The separation of Ti(IV) from Fe(II)

and Fe(III) can effectively be carried out through

extraction by organophosphorous extractants [5-8].

Recently [9], the extraction behavior of Ti(IV) by

Cyanex 301 in kerosene-5% heptan-1-ol has been

reported from the equilibrium point of view. This

paper reports the kinetics of this process using Lewis

cell technique to elucidate the rate parameters and the

mechanism of extraction.

II. EXPEIMENTAL

A. Materials

Cyanex 301 was supplied by Cytec Canada Inc.

and used without further purification. Locally

available kerosene was distilled to collect colorless

fraction obtained within 473-533 K. Other chemicals

were of A. R. grade (E. Merck-BDH) products and

used without further purification.

B. Analytical

The aqueous Ti(IV) concentration was estimated

by the H2SO4-H2O2 method at 420 nm [10] using a uv-

visible spectrophotometer (UV-1650 PC, Shimadzu,

Japan). A Mettler Toledo pH – meter was used for pH

measurement. For pH adjustment, either anhydrous

Na2CO3 or dilute H2SO4 was used.

C. Preparation of solutions of Ti(IV) from TiO2

The stock solution of Ti(IV) was prepared by

digesting 50 g TiO2 in 50 mL conc. H2SO4 for 2 h

with constant stirring at a low heat (323-393 K)

followed by its partial lixiviation in 15% (v/v) H2SO4

solution. The insoluble part was filtered out to obtain

1 L solution containing 22.56 g Ti(IV) and 3.45 mol

SO42-

. On the other hand, the standard solution of

Ti(IV) was prepared on fusion of 1 g TiO2 with 10 g

KHSO4 (Pt- crucible, 2 h) followed by cooling and

complete dissolution in 15% (v/v) H2SO4 solution to

obtain 1 L solution (1 mL = 0.60 mg Ti(IV)). The

former solution on proper dilution, sulfate addition

and pH adjustment was used in flux measurement;

whereas the later solution was used for construction of

calibration curve for colorimetric analysis of Ti(IV).

D. Preparation of organic phase

Unlike other acidic organophosphorous acids,

Cyanex 301 is monomeric [11]; and on this basis,

169.50 mL of Cyanex 301 (Mol. wt. 322 and density

0.95 g/mL) was diluted by distilled kerosene

(containing 5% (v/v) heptan-1-ol) to 250 mL for

preparing 2 mol/L Cyanex 301 stock solution. This

solution was properly diluted by distilled kerosene

containing 5% (v/v) heptan-1-ol (de-emulsifier) for

use in flux measurement.

E. Cell and operating procedure

The cell consists of a jacketed glass container

facilitating temperature control. An aliquot (100 mL)

of aqueous solution is taken in this container. The

container has an air-tight lid having three bores: one

for inserting the shaft of an electric stirrer, another for

introducing a funnel having bend-tail directed towards

the wall of the beaker, to pour down 100 mL organic

phase without much disturbance of the interface, and

the rest for introducing a glass tube to take out

aqueous solution from the middle section of the

aqueous phase with the aid of a polythene tube and a

syringe. An electric stirrer having stirring blades at

two levels (1 cm long two blades at each level)

rotating at 3 Hz enables phase agitation without

interface waving. After certain interval, 2 mL aqueous

phase is taken out for analysis of its Ti(IV)- content.

The interfacial area is kept at 3.75×10-3

m2, which can

be changed by setting the circular plastic rings within

the container where interface being formed.

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

44

F. Treatment of experimental data

The flux (F) of Ti(IV)- transfer can be calculated

from the relation:

F (kmol/m2s) =

/Ai.t (1)

At a constant temperature, F is related to

concentration terms as follows: F (kmol/m

2s) = kf [Ti(IV)]

a [H

+]

b [HA](o)

c [SO4

2-]

d (2)

On taking logarithm of both sides of Eq. (2), one gets: log(F, kmol/m2s) = logkf + a log[Ti(IV)] + b log[H+] + clog

[HA](o) + d log [SO42-] (3)

Equation (3) states that when [H+], [HA](o) and [SO4

2-

] are kept constant at (h), (ha)(o) and (so42-

),

respectively, then the plot of log F vs. log [Ti(IV)]

should yield a straight line with „s‟ equaling to „a‟

and „I‟ equaling to log kf (h)b (ha)(o)

c (so4

2-)

d from

which the value of kf can be evaluated after finding

the values of „b‟, „c‟ and „d‟. These values can be

obtained from slopes of the log F vs. log [H+] (or, pH

for which „s‟ = -b), log F vs. log [HA](o) and log F vs.

log [SO42-

] plots, respectively.

The effect of temperature can be treated by the

Arrhenius equation:

log F = constant – Ea/2.303 R T (4)

Moreover, these can also be treated by the Activated

Complex Theory of reaction rate:

log(Fh/kT) = -H±/2.303 RT + S

±/2.303 R + logf (R)

(5)


The effects of Ai, [Ti(IV)], [H+], [HA] and [SO4

2-]

on F have been measured. It is seen that flux is

independent of A; which means that the cell of any

dimension can be used for F – measurement. The log

F vs. log [Ti(IV)] plots are shown in Fig. 1. For each

parameter, pairs of straight line intersecting of

[Ti(IV)] of ~1.25 g/L is obtained. At lcr, s 1 i.e. „a‟

in Eq. (2) is unity. At hcr, s = „a‟ = a negative value is

contrary to the general principle of chemical kinetics.

It is possibly due to formation of non-extractable

polymerized aqueous Ti(IV) species that starts

formation at [Ti(IV)] near to 1.2 g/L.

The log F vs. pH plots are not straight lines; rather

curves are obtained which can be fitted to Eq.: log F

= constant - log (1 + 447[H+]). This equation

indicates that log F vs. – log (1 + 447 [H+]) plot

would be a straight line with unity slope. Such plots

are shown in Fig. 2. It is therefore concluded that F

(1 + 447[H+])

-1; i.e. rate of extraction is directly

proportional to pH in its lower region; whereas, it is

independent of pH in its higher region.

The plots in Fig. 3 represents the variation of flux

with [HA](o). In each case, log F vs. log [HA](o) plot is

a straight line with unity slope. Therefore, the rate of

extraction is directly proportional to the extractant

concentration in the organic phase.

Fig. 1. Effect of [Ti(IV)] on flux. [SO4

2-] = 0.50 mol/L, Ai

= 0.00375 m2, o/a = 1 (o = 100 mL).

Fig. 2. Effect of pH on flux. [SO42-] = 0.50 mol/L, Ai =

0.00375 m2, o/a = 1 (o = 100 mL).

The log F vs. log [SO42-

] plots are curves which

can be fitted to Eq.: log F = constant – log (1 +

1.8[SO42-

]). This equation indicates that log F vs. –

log (1 + 1.8[SO42-

]) plot should be a straight line with

unity slope. Such plots are shown in Fig. 4. It is,

therefore, concluded that F (1 + 1.8[SO42-

])-1

; i.e.

rate of extraction is inversely proportional to [SO42-

]

in its hcr and independent of [SO42-

] in its lcr.

The Arrhenius i.e. log F vs. 1/T plots are shown in

Fig. 5. In all cases, straight lines are obtained. Ea

values are measured to be within 37 to 60 kJ/mol.

Treatments of temperature dependence data by the

Activated Complex Theory (log (Fh/kT) vs. 1/T plot)

yield straight lines (not shown). The estimated H±

value varies within 36 to 60 kJ/mol; and the S±

value varies within -127 to -205 J/mol K depending

on experimental paremeters.

From the intercepts of lines in Figs. 1-4, the

values of kf are calculated to be 10-4.288

and 10-3.581

at

293 K and 318 K, respectively, yielding Ea value of

50.4 kJ/mol.

From the above measurements, the flux equation,

at 293 K, for Ti(IV) transfer can be represented by:

F = 10-4.288 [Ti(IV)] (1 + 447[H+])-1 [HA](o) (1+1.8[SO42-]-1

(6)

-3.0 -2.5 -2.0 -1.5 -1.0-9.5

-9.0

-8.5

-8.0

-7.5

-7.0

-6.5

-6.0

-5.5

log [Ti(IV)], mol/L

log

(F

, km

ol/m

2s)

(), pH = 2.50, [HA](o) = 0.06 mol/L, Temp. = 293 K; s = 0.98, I = -6.055




-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0-9.0

-8.5

-8.0

-7.5

-7.0

-6.5

-log (1+447x10-pH

)

log

(F

, km

ol/m

2s)

(), [Ti(IV)](ini) = 1000 mg/L, [HA](o) = 0.06 mol/L, Temp. = 293 K; I = -7.50

(), [Ti(IV)](ini) = 1000 mg/L, [HA](o) = 0.40 mol/L, Temp. = 293 K; I = -6.70

(), [Ti(IV)](ini) = 1000 mg/L, [HA](o) = 0.06 mol/L, Temp. = 318 K; I = -6.94 (), [Ti(IV)](ini) = 100 mg/L, [HA](o) = 0.40 mol/L, Temp. = 318 K; I = -6.795

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

45

Fig. 3. Effect of [HA](o) on flux. [SO42-] = 0.50 mol/L, Ai =

0.00375 m2, o/a = 1 (o = 100 mL)

Fig. 4. Effect of [SO4

2-] on flux. Ai = 0.00375 m2, o/a = 1

(o = 100 mL), Temp = 293 K.

whence, [Ti(IV)] < 1.20 g/L. This equation yields the

following four limiting cases:

Case I: at lcr of H+ and SO4

2-

F = 10-4.288

[Ti(IV)] [HA](o) (7)

Case II: at lcr of H+ but hcr of SO4

2-

F = (10-4.288

/1.8) [Ti(IV)] [HA](o) [SO42-

]-1

(8)

Case III: at hcr of H+ but lcr of SO4

2-

F = (10-4.288

/447) [Ti(IV)] [HA](o) [H+]

-1 (9)

Case IV: at hcr of H+ and SO4

2-

F = (10-4.288/(447×1.8)) [Ti(IV)] [HA](o) [H+]-1 [SO4

2-]-1 (10)

At lcr of H+ (higher pH region), Ti(IV) exists most

likely as TiO(OH)+; so that [TiO(OH)

+] = βTiO(OH)

[TiO2+

] [OH-]. HA partition between organic phase

and interface (Po/I = [HA](o)/[HA](i)) and at interface it

is ionized (Ka = [H+](i) [A

-](i)/[HA](i)). The H

+ and A

-

are then partitioned between interface and aqueous

phase ( ⁄ = [H+](i)/[H

+](a); ⁄ = [A

-

](i)/[A-](a). In such a case, [HA](o) = Po/i Ka

-1 ⁄

⁄ [H+] [A

-]; so that Eq. (7) takes the form:

F = 10-18.288 Po/i Ka-1 ⁄ ⁄ [TiO2+]

[A-] (11)

Equation (11) suggests that the rate determining step

in this process is the following chemical reaction:

TiO2+

+ A- → TiOA

+ (12)

The Ea value of 37-60 kJ/mol at lcr of H+ indicates

that the process is either intermediate or chemical

control. Depending on experimental condition, either

Eq. (12) alone is slow; or, this step along with

diffusion of at least a reactant to the reaction site or a

product from the reaction site are equally slow to be

rate determining. High negative S± values suggest

that Eq. (12) occurs via an SN2 mechanism i.e. the

attack of 1st anionic ligand (A

-) on hydrated TiO

2+ to

form higher co-ordinated activated complex

[TiO(H2O)n.A]+ is slower than the dehydration step to

form normal co-ordinated [TiO(H2O)n-1A]+ and also

the addition of 2nd

A- to form [TiOA2].

Similarly, on consideration of the prevailing Ti(IV)

species at the conditions cited, Eqs. (8), (9) and (10)

can be modified, respectively, to:

F = (10-18.288

/1.8) Po/i

Ka-1

⁄ ⁄ [TiO2+

] [A-] (13)

Fig. 5. Effect of temperature on flux (Arrhenius plots).

[SO42-] = 0.50 mol/L, Ai = 0.00375 m2, o/a = 1 (o = 100

mL).

F = (10-4.288/447) Po/i Ka-1 ⁄ ⁄ [TiO2+] [A-]

(14)

F = (10-4.288/(447×1.8)) Po/i Ka-1 ⁄

⁄ [TiO2+] [A-]

(15)

Equations (13) – (15) are similar to Eq. (11); the

difference is only with the constant terms. So same

mechanism holds in cases II, III and IV.

IV. CONCLUSION

The initial rates per unit area of Ti(IV) transfer in

the system: Ti(IV) – SO4 (H+, Na

+) – Cyanex 301 –

kerosene – 5% (v/v) heptan-1-ol has been measured at

different experimental parameters to establish a rate

equation. This equation has been analyzed to provide

mechanism of extraction. Whatever be the

experimental condition the addition of the first anionic

ligand of the extractant (A-) to TiO

2+ to form TiOA

+ is

the slowest step which is supported by high activation

energy. This rate determining chemical reaction step

occurs via SN2 mechanism; i.e. addition of A- to

TiO(H2O)x2+

in forming higher co-ordinated activated

complex [TiO(H2O)xA]+ is the slowest step.

V. ACKNOWLEDGEMENT

Authors are grateful to Cytec Canada Inc. for

supplying Cyanex 301 as gift.

-1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0-8.5

-8.0

-7.5

-7.0

-6.5

log [HA], mol/L

log

(F

, km

ol/m

2s)

(), pH = 1.6, [Ti(IV)](ini) = 1000 mg/L, Temp. = 318 K; s = 0.99, I = -6.785



-0.7 -0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0-8.0

-7.8

-7.6

-7.4

-7.2

-7.0

-log (1+1.8x[SO2-

4 ]

log

(F

, km

ol/m

2s)

(), pH = 1.80, [HA](o) = 0.40 mol/L, [Ti(IV)](ini) = 1000 mg/L

(), pH = 2.50, [HA](o) = 0.20 mol/L, [Ti(IV)](ini) = 100 mg/L

3.10 3.15 3.20 3.25 3.30 3.35 3.40 3.45 3.50-8.5

-8.0

-7.5

-7.0

-6.5

-6.0

(1/T)x103, K

-1

log

(F

, km

ol/m

2s)

(), pH = 2.50, [Ti(IV)](ini) = 1000 mg/L, [HA](o) = 0.06 mol/L; s = -2100, Ea = 40.17 kJ/mol




ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

46

NOTATIONS AND ABBREVIATIONS

HA = Cyanex 301 (bis-2,4,4-

trimethylpentyl dithiophosphinic

acid)

= Amount of Ti(IV) transferred in

100 mL organic phase (if

concentration is expressed in

mg/L, then it equals to

c/10×1000×48), kmol

kf = Forward extraction rate constant

Ea = Activation energy, kJ/mol

H± = Enthalpy change on activation,

kJ/mol

S± = Entropy change on activation,

J/mol K

F = Flux of Ti(IV) transfer,

kmol/m2s

Ai = Interfacial area, m2

t = Time of phase contact, s

β = Stability or formation constant

a, b, c, d = Reaction order with respect to

(wrt) Ti(IV), H+, HA and SO4

2-

concentrations, respectively

h = Planck‟s constant, 6.626×10-34

J

s

k = Boltzman constant, 1.381×10-23

J/K

T = Absolute temperature, K

I = Intercept

s = Slope

(ti), (h), (ha),

(so42-

)

= Constant concentrations of

Ti(IV), H+, HA and SO4

2-,

respectively

P = Partition coefficient

R = Molar gas constant, 8.314 J/K

mol

= Acid dissociation constant of

HA

f(R) = Function of reactants, (ti)a (h)

b

(ha)c(o) (so4

2-)

d

Subscript (o) = Organic phase

Subscript (i) = Interface

Subscript (a) = Aqueous phase

wrt = With respect to

lcr = Lower concentration region

hcr = Higher concentration region

SN2 = Substitution neucleophilic

bimolecular

REFERENCES [1] M. Mozammel and A. Mohammadzadeh, “The

influence of pre-oxidation and leaching parameters on

Iranian ilmenite concentrate leaching efficiency:

Optimization and measurement,” Measurement, vol.

66, pp. 184-194, 2015.

[2] A. A. Baba, S. Swaroopa, M. K. Ghosh and F. A.

Adekola, “Mineralogical characterization and leaching

behavior of Nigerian ilmenite ore,” Trans. Nonferrous

Met. Soc. China, vol. 23, pp. 2743-2750, 2013.

[3] R. K. Biswas, M. F. Islam and M. A. Habib,

“Processing of ilmenite by roasting with reformed

product of LPG-water mixture in presence of nickel

powder and subsequent leaching,” Bangladesh J. Sci.

Ind. Res., vol. 33, pp. 425-433, 1998.

[4] R. K. Biswas, M. F. Islam and M. A. Habib,

“Processing of ilmenite through salt-water vapor

roasting and leaching,” Hydrometallurgy, vol. 42, pp.

367-375, 1996.

[5] F. Islam, M. Ali and S. Akhter, “Separation and

recovery of titanium from iron bearing leach liquors

by solvent extraction with di-2-ethylhexyl phosphoric

acid – tributyl phosphate -thiocyanate system,”

Bangladesh J. Sci. Ind. Res., vol. 13, pp. 222-230,

1978.

[6] F. Islam, R. K. Biswas and C. M. Mustafa, “Solvent

extraction of Ti(IV), Fe(III) and Fe(II) from acidic

sulphate medium with di-o-tolylphosphoric acid –

benzene-hexan-1-ol system: A separation and

mechanism study,” Hydrometallurgy, vol. 13, pp. 365-

376, 1985.

[7] K. C. Sole, “Recovery of titanium from the leach

liquor of titaniferrous magnetites by solvent

extraction. Part I, II and III,” Hydrometallurgy, vol.

51, pp 239-274, 1999.

[8] F. Islam and R. K. Biswas, “The solvent extraction of

Ti(IV), V(IV), Fe(III), Cr(III) and Mn(II) from acidic

sulphate-acetate media with bis(2-ethyl hexyl)

phosphoric acid in benzene: A theoretical separation

study,” J. Bang. Acad. Sci., vol. 5, pp. 61-70, 1981.

[9] R. K. Biswas and A. K. Karmakar, “Solvent extraction

of Ti(IV) from acidic sulphate medium by Cyanex 301

dissolved in kerosene,” Sep. Sci. Technol., vol. 49, pp.

278-289, 2014.

[10] J. Bassette, R. C. Denny, G. H. Jeffery and J.

Mendham, “Vogel’s Textbook of Quantitative

Inorganic Analysis,” 4th ed.; ELBS: London, p. 750,

1979.

[11] B. K. Tait, Cobalt-nickel separation: the extraction of

cobalt(II) and nickel(II) by Cyanex 301, Cyanex 302

and Cyanex 272. Hydrometallurgy, vol. 32, pp. 365-

372, 1993.

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

47

Production and Improvement of Waste Tire pyrolysis Oil to

be Utilized with Diesel in CI Engine

Md. Nurul Islam

Department of Mechanical Engineering

Rajshahi University of Engineering & Technology

Rajshahi, Bangladesh.

[email protected]

Md. Rafsan Nahian

Department of Mechanical Engineering

Rajshahi University of Engineering & Technology

Rajshahi, Bangladesh.

[email protected]

Abstract—The standard of living, quality of life and

development of a nation depend on its per capita energy

consumption. Global energy supply that mainly depends

on fossil fuel is decreasing day by day. It is estimated

that the energy demand will be increased five times by

the year 2021 from present scenario. Due to the fossil

fuel crisis, the development of alternative fuel

technologies are drawn more attraction to deliver the

replacement of fossil fuel. Pyrolysis is one of the

promising alternative fuel technology that produces

valuable oil, char and gas product from organic waste.

Early investigations report that tire pyrolysis oil

extracted from vacuum pyrolysis method seemed to

have properties similar to diesel fuel. The main concern

of this paper is to produce and improve the properties

of crude tire pyrolysis oil by desulfurizing, distilling and

utilize it with diesel in CI engine to analyze the

efficiency for various compositions.

Keywords—solid tire waste; pyrolysis; crude pyrolysis

oil; improvement; alternative fuel.

I. INTRODUCTION

Approximately 1.5 billion tires are produced each

year which will eventually enter the waste stream

representing a major potential waste and

environmental problem [1]. In Bangladesh, total waste

tire generation of each year is about 90000 tons [2].

Vehicle tires contain long chain polymer (butadiene,

isoprene and styrene- butadiene) which cross-linked

with sulpher thus have excessive resistant to

degradation. On the other hand, as a result of burning

of these tires excessive damage to human health

caused by the pollutant emissions such as poly-

aromatic hydrocarbons (PAHs), benzene, styrene,

butadiene and phenol-like substances [3]. Conversion

of these waste tires to energy through pyrolysis is one

of the recent technology in minimizing not only the

waste disposal but also to be utilized as an alternative

fuel for internal combustion engines. Pyrolysis is

generally described as the thermal decomposition of

the organic wastes in the absence of oxygen at

mediate temperature about 450 oC [4]. The advantage

of pyrolysis process is its ability to handle waste tire.

It was reported that pyrolysis oil of automobile tires

contain 85.54% C, 11.28% H, 1.92% O, 0.84% S and

0.42% N components [5]. Pyrolysis is also non toxic

or environmental harmful emission unlike incineration

[6]. Tire pyrolysis oil has been found to have a high

gross calorific value of around 41-44 MJ/Kg. It would

encourage their use as replacement for diesel fuel if it

is properly distilled [7]. Therefore, these waste tires

should be utilized by converting to new and clean

energies.

II. PRODUCTION OF CRUDE TIRE PYROLYSIS OIL (TPO)

At first, automobile tires are cut into a number of

pieces and the bead, steel wires and fabrics are

removed. The tire chips are washed, dried and fed in a

mild steel fixed bed reactor unit.

Fig. 1. Steps of pyrolysis process

The feedstock is externally heated up in the reactor

in absence of oxygen. The pyrolysis reactor design for

the experiment is a cylindrical chamber of inner

diameter 110 mm, outer diameter 115 mm, height 300

mm and fully insulated. 2kW of power is supplied to

the reactor for external heating. The temperature of

the reactor is controlled by a temperature controller.

The process is carried out between (450-650) oC. The

heating rate is maintained at 5 K/min. The residence

time of the feedstock in the reactor is 120 minutes.

The products of pyrolysis in the form of vapour are

sent to a water cooled condenser and the condensed

liquid is collected as fuel. Three products are obtained

in the pyrolysis namely; Tire Pyrolysis Oil (TPO),

Pyro gas and Char. 1.9 kg of feedstock is used to

produce 1 kg of Tire Prolysis Oil. The heat energy

required for pyrolysis process per kg of TPO produced

is around 6 MJ/kg [8]. The percentages of pyrolysis

products are given below in TABLE I.

TABLE I. PERCENTAGE OF PYROLYSIS PRODUCTS

Pyrolysis

products

Tire

Pyrolysis Oil

Char Pyro gas Moisture

Percentage

(%)

55 34 10 1

Heat

Solid waste

Heat

Thermodynamic decomposition Char

Condenser

Moisture

Liquid

Gases (CO2+CO+CH4)+ Volatile

Non condensable

gases

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

48

Fig. 2. Crude tire pyrolysis oil from waste tire

III. IMPROVEMENT OF CRUDE TIRE PYROLYSIS OIL

(TPO)

The improvement of crude TPO involves three stages,

A. Removal of moisture.

B. Desulphurization.

C. Distillation.

A. Removal of moisture

Initially crude TPO is heated up to 100 oC, in a

cylindrical vessel for a particular period to remove

the moisture, before subjecting it to any further

chemical treatment.

B. Desulphurization

The moisture free crude TPO contains impurities,

carbon particles and sulpher particles. A known

volume of concentric hydrosulphuric acid (8%) is

mixed with the crude TPO and stirred well. The

mixture is kept for about 40 hours. After 40 hours, the

mixture is found to be in two layers. The top layer is a

thin mixture and the bottom layer is thick sludge. The

top layer is taken for atmospheric distillation and the

sludge is removed and disposed off.

C. Distillation

Distillation is a commonly used method for purifying liquids and separating mixtures of liquids into their individual components. The distillation process is shown in Fig. 3.

Fig. 3. Sequence of distillation process

Atmospheric distillation process is carried out to

separate the lighter and heavier fraction of

hydrocarbon oil. A known sample of chemically

treated crude TPO is taken for vacuum distillation

process. The sample is externally heated in a closed

chamber by electric heater of 1.5 KW. The vapour

leaving the chamber is condensed in a water

condenser and the distilled tire pyrolysis oil (DTPO)

is collected separately. Non condensable volatile

vapours are left to the atmosphere. The distillation is

carried out between (150-200) oC. Nitrogen gas is

supplied to carry out producer gas from the reactor to

the condenser and also create inert environment to the

reactor. 80% of TPO is distilled in the distillation

whereas 5% of TPO is left out as pyro gas and 15% is

found as sludge.

Fig. 4. Experimental setup of the distillation plant

The DTPO has irritating odor like acid smell. The

odor can be reduced with the help of adding some

masking agents or odor removal agents. Fig. 5 shows

the physical view of distilled tire pyrolysis oil

(DTPO).

Fig. 5. Distilled tire pyrolysis oil

The properties of tire pyrolysis oil (TPO), distilled

tire pyrolysis oil (DTPO) and diesel fuel are shown in

TABLE II.

TABLE II. PROPERTIES OF TPO, DTPO AND DIESEL FUEL

Properties Tire

pyrolysis oil

Distilled tire

pyrolysis oil

Diesel fuel

Density at 15 oC, kg/L

0.9563 0.8355 0.8200-

0.8600

Kinematic

Viscosity at

40 oC, cst

16.39 0.89 2.00

Pour point, oC

-3.00 Below -6.00 -42 to -30

Flash point, oC

50.00 Below 10.00 Above 55

Gross

Calorific

Value, MJ/kg

42.00 43.56 44.00- 46.00

Heating

Evaporating Condensing

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

49

IV. PERFORMANCE TEST OF DISTILLED TIRE

PYROLYSIS OIL (DTPO)

Engine performance indicates the effect of a fuel in the engine. It shows the trend and possibility of using distilled tire pyrolysis oil to replace diesel fuel without any engine modifications [9]. It is necessary to determine engine brake power, brake specific fuel consumption and brake thermal efficiency. The performance parameters can be calculated by following equations [10].

A. Engine Brake power

Engine brake power (P) is delivered by engine and

absorbed load. It is the product of torque and angular

engine speed where P is engine brake power in KW;

N is angular speed of the engine in RPM as:

P=

B. Brake specific fuel consumption

Brake specific fuel consumption (BSFC) is the

comparison of engine to show the efficiency of the

engine against with fuel consumption of the engine in

kg/KWhr where (mf) is the fuel consumption rate in

kg/hr as:

BSFC=

C. Brake thermal efficiency

The percentage of brake thermal efficiency of the

engine is related to engine brake power and total

energy input to the engine.

The quality of the blended DTPO with diesel fuel is tested in Beco diesel engine. The engine is kept fixed at 27% part load. The specifications of the engine are shown in TABLE III.

TABLE III. ENGINE SPECIFICATIONS

Engine type 4 Stroke CI engine

Cooling Water cooling

Speed 1500 RPM

Rated Power 7.5 HP

DTPO has about 7% higher heating value than crude TPO. This is due to the elimination of the impurities, moisture, carbon particles, sulpher and sediments. Four test fuels have been taken for the performance test. These are 100% diesel fuel, 75% diesel with 25% distilled pyrolysis oil (DTPO 25), 50% diesel fuel with 50% distilled pyrolysis oil (DTPO 50) and 25% diesel with 75% distilled pyrolysis oil (DTPO 75).

TABLE IV. PERFORMANCE RESULTS FOR DIFFERENT BLENDED

FUELS

Fuel Brake

Power

(KW)

Efficiency

(%)

Brake specific fuel

consumption,

kg/KWhr

100%

Diesel

0.45 9.500 0.852

0.55 9.798 0.827

0.65 9.806 0.820

75%

Diesel+

25%

DTPO

0.45 9.498 0.852

0.55 9.706 0.829

0.65 9.801 0.824

50%

Diesel+

50%

DTPO

0.45 9.398 0.862

0.55 9.606 0.836

0.65 9.707 0.828

25%

Diesel+

75%

DTPO

0.45 9.304 0.866

0.55 9.606 0.838

0.65 9.705 0.830

The graphical representation of Performance of the engine with neat diesel and DTPO blends are described below in Fig. 6 and 7.

Fig. 6. Variation of efficiency with respect to brake power at 27% part load

Fig. 6 shows the comparison of the brake thermal efficiency with brake power for the tested fuels at 27% part load. It is observed from the figure that at 0.45 KW, the thermal efficiency is 9.5% for diesel fuel (DF) whereas for blending of 25% DTPO, 50% DTPO and 75% DTPO with diesel are 9.498%, 9.398% and 9.304% respectively. The thermal efficiencies of DTPO-DF blends are lower compared to diesel fuel. Reduction in thermal efficiencies by about 0.0212%, 1.07% and 2.06% for blending of 25% DTPO, 50% DTPO and 75% DTPO with diesel compared to diesel fuel.

9.2

9.3

9.4

9.5

9.6

9.7

9.8

9.9

0.4 0.5 0.6 0.7

Eff

icie

ncy (

%)

Brake Power (KW)

Efficiency Vs Brake Power

100%Diesel

75%Diesel+25% DTPO

50%Diesel+50% DTPO

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

50

Fig. 7. Variation of BSFC with respect to brake power at 27% part load

Fig. 7 shows the comparison of the break specific fuel consumption (BSFC) with brake power for the tested fuels at 27% part load. It is observed from the figure that BSFC increases with increase in the concentration of DTPO in DTPO-DF blend. At 0.45 KW, the BSFC is 0.852 for diesel fuel whereas for blending of 25% DTPO, 50% DTPO and 75% DTPO with diesel are 0.852, 0.862 and 0.866 respectively. The BSFC of DTPO-DF blends are higher compared to diesel fuel. Increase in BSFC by about 0.046%, 1.17% and 1.64% for blending of 25% DTPO, 50% DTPO and 75% DTPO with diesel compared to diesel fuel.

V. CONCLUSION

In the presented study, it is found that the distilled

tire pyrolysis oil is similar to diesel fuel and able to

replace diesel fuel in small engine. Blends of DTPO

25 gives better results than DTPO 50 and DTPO 75.

Following are the conclusions based on the

experimental results obtained while operating single

cylinder diesel engine with DTPO blends.

I. DTPO 25 blends can be directly utilized in

diesel engine without any engine

modification.

II. The brake thermal efficiency of DTPO 25

is slidely lower than diesel fuel. But for

DTPO 50 and DTPO 75 it is much lower

with compared to diesel fuel.

III. Brake specific fuel consumption of DTPO

25 blend is very close to the specific fuel

consumption of diesel. But for DTPO 50

and DTPO 75 it is slidely higher.

So it is advisable not to use DTPO 50 and DTPO 75

in CI engines.

REFERENCES

[1] P.T Williams, “Pyrolysis of waste tire: a review.” 2013 Aug;33(8):1714-28. doi: 10.1016/j.wasman.2013.05.003

[2] Bangladesh Bureau of statistics, Government of Peoples Republic of Bangladesh, Statistical Year book of Bangladesh 2008, 24th editon.

[3] Reisman JI. Air emissions from scrap tire combustion, EPA-600/R-97-115; 1997

[4] P.T Williams, S Besler, Environmental Science and Technology Fuel 74(9) 1277-1283, 1995

[5] Mastral AM, Murillo R, Callen MS, Garcia T. “Optimisation of scrap automotive tires recycling into valuable liquid fuels.” Resour conserv Recycl 2000;29:263-72

[6] J. Scheirs and W. Kaminsky, “Feedstock Recycling and Pyrolysis of Waste Pastic: Converting Waste Plastics into Diesel and Other Fuels,” John Wiley & Sons Ltd, Chichester, 2006. doi: 10.1002/0470021543

[7] M.R. Islam, H. HANIU, R.A. Beg, “Liquid fuels and chemicals for pyrolysis of motorcycle tire waste: product yield, compositions and related properties” Elsevier, Fuel, Vol: 87, pp. 3112-3122, 2008

[8] Isabel de Marco Rodriguez, et al “Pyrolysis of Scrap Tires”. Fuel processing technology; 72:9-22, 2001

[9] C. Wongkhorsub, N. Chindaprasert, “A comparison of the use of pyrolysis oils in diesel engine.” Enrgy and power engineering, 2013,5, pp. 350-355

[10] O. Arpa, R. Yumrutas and Z. Argumhan, “Experimental investigation of the effect of diesel-like fuel obtained from waste lubrication oil on engine performance and exhaust emissions.” Fuel process technology, Vol. 91, 2010, pp.1241-1249

0.81

0.82

0.83

0.84

0.85

0.86

0.87

0.88

0.4 0.5 0.6 0.7

BS

FC

(k

g/K

Wh

r)

Brake Power (KW)

Brake specific fuel consumption (BSFC) Vs

Brake Power

100% Diesel

75% Diesel+25% DTPO

50% Diesel+50% DTPO

25% Diesel+75% DTPO

ISBN: 978-984-34-0889-1

International Conference on Computer, Communication, Chemical, Materials and Electronic Engineering IC4ME2-2016, 24~25 March, 2016

51

Biological Evaluation of Radiotherapy Treatment Plan for Different Field Techniques in 3-Dimensional Conformal

Radiotherapy (3DCRT) Kausar A*, Azhari H A, Chaudhury S, Bhuiyan M A, Zakaria G A

Department of Medical Physics and Biomedical Engineering. Gono University

Dhaka, Bangladesh *[email protected]

Abstract— The purpose of this study is to evaluate

the 3D radiation treatment plan variants considering

biological parameters in external beam radiotherapy.

The biological parameters was calculated for 4-

fields, 6-fields, 7-fields and 9-fields beams for cervical

and prostate carcinoma. In biological parameters, the

tumor control probability (TCP) and normal tissue

complication probability (NTCP) calculation done by

the Poisson statistics model and Lyman-Kutcher-

Burman model respectively.

In cervical carcinoma, the TCP of four different

fields satisfied the biological criteria (TCP≥0.5).

However, only the NTCP of bladder for all fields

comply with the protocol (NTCP≤0.05) where the

rectum and the right & left femour go beyond the

tolerance limit. Similarly, in prostate carcinoma, the

TCP provides the agreeable results for all fields. On the

other hand, NTCP of bladder for 4-fields and 7-fields,

the rectum and the right & left femour exceeds the

acceptable limit where only the 6-fields and 9-fields of

rectum assure the protocol.

It was observed that the no treatment plan complies

the biological criteria in both cases, thus it is important

to evaluate the treatment plan biologically to achieve the

better outcomes. Hence the biological evaluations of

treatment plan need to be practiced by the radiation

oncologist as well as the medical physicist. Moreover,

TPS should integrate the biological evaluation tools and

should be used appropriate parameters for biologically

selecting the best treatment plan.

Keywords: 3DCRT, TCP, NTCP, Treatment plan.

I. INTRODUCTION

The goal of radiation therapy (RT) is to deliver a therapeutic dose of radiation to target tissues while minimizing the risks of normal tissue complications. Until recently, the quality of a RT plan has been judged by physical quantities, i.e., dose and dose-volume (DV) parameters, thought to correlate with biological response rather than by estimates of the biological outcome itself [1]. There are many tools used to evaluate the treatment plan biologically. Nowadays, the evaluation of treatment plans is usually done by analysis of dose volume histogram (DVH) as well as two-dimensional and three-dimensional spatial dose distributions [2].

In the early days of radiation oncology, the biological consequences of treatment were judged mainly by the dose absorbed in the tumor and surrounding normal tissues, with experience driven accounting for overall treatment time and fractionation. To correct the later two factors nominal standard dose (NSD), cumulative radiation effect (CRE), and time dose fractionation (TDF) formalisms were developed [3] [4] [5].

Different TCP model can be used for evaluating the treatment plan radio-biologically such as; Poisson statistics model, Zaider-Minerbo TCP model etc. The roots of normal tissue complication probability (NTCP) modeling lie in attempts to quantify the dependency of the tolerance dose for a certain radiation effect on the size of the treated region [6]. NTCP modeling gained more attention with the advent of three-dimensional conformal radiation therapy (3DCRT). Different NTCP models may be used for calculation such as, the Lyman-Kutcher-Burman (LKB) model, Relative Seriality model (Kallman K-and-S model), sigmoidal dose response NTCP model, and Critical volume NTCP model.

In this study, the Poisson statistics model has been used for TCP and the LKB model used for NTCP calculation. The biological evaluation has been done on two cancer cases i.e. Cervical and Prostate carcinoma.

II. MATERIALS AND METHODS

For evaluating a treatment plan biologically, two common cancer cases were selected. A case of cervical carcinoma having 2b stage; size of the tumor (T2), the number of node involvement (N1) and the metastasis (M0) had been taken. This patient undergone radiotherapy treatment as follows; EBRT dose 50Gy (Cervix with Nodal pelvis) is delivered in 25 fractions in 3DCRT. Further, the brachytherapy: 21Gy is delivered in 3 fractions.

A case of prostate carcinoma having the 2b stage (adenocarcinoma), size of the tumor T3a, number of nodes involved (N0) and the metastasis (M0) had been taken. This patient undergone radiotherapy treatment as follows; total EBRT radiation dose delivered by 76Gy (prostate with nodal pelvis) and the nodal pelvis irradiated by 50 Gy by 25 fractions in

ISBN: 978-984-34-0889-1


52

25 days and other 26 Gy is delivered only as the prostate boost in 3DCRT technique.

Table 1. Tumor data for TCP calculation [7] [8] [9].

Organ D50[Gy] 50 α/β[Gy]

Prostate-T3 46.29 0.95 10

Prostate, T0 - T4 38.39 0.74 10

Prostate, T4 41.78 0.6 10

Prostate, T2 45.18 1.16 10

Prostate, T0 and T1 28.34 1 10

Cervix 52 4 13.9

For biological evaluation, TCP was calculated by TCP based Poisson statistics model and the NTCP calculation was done by the Lyman-Kutcher-Burman (LKB) model.

TCP models generally rely on the assumption that tumor control requires the killing of all tumor clonogens. Poisson statistics predict that the probability of this occurring is:

…….............................. (1) Where, N=initial number of clonogens Ps (D) =cell survival fraction after a dose D. If it is assumed that cell survival can be described by single-hit mechanics, ………………................. (2)

The expression in Eq. (11) can be rewritten in terms of the two parameters describing the dose and normalized slope at the point of 50% probability of control, D50 and γ50 and:

………................ (3)

Using the assumption of independent subvolumes,

for the case of heterogeneous irradiation, the overall probability of tumor control is the product of the probabilities of killing all clonogens in each tumor subvolume described by the DDVH: ∏ Thus, for a given DDVH Di,vi, the TCP can be calculated using the following two-parameter TCP formula:

∑

⁄ ........................(4)

The above formula originates from an attempt to predict the TCP for an individual patient from a mechanistic perspective [2].

The most widely used phenomenological approach is the LKB (Lyman-Kutcher-Burman) model to account the probability of risk in normal tissues induced by radiation. A mathematically equivalent but more conceptually transparent formulation of the LKB model was first proposed by Mohan et al. (1992) [1]. According to this model, NTCP is calculated using the following equations:

∫

(

)

Where,

and ∑

Deff = is the dose that, if given uniformly to the entire volume, will lead to the same NTCP as the actual non-uniform dose distribution which is conceptually identical to the gEUD.

i = fractional organ volume receiving a dose Di

TD50 = dose where NTCPi = 50% for the organ of risk.

m = measure of the slope of the sigmoid-curve.

n = the volume effect parameter.

NTCP is in the range of:

∫

(

)

√

√

Table 2. Normal tissue end points and tolerance parameters [7].

Organ Fit Parameters

End Point Vref n m TD50

Bladder Whole organ 0.5 0.11 80

Symptomatic bladder contracture and volume loss

Rectum Whole organ 0.12 0.15 80

Severe proctitis/necrosis/stenosis/ festula

Femoral Head and

Neck

Whole organ 0.25 0.12 65 Necrosis

ISBN: 978-984-34-0889-1


53

III. RESULTS AND DISCUSSIONS

A. Comparison of Biological parameters for four different field Techniques in cervical carcinoma.

In TCP, the calculated result for four different fields shows the agreeable values (TCP≥ 0.5) [10]. Hence, all plan techniques TCP results were satisfactory. Table 3 Comparison of Biological parameters for four different field techniques in cervical carcinoma.

*f indicate field.

In (NTCP), the calculated results for the bladder of different fields satisfied the tolerance limit (NTCP≤ 0.05) [10]. Moreover, NTCP of the rectum and right & left femour for all fields are beams do not accept the NTCP tolerance limit.

Hence, according to the biological estimation among the four different fields, only the TCP provides the pleasurable value for all fields but the NTCP is very high for all risk organs excluding the bladder.

B. Comparison of Biological parameters for four different field techniques in Prostate carcinoma.

In TCP, the calculated results for four different fields provided the agreeable values (TCP≥ 0.5) [10]. Hence, the all plan techniques TCP provided very good results.

Table 4. Comparison of Biological parameters for four different field techniques in prostate carcinoma.

In NTCP, only the bladder of 6-field and 9-field are satisfied the criteria (NTCP≤ 0.05) [39]. Moreover, NTCP of rectum and right & left femour for all fields were very much higher than the tolerance limits (NTCP≤ 0.05). Hence, according to

the biological estimation among the four different fields, only the TCP fulfill the biological criteria for all fields but the NTCP is very high for all risk organs excluding bladder.

4-field 4-field DVH

6-field 6-field DVH

7-field 7-field DVH

9-field 9-field DVH Fig 1. An Example of Field arrangements and DVH of four different fields in Prostate Carcinoma .

Although, biological criteria includes TCP and NTCP parameters but in cervical carcinoma, no treatment fields provide the acceptable value according to the biological evaluation.

Finally, no plans were not accepted according to the biological evaluation of the treatment plan and organs at risk (OAR) doses are very much higher than the tolerance limit. Therefore, the physicist should evaluate the treatment plan very carefully. If the treatment plan can be done in IMRT technique or through optimization between target dose and OARs than NTCP may be minimized. So that, OAR have to be contoured accurately.

IV. CONCLUSION

In this study, there was a significant difference biological treatment plan evaluation, therefore, the

Parameters 4f 6 f 7f 9f

Biological

TCP 1.00 0.99 0.99 0.99 N NTCP Bladder 0.01 0.01 0.01 0.01

NTCP Rectum 1.00 1.00 1.00 1.00 NTCP Lt. femour 1.00 0.99 1.00 1.00 NTCP Rt. femour 0.99 1.00 0.99 0.99

Parameters 4f 6f 7f 9f

Biological

TCP 0.99 0.99 0.99 0.99 NTCP Bladder 0.99 0.01 0.99 0.01 NTCP Rectum 1.00 1.00 1.00 1.00

NTCP Lt.femour 1.00 1.00 1.00 1.00 NTCP Rt.femour 1.00 1.00 1.00 1.00

ISBN: 978-984-34-0889-1


54

biological evaluation of the treatment plan need to be introduced in TPS parallel to physical treatment planning. This study shown how to make out the physical evaluation and make more accessible current radiobiological modelling knowledge, and may serve as a useful aid in the prospective and retrospective analysis of radiotherapy treatment plans. Thus, it is important to evaluate the treatment plan considering biological criteria then the treatment plan may achieve better outcomes. Therefore, the medical doctors and medical physicists should be aware to integrate biological information into treatment plans for better selection in next generation of Radiotherapy.

ACKNOWDGMENT

I would like to show my greatest appreciation to Professor Dr. Golam Abu Zakaria, Department of Medical Physics and Biomedical Engineering, Gono Bishwabidyalay, Dhaka, Bangladesh and Professor and Chief Medical Physicist, Department of Medical Radiation Physics, Academic Teaching Hospital of the University of Cologne, Gummersbach, Germany.

I would like to gratefully acknowledge the enthusiastic supervision of Dr. Hasin Anupama Azhari, Department of Medical Physics and Biomedical Engineering, Gono Bishwabidyalay

I would like to express my gratitude towards my family, friends and other colleagues for their understanding, endless patience and encouragement

REFERENCES

[1] L.Allen, A. Markus, D. Joseph, J. Kyung Wook, M. Mary, M. Charles. "The use and QA of biologically related models for treatment planning: Short report of the TG-166 of the therapy physics committee of the AAPM," vol. 39 (3), pp. 1387, 2012.

[2] S. Arun, Oinam, L. Singh, "Dose volume histogram analysis and comparison of different radiobiological models using in-house developed software," Journal of Medical Physics, vol. 36(4), pp. 220-229, 2011.

[3] M. Strandqvist, “Studien uber die Kumulative Wirkung der Rontgenstrahlen bei Fraktionierung”, Acta Radiol Suppl, vol. 55, pp.1–300, 1944. [German].

[4] J.Kirk, W. Gray, and E. R. Watson, “Cumulative radiation effect. I. Fractionated treatment regimes,” Clin Radiol, vol. 22(2), pp.145–155, 1971.

[5] F Ellis. “Dose, time and fractionation: A clinical hypothesis.” Clin Radiol, vol.20 (1), pp.1–7, 1961.

[6] T.E. Schultheiss, C. G. Orton, and R. A. Peck. “Models in radiotherapy: Volume effects,” Med Phys, vol. 10(4), pp. 410–415, 1983.

[7] C. Burman, G.J. Kutcher, B. Emami, and M. Goitein, “Fitting of normal tissue tolerance data to an analytic function,” Int. J RadiatOncolBiolPhys, vol. 21 (1), pp.123-135, 1991.

[8] P. Källman, B.K. Lind, and A. “Brahme An algorithm for maximizing the probability of complication free tumor control in radiation therapy,” Phys Med Biol., vol. 37 (4), pp.871-890, 1992.

[9] P. Okunieff, D. Morgan, A. Niemierko, and H.D. Suit, “ Radiation dose-response of human tumors, ” Int J RadiatOncolBiolPhys, vol. 32(4), pp.1227-1237.1995.

[10] E. B. Podgorsak, Basic Radiobiology, Review of Radiation Oncology Physics: A Handbook for Teachers and Students, International Atomic Energy Agency: Vienna, Austria, pp: 408, May 2003.

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

55

Design of a Linearly Polarized Multi-band Transmission Line

Feed Microstrip Patch Antenna for Wireless Communications

Sheikh Dobir Hossain1*

Department of Physics

Jessore University of Science and Technology

Jessore-7408, Bangladesh

*[email protected]

Md. Khalid Hossain2

Institute of Electronics

Atomic Energy Research Establishment

Savar, Dhaka, Bangladesh

[email protected]

Rebeka Sultana3

Department of Computer Science & Engineering


Rajshahi 6205, Bangladesh

[email protected]

Abstract— A linear polarized transmission line feeding

dual band rectangular micro-strip patch antenna is

designed for the application in wireless communication.

The microstrip antenna contains a rectangular patch on

the upper layer of the dielectric material with dielectric

constant of 2.4 and there is a ground plane below the

dielectric material. Here the introduced of cavity model

with transmission line feed has the favor of low profile,

high gain and wide bandwidth of the antenna. The

antenna has overall size of 46.9 mm by 38.01 mm and

gives bandwidth of about 90 MHz at resonance

frequency of 2.45 GHz and that of 115 MHz at 4.1 GHz

frequency with Defected Ground Structure (DGS)

which are found to be favorable for wireless

communications.

Keywords- Micro-strip Antenna; Smith Chart; Cavity

Model; Dual Band Antenna; Transmission Line Feed .

I. INTRODUCTION

The electronic circuit miniaturization increases the

importance of wireless communication systems. In

commercial and government communication systems,

it is required to develop. This technological trend has

focused on the development of micro-strip antennas

(MSA) with low cost, minimal weight and low profile

antennas that are capable of maintaining high

performance over a large spectrum of frequencies.

The disadvantageous features of MSA such lower

value of efficiency, higher value of Q factor, poor

polarization purity and spurious feed radiation have

diminished their versatility. However it is possible to

improve the bandwidth (as long as 90 percent) and

efficiency (up to about 35 percent) of a microstrip

antenna by increasing the thickness of the dielectric

materials with cavity model [1]-[3].

II. EXPERIMENTAL MODEL

The proposed microstrip antenna is obtained using copper (annealed) rectangular patch of length 38.01 mm, width 46.9 mm and thickness 0.1 mm on the upper layer of the substrate whose thickness is 2.40 mm. Also there is a ground plane on the lower side of substrate with the thickness of 0.01 mm. Here we have

introduced two I slot on the patch with length and width are 14.2 mm and 1.4 mm respectively to obatain the dual band antenna operating at the resonance frequencies of 2.45 GHz and 4.1 GHz respectively.

Fig.1. Geometry of dual band MSA

The very popular and practical approximate for

different parameters of rectangular microstrip patch

antenna are [7]-[9]

the width that’s leads to good radiation efficiencies

is-

√

(1)

Here, =Velocity of light= Resonant frequency =Dielectric constant of the substrate

The value of effective dielectric constant is

√

(2)

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

56

Where, h is the thickness of the substrate and must

be in mm unit the normalized extension of the length

is

( )

( )

(3)

The effective length of the patch is

(4)

Where actual length is

√ (5)

III. RESULTS

The studied parameters are return loss (RL), voltage standing wave ratio (VSWR), smith chart, directivity and gain. The RL indicates how amount of power is lost in the load and does not return as a reflection. Our proposed antenna shows the return losses of -21.25 dB and -27.5 dB at the resonance frequencies of 2.45 GHz and 4.1 GHz, respectively. As it is lower than the acceptable value of return loss i.e. -10 dB so the designed antenna is perfectly matched and the power loss is minimum.The parameter VSWR determines how well the antenna is matched. Our designed antenna shows the VSWR are of 1.3883 at 2.45 GHz and that of 1.0825 at 4.1 GHz frequency which is below 2 (desired value for good antenna). Hence our designed antenna is perfectly matched with minimum loss. The study of smith chart is very importan during the design of a MSA. Using smith chart it is possible to obtain proper impedance matching between antenna and transmission line feeding. The impedance of our designed dual band antenna is 49 ohms which is approximately equal to the desired value of 50 ohms, indicating the minimum power loss.

The directivities of our designed antenna are 7.2 dBi in positive Z direction with angular width of 75.7 deg and 6.3dBi at an angle 49.0deg from positive Z direction with angular width of 68.5 deg at the resonance frequencies of 2.45 GHz and 4.1 GHz respectively and the gains are 6.698 dB and 6.797 dB at that frequencies, respectively which agrees well with the previous results [3]-[6].

Fig.2. Simulated return losses of dual band MSA at 2.45 GHz and

4.1 GHz

(a)

(b)

Fig.3. The VSWR of dual band MSA at (a) 2.45 GHz; (b) 4.1 GHz

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

57

Fig.4. Smith Chart of dual band MSA at 2.45 GHz and 4.1 GHz

(a)

(b)

Fig.5. Directivity of dual band MSA at (a) 2.45GHz; (b) 4.1GHZ

(a)

(b)

Fig.6. Gain of dual band MSA at (a) 2.45GHz; (b) 4.1GHZ

IV. SUMMARY OF THE RESULTS

The results of the dual band rectangular microstrip antenna operating at 2.45 GHz and 4.1GHz are summarized in the following table I.

TABLE I. OUTPUT PARAMETERS OF THE DUAL BAND MSA

RESONATING AT 2.45GHZ AND 4.1 GHZ FREQUENCIES

Resonating

frequency

fr (GHz)

Return

loss (dB)

Band-

width

(MHz)

VSWR Directivity

(dB)

Gain

(dB)

2.45 -21.25 90 1.3846 7.190 6.698

4.1 -27.5 115 1.082 6.502 6.797

V. CONCLUSIONS

In this paper, firstly we have looked on the design and simulation of single band antenna and then extend it to dual band antenna. The various parameters like return loss, VSWR, smith chart, directivity, gain, bandwidth and operating frequency are studied and also the effects of physical parametric on the performance of the designed antenna are studied. The designed antenna shows good impedance matching of approximately 49 ohm’s also it provides good gain and efficiency at the resonant frequencies of 2.45 GHz and 4.41 GHZ which indicate that the designed antenna can be used for various applications like RADAR, Bluetooth, Biomedical instruments etc.

ACKNOWLEDGMENT

We would like to thank all concerned with the Department of Applied Physics, Electronics & Communication Engineering, Islamic University, Kushtia 7003, Bangladesh for their all-out effort to support us for completing this research.

REFERENCES

[1] Shagun Maheshwari, Priyanka Jain and Archana Agarwal, “CPW-fed Wideband Antenna with U-shaped Ground Plane,” I.J. Wireless and Microwave Technologies (IJWMT). Volume 5, November 2014.

ISBN: 978-984-34-0889-1


IC4ME

2-2016, 24~25 March, 2016

58

[2] Ali A. Saleh and Abdulkareem S. Abdullah, “A Novel Design of Patch Antenna Loaded with Complementary Split-Ring Resonator and L- Shape Slot for (WiMAX/WLAN) Applications,” I.J. Wireless and Microwave Technologies (IJWMT), Volume 3, October 2014.

[3] C.A. Balanis, "Antenna Theory: Analysis and Design," Third Edition, ISBN 0-471-66782-X, Copyright 2005 John Wiley & Sons, Inc.

[4] D.M. Pozar, “Microstrip Antennas,” Proc. IEEE, Vol. 80, No. 1, pp. 79–81, January 1992.

[5] C.M. Krowne, “Cylindrical-Rectangular Microstrip Antenna,” IEEE Trans. Antennas Propagat., Vol. AP-31, No. 1, pp. 194–199, January 1983.

[6] I. Lier and K. R. Jakobsen, “Rectangular Microstrip Patch Antennas with Infinite and Finite Ground-Plane Dimensions,” IEEE Trans. Antennas Propagat., Vol. AP-31, No. 6, pp. 978–984, November 1983.

[7] Y.X. Guo, K.M. Luk and K.F. Lee, “U-slot circular patch antennas with L-probe feeding,” IEE Electronics Letters, Vol.35, No.20, pp. 1694-1695, 1999.

[8] Carver, Keith R. and James Mink, “Microstrip antenna technology,” Antennas and Propagation, IEEE Transactions , pp 2-24, Feb 1981.

[9] C.A. Balanis, "Advanced Engineering Electromagnetics," JohnWiley & Sons, New York, 1989.

ISBN: 978-984-34-0889-1

international conference on computer, communication...

Documents