PROCEEDINGS BOOK OF 1th INTERNATIONAL CONFERENCE ON ...

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PROCEEDINGS BOOK OF 1th INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE

SUPPORTED BY JOURNAL OF THERMAL ENGINEERING INTERNATIONAL JOURNAL OF ADVANCES ON AUTOMOTIVE AND TECHNOLOGY

ICPAS 2017 JANUARY 4-6,2017 ISTANBUL, TURKEY I

POSTER PRESENTATIONS AUTHORS RAHOU MOHAMED SEBAA FETHI CHEIKH ABDELMADJID RAHOU MOHAMED SEBAA FETHI CHEIKH ABDELMADJID ABDELHAMID BENHAMEL FETHI HADJOUI TENNOUGA LAHCENE MANSRI ALI MOHAMMED OMAR BENAISSA SAMIR HADJERI SID AHMED ZIDI ALA ABDESSEMED KAMEL E. DJEBBAR AMER S. EL-KALLINY T. SEHILI SEVDA ESMA AKKAYA ONUR YONTAR OSMAN NURI ERGUN BOUMEDIENE LASRI MOHAMMED SAHLAOUI FATIMA BOUASRIA MAMMAR BOUAMOUD MEVLUT DOGAN

PAPER TITLE

PAGE NUMBER

COMPARATIVE STUDY BETWEEN NC PROGRAMS

1

DEVELOPMENT OF NEW TECHNIQUE FOR HELP IN TECHNICAL TEACHING

5

IMPACT OF WELDED JOINT DEFECTS ON PIPE LIFE EFFECTS OF MECHANICAL SHOCKS VISCOMETRIC STUDY OF THE INTERACTION BETWEEN POLYELECTROLYTE COMPLEX AND SURFACTANT HIGH PERFORMANCE FUZZY LOGIC CONTROL OF INDUCTION MOTOR DRIVES POWERED BY PHOTOVOLTAIC PANEL USING FUZZY MPPT CONTROLLER THE IMPACTS OF UV DIRECT PHOTOLYSIS AND (UV/H2O2, UV/NAOCL) ADVANCED OXIDATION PROCESSES ON THE DEGRADATION OF MONOCHLORAMINE USING LOW PRESSURE LAMP

9 13

17

23

NOISE POLLUTION IN THE METROPOLITAN CITY CENTER OF SAMSUN, TURKEY

34

TRIPLE DIFFERENTIAL CROSS SECTIONS FOR THE SINGLE IONIZATION OF METHANE MOLECULE (CH4) BY ELECTRON IMPACT

38

ABDELKRIM KAHOU ROUMAISSA AIDOUD

INHIBITION OF CALCIUM CARBONATE DEPOSITION ON STAINLESS STEEL USING OLIVE LEAF EXTRACT AS A GREEN INHIBITOR OF CALCIUM CARBONATE

41

KHALFAOUI AMEL MENIAI ABDESSALAM HASSEN DERBAL KERROUM

MACROSCOPIC STUDY OF THE RETENTION CAPACITY OF ORANGE PEEL TO THE ORGANIC AND INORGANIC POLLUANTS IN WATER

46

DJEDDOU FERHAT SMATA LAKHDAR

DETERMINISTIC OPTIMIZATION AND A RELIABILITY BASED DESIGN OF A CAMFELLOWER MECHANISM

50

KERROUM DERBAL BANI KHEIREDINE MOSSAAB BENCHEIKHLEHOCINE

STUDY OF INHIBITING EFFECT OF NACL ON THE PRODUCED BIOGAS FROM ALGERIAN DAIRY WASTES IN MESOPHILIC CONDITION

58

ABDERREZZAQ BENALIA KERROUM DERBAL

STUDY OF CHEMICAL ACTIVATION OF CACTUS: USED AS BIO-COAGULANT FOR WASTEWATER TREATMENT

63

M.N. AMROUN M. KHADRAOUI R. MILOUA N. BENRAMDANE K. SAHRAOUI BOUKHARI.A BOUKHELF.F SEKKAL.M MERADJAH.M TOUNSI.A

STRUCTURAL, OPTICAL AND AC CONDUCTIVITY STUDIES ON ALLOY CD1-X SNX S THIN FILMS

A NEW SHEAR DEFORMATION THEORY FOR WAVE PROPAGATION OF THICK FUNCTIONALLY GRADED MATERIALS PLATES UNDER THERMAL EFFECT

II

70

76

BEHROZ DAVARI FIROUZ NAZARI ALAM MANSOUR NAZARI . H. YAHI A. BOUZIDI A. NAKRELA M. MEDLES H. TABET-DERRAZ RADJAA BENABBOUN DALILA MESRI ASMAA BOUABÇA ABDELKADER TADJER ABDELAZIZ LAKDJA ABDULLAH A. AWNI ZAINAB O. HAMED DORUK GÜRKAN MIHRIGÜL ALTAN KAHINA IGGUIA MUSTAPHA KACIA NICOLAS LE MOIGNEB ANNE BERGERETB MOHAMED MAHLOU KHALID MUHAMMAD KAREEM AL-KHAFAJI MELTEM ERYILMAZ ARIANE KHALISSA CHORFA ABDELLAH SMATA LAKHEDAR RUBIO FAUSTO ABBAS ISMAEL ALI MIRDAN AHMET DABANLI

MARINA GONZÁLEZPÉREZ SARA MARGARIDA DE OLIVEIRA BAPTISTA ANTÓNIO PEREIRA ANTÓNIO CANDEIAS ANA TERESA CALDEIRA MARINA GONZÁLEZPÉREZ SARA MARGARIDA DE OLIVEIRA BAPTISTA ANTÓNIO PEREIRA ANTÓNIO CANDEIAS ANA TERESA CALDEIRA BERRICHI YAMINA GHAFFOUR KHEIRREDDINE KESKES BOUALEM ABDERRAHMANE BENTOUHAMI

STUDY ON SOME ECOLOGICAL FACTORS OF SOFT TICK IN LORESTAN PROVINCE, IRAN

EFFECT OF TEMPERATURE ON THE STRUCTURAL AND OPTICAL PROPERTIES OF SNO2 THIN FILMS PREPARED BY SPRAY PYROLYSIS FIRST-PRINCIPLE CALCULATIONS OF THE STRUCTURAL, ELECTRONIC, MAGNETIC PROPERTIES OF HALF-HEUSLER COMPOUNDS XSRC (X=K, RB) FIMH GENE POLYMORPHISM AND ITS RELATION TO ANTIMICROBIAL AGENTS IN UROPATHOGENIC ESCHERICHIA COLI (UPEC) IMPROVEMENT PROPERTIES OF MOLDING POLYPROPYLENE FOAMS OBTAINED BY INJECTION GAMMA IRRADIATION EFFECTS ON THERMAL AND MECHANICAL PROPERTIES OF POLY (3HYDROXYBUTYRATE-CO-3-HYDROXYVALERATE) (PHBV)/CLOISITE 30B NANOBIOCOMPOSITES AUDITOR TECHNOLOGY AND PRIVACY CONTROL TO SECURE E-LEARNING INFORMATION ON CLOUD STORAGE ELABORATION OF GLASS-CERAMICS BY THE CONTROLLED CRYSTALLISATION: INFLUENCE OF THE ADOPTED THERMAL PROTOCOL. OPTIMIZE THE SLOPE, PATH, AND COST OF EXTENSIONS OF THE EXISTING SEWERAGE NETWORK BY USING GIS SYSTEMS CASE STUDY: THE KIRKUK SEWERAGE DIRECTORATE

A SHORTENED RNA-FISH PROTOCOL FOR ANALYZING ARTWORKS’ MICROCOLONIZERS

DETECTION OF SPORES AND HYPHAE OF ARTWORKS’ BIODETERIOGENIC FILAMENTOUS FUNGI BY RNA-FISH

INP/INGAAS DOUBLE HETEROJUNCTION BIPOLAR TRANSISTOR EXPERIMENTAL AND THEORETICAL INVESTIGATIONS OF LOW VELOCITY IMPACT ON NOMEX AND ALUMINUM SANDWICH PANELS

III

81

85

88

92

104

112

121

127

131

136

141

147

152

A. ARFAOUI S. TOUIHRI

GLEDJAN CAKA

B. SEIF-EDDINE

B. SEIF-EDDINE, CANSU AKBULUT BURCU ÖZTÜRK CEYDA ÖZTÜRK NAZAN DENIZ YÖN CANSU AKBULUT BURCU ÖZTÜRK CEYDA ÖZTÜRK NAZAN DENIZ YÖN CANSU AKBULUT BURCU ÖZTÜRK CEYDA ÖZTÜRK NAZAN DENIZ YÖN TAREK BOUDIAR CHAWKI BENSOUICI ABDESLEM BOUZINA

SOUMIA BENGUEDIAB

TUĞBA ÇORLU

N.BOUKABCHA MOHAMED SEGHİR ZAHİRA AMİNA MEZOUAGH MHAMED DJENNAD A. MEZOUAGH Z. MOHAMED SGHİR A. FEDDAG GÖZDE CANLI Z. ULYA NURULLAHOĞLU

ANNEALING EFFECT ON PHYSICAL PROPERTIES OF EVAPORATED MOLYBDENUM OXIDE THIN FILMS FOR ETHANOL SENSING

158

INHIBITORY EFFECTS OF BIOTECHNOLOGICAL DRUGS ON THE SIGNALING OF ACUTE MYELOID LEUKEMIA

159

TYPES OF CROSSOVER AND MUTATION OPERATOR METHODS FOR GENETIC ALGORITHM USED IN PERMUTATION PROBLEMS BEHAVIOURAL MODELLING OF CORUNDUM UNDER THE EFFECT OF POROSITY RATE

163

DRY SLIDING WEAR BEHAVIOUR OF TI3SIC2 AND THE EFFECT OF TIC ON ITS. B. SEIF-EDDINE, HISTOLOGICAL EFFECTS OF TRIBENURON METHYL ON LIVER TISSUE OF ZEBRAFISH

171

170

172

ISTOLOGICAL EFFECTS OF MANCOZEB OVARY TISSUE OF ZEBRAFISH

173

OXICOLOGICAL EFFECTS OF TRIBENURON METHYL ON TESTIS TISSUE OF ZEBRAFISH

174

IN VITRO ANTIOXIDANT ACTIVITY OF METHANOL AND CHLOROFORM EXTRACTS OF ALGERIAN ROSMARINUS TOURNIFORTII DE NOÉ LEAVES ULTRASOUND ASSISTED SYNTHESIS OF AMINOPHOSPHONATES DERIVED OF AMINO ALCOHOL CATALYZED BY TIO2 AND SOLVENT FREE CONDITION DETERMINATION OF THERMAL BUCKLING PROPERTIES OF CARBONE NANOTUBE USING NON LOCAL TIMOCHENKO BEAM MODÈLE LOW NO GAS CONCENTRATİON PROPERTİES OF ZN0.75SN0.25O NANOSTRUCTURES GROWN BY SUCCESSİVE İONİC LAYER ADSORPTİON AND REACTİON METHOD INVESTİGATİON THEORİQUE AND ELECTRON DENSİTY STUDY OF 4-METHYL-N-[(5NİTROTHİOPHEN-2-YLMETHYLİDENE)] ANİLİNE COMPOUND POLYMERIZATION OF STYRENE 4 SULFONATE WITHIN MACROPOROUS HYDROTALCITE AND THE SUBSEQUENT CARBONACEOUS REPLIQUA USED IN THE WASTEWATER TREATMENT ELIMINATION OF METHANOL AND ETHANOL BY SYNTHETIC ZEOLITES (4A)

175

EFFECTS OF TITANIUM DIOXIDE NANOPARTICLE ON THE MITOTIC INDEX AND FORMATION OF MICRONUCLEI ON GALLERİA MELLONELLA (L.) (LEPIDOPTERA: PYRALIDAE) LARVAL HEMOCYTES

182

IV

176

177

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181

KARİMA MENAD AHMED FEDDAG SMATA LAKHEDAR

AKRAMMUDHERKAREEM ALJBORI HUSSEİN MUDHEHER KAREEM ALGBURI HACİ AHMET DEVECİ GÖKHAN NUR CANAN CAN

STUDY OF ION EXCHANGE ON ZEOLITES MATERIALS ELABORATION OF GLASS-CERAMICS BY THE CONTROLLED CRYSTALLISATION: INFLUENCE OF THE ADOPTED THERMAL PROTOCOL.

EFFECT ON LEVEL OF PLASMA MALONDIALDEHIDE OF BELLIS IN CYPRINUS CARPIO

183

184

185

OPENING SPEECH

Dear our audience, It gives me great pleasure to extend to you all a very warm welcome on behalf of the organizing committee. It is an opportune time to have collaboration with other researchers and discuss problems of mutual interest with participants from the world now. First of all, we need to thank our rector again for his support to this organization. There were over 200 accepted abstracts and 4 invited speakers as they can be seen from our conference website. Unfortunately, we have got 90 submitted full papers and posters in our conference proceedings. Finally, we would like to reveal that our aim is to gather over 1000 participants from all over the world in the near future. Make sure that we will do our best to reach this aim as we have been doing for all our involved social and scientific works. We would like emphasize the importance of the use of energy sources efficiently again here. We are in a new period where we should surpass traditional power generating systems, owing to critical energetic, environmental and sustainability subjects. The existing energy situation of the world has presented some difficulties to be solved such as the integration of clean energy generation and the usage of efficient high-power and energy storage systems. The energy industry

V

has to struggle against difficulties brought by the integration of renewable energy systems regarding with reliability and stability of the power grid. In any case, it becomes extremely significant to benefit from energy storage systems in order to stabilize and improve the efficiency of the power systems using ultimate generation batteries, ultra-capacitors, hydrogen based systems and mechanical systems, among others. Recently, the power electronics suggests effective way outs to be applied to the new spread energy grid idea. A micro power generation with diesel systems and renewable energy is considerably depending on instabilities directly attributed to the fluctuations and the range ability of the resources. It seems extremely suggested to use storage units in order to confirm the accessibility of energy, endurance and efficiency of the system. Consistent with the formulation of the problem of energy storage, time or regularity properties tied to the existing technologies should be connected to the problem of multi-objective management of energy. The related offered proposals deal with strategies for managing energy in a power system including wind, diesel engine, flywheel, battery and super capacitor as hybridization nominees. In concluding, I wish you every success in your deliberations and a very pleasant stay in Istanbul. Regards, Ahmet Selim Dalkilic

CONFERENCE CHAIRMAN Ahmet Selim Dalkılıç, Yildiz Technical University, TR

ORGANISING COMMITTEE 1. Ahmet Selim Dalkılıç, Yildiz Technical University, TR (ConferenceChair) 2. Övün IŞIN, Yildiz Technical University, TR 3. Tarkan SANDALCI, Yildiz Technical University, TR 4. Levent YÜKSEK, Yildiz Technical University, TR 5. Orkun ÖZENER, Yildiz Technical University, TR 6. Yasin KARAGÖZ, Yildiz Technical University, TR 7. Emre ORAK, Yildiz Technical University, TR

SCIENTIFIC COMMITTEE

VI

1. Hakan KALELİ, Yildiz Technical University, TR 2. Ümit KÖYLÜ, Missouri University of Science and Technology, USA 3. Balaram Kundu, Jadavpur University, India 4. Dongsheng Wen, University of Leeds, United Kingdom 5. Godson Asirvatham Lazarus, Karunya University, India 6. Enrico Scıubba, Roma University, Italy 7. Ehsan Ebrahimnia-Bajestan, Graduate University of Advanced Technology, Iran 8. Tzvetelin Georgiev, University of Ruse, Bulgaria 9. Ioan Pop, Emanuel University Oradea Oradea, Romania 10. Moh'd A. Al-Nımr, Jordan University of Science and Technology, Jordan 11. Mohamed Awad, Mansoura University, Egypt 12. Patrice Estelle, Université Rennes 1, France 13. Somchai Wongwises, King Mongkut's University of Technology Thonburi, Thailand 14. Ahmed Kadhim Hussein, University of Babylon, Iraq 15. Ahmet Selim Dalkılıç, Yildiz Technical University, TR 16. Tarkan SANDALCI, Yildiz Technical University, TR 17. Övün IŞIN, Yildiz Technical University, TR 18. Orkun ÖZENER, Yildiz Technical University, TR 19. Levent YÜKSEK, Yildiz Technical University, TR 20. Jamal KHATIB, University of Wolverhampton, UK

ADVISORY COMMITTEE 1. Hakan KALELİ, Yildiz Technical University, TR 2. Brian AGNEW, Northumbria University, UK 3. Dongsheng WEN, University of Leeds, United Kingdom 4. Ümit KÖYLÜ, Missouri University of Science and Technology, USA

VII

VIII

ISTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

COMPARATIVE STUDY BETWEEN NC PROGRAMS * RAHOU Mohamed ESSA –Tlemcen IS2M Laboratory Tlemcen, Algeria

SEBAA fethi Tlemcen University IS2M Laboratory Tlemcen, Algeria

CHEIKH Abdelmadjid Tlemcen University IS2M Laboratory Tlemcen, Algeria Keywords: NC, programs, address * Corresponding author:, +213779545990 E-mail address: [email protected]

ABSTRACT The programming of NC machines based on standard programming commands. These standards are incomplete. Builders directors CNC fit the specifications of their machines. This work aims to study the statistical inconsistencies addresses digital control FANUC, FAGOR, NUM SINUMRIK in turning and milling. Both parties have been developed. The first is to highlight the differences preparatory functions and their impact on programming. The second part presents a statistical study of the NC addresses for different programming languages to aid selection of the Director of CNC. INTRODUCTION The NC is a technique of controlling the operation of a machine from a program without direct operator intervention during execution. With the advances in microelectronics and computer industry, whose costs have continued to decline while the performance and usability have increased significantly, this method of control is increasingly present in the workshops. This technological evolution has replaced controls hardwired equipment by microprocessors that provide real-time calculations that previously had to be done when programming. With the help of computers, parametric programming enables adaptation procedures. In addition to reducing outstanding (splitting long series production and just-in-time), the flexibility of labor, the development of CN's goal is compliance with more stringent time by optimizing the time of preparation of dead time and machining time as well as accurate and easily reusable machining programs.

The program content is developed with reference to the ISO regarding the machine language frequently in control manager regarding the specificities of each manufacturer DNC[1]. Given that each manufacturer of control manager by trying all means of differentiate its products from those of the competition and develops programming languages standard FANUC SINUMERIK, NUM, PHILIPS, BOSCH, FAGOR, MAZOL,… Some manufacturers offer features that differentiate the potential of their governing control compete on the guiding control microprocessor, the programming language is interpreted to be translated into a workable framework. Despite numerous efforts to standardize the machines have different languages, resulting in the need to adapt to the peculiarities of the machine on which they should be loaded. NF standards (ISO 6983-1) (NF Z68-037), NF [ISO 4342] describe programming languages. Each manufacturer of control manager tries by all means to differentiate their products from the competition and develop standard programming languages. These incompatibilities have despite many efforts to standardize.. The non-uniformity of the language used creates confusion such as differences in the timing of a function, the ambiguities of appointment and the programming of machines of the same manufacturer [2]. This work aim to study the incompatibility of NC commands the most used.

Conference Paper

CONFLICTS OF PREPARATORY FUNCTIONSPUT Table 1 show the differences G preparatory functions most used in industry controls (FANUC [3,7] SINUMERIK [4]

NUM [5,9] and FAGOR [6,8]). Common codes to four commands such as G00, G01, G02, G03, G40, G41, G42 ....

Table 1: Statistical Study CODE G 05 07 09 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 36 37 38 39 43 44 45 46 47 48 49 50 51 52 53 54 55

FANUC SINUM NUM FAGOR TR ML TR ML TR ML TR ML + + + + + + + + + + * * * * + * * + + + + + + + + + + * * + * * + * * * * * * + * * + * * * * * * + + * * + + + + * * + + + + + + + + + + + + + + + + * * + * * + * * * * * * + * * + * * + + +

CODE G 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99

FANUC SINUM NUM FAGOR TR ML TR ML TR ML TR ML + + + + + + + + + + + + + + + + + * * + * * + * * * * * * * * + + + * * + * * + * * * * + + + + + + + * * + + * * + + * * + + * * + + * * * * + * * * * + + * * + * * * * + * * + + + * * + + + + + + + * * + * * +

Conference Paper

+: Code in turning or in Milling. * : The same code has two different designations in turning or millin The advantage of the Sinumerik (Siemens) lies in the lack of differences for the same code when there and turning and milling unlike Fagor or the difference is relatively large order. NC programming in ISO code is considered unfriendly given the complexity of the addresses used in the programming of machining cycles such instructions: G.. EH .. EF .. EI .. EJ .. EQ .. ER ... ranging from one code to another, hence the diversity of managers control Regarding the auxiliary functions, there is a correlation between the main functions such as starting, stopping the spindle lubrication, rotation, change tools, end of the program .... With the exception of auxiliary functions used by different manufacturers in a competitive purpose, the main difference lies in the subroutine call and end subroutine respectively coded M98 and M99 in the case of FANUC, unlike other commands (FAGOR, NUM) using preparatory functions G, while SINUMERIK uses the letter L followed by the number of the desired machining cycle.

STATISTICAL STUDY OF PREPARATORY FUNCTIONS Statistical analysis showed differences in the command codes studied in terms of existence of code, number of codes used number of standardized codes and other criteria as shown in Table 2. This study highlights a proposal for the following classification:    

SINUMERIK FANUC NUM FAGOR

On the commercial side, the manufacturer FANUC offers two control options to reduce the existing differences in relation to other competing manufacturers, allowing it to be used in the majority of CAM software.

Table 2: Statistical Study FANUC TR

ML

Number of codes 53 used

75

unstandardized Common codes Code turning

in

Code milling

in

Code turning milling

in and

TR FR TR FR

25

23

47,16 31,50 52,83

28

37,33

12

13

%

NUM TR

ML

61

97

22

16

13

02,96 00

36,06 16,49 82,45

22,63 14 45,33

%

77,04

47

34

SINUMERIK TR

ML

34

45

08

08

16,94

00

17,77 71,11

TR

ML

73

93

30

38

28,26

00

33

%

41,09 40,86 52,05

38

40,86

08,57 02 13

00

23,52 91,42

32

22,95 03 10

%

FAGOR

02,73 22

34,37

33

27,52

Conference Paper

[4] CONCLUSION This work has helped to highlight the differences and incompatibilities between the addresses of the various commands. We find that 62.50% of the addresses using one or two appointments, while the remaining addresses, or 37.50%, using four to nine nominations. This study could be used as a criterion of choice of material depending on the desired goal. About a third of the addresses do not change regardless of the order designations used. The syntax for writing a block of program database used for the development of an adaptation module of the NC machining instructions and learning NC programming REFERENCES [1]

[2]

[3]

C. MARTY, C. CASSAGNES, P. MARIN, septembre 1993, la Pratique de la Commande Numérique des Machines Outils, Editions LAVOISIER, Paris. SEBAA F, CHEIKH A, Module d’adaptation des instructions d’usinage des MOCN, JEM 03,Annaba ,2003. FANUC, 1995, Manuels de tournage B62634/02 et fraisage B62644/02, FANUC GE LTD, Tokyo.

[5] [6]

[7]

[8]

[9]

EMCO WIN, 2003, Manuel de programmation sinumerik 810/820 (DIN 66025), EMCO, Autriche. J-P. URSO, mars 1999, Commande Numérique Programmation, Editions CASTEILLA, Paris. SEBAA. F., RAHOU M. , CHEIKH A., Contribution à la programmation des adresses CN pour différents langages dans un environement FAO, 9ème Congrés de Mécanique, Marrakech, Maroc,2009. F.SEBAA , A. CHEIKH , Incompatibilités des commandes des MOCN et leurs impacts sur la programmation assistée en CFAO,STEMA'03,Tlemcen ,Algerie,2003. SEBAA F, Cheikh A et MEDJADI N Integration De L’outil Multimedia Dans La Programmation CN Conversationnelle Dans Un Environnement FAO, CIP'2005,Tlemcen ,algerie.2005 RAHOU M., SEBAA. F. et Cheikh A., Etude statistique des incompatibilités des adresses CN de différents langages de programmation, 9ème Congrés de Mécanique, Marrakech, Maroc,2009.

ISTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

DEVELOPMENT OF NEW TECHNIQUE FOR HELP IN TECHNICAL TEACHING *SEBAA Fethi Tlemcen University IS2M Laboratory Tlemcen, Algeria

RAHOU Mohamed EPST –Tlemcen IS2M Laboratory Tlemcen, Algeria

CHEIKH Abdelmadjid Tlemcen University IS2M Laboratory Tlemcen, Algeria Keywords:CAM,Tool,Teaching,NC * Corresponding author:, +21366584579 E-mail address:[email protected]

ABSTRACT With the proliferation of acronyms using the CA prefix (Computer Aided), a summary effort is required. The use of computers allows capacity to grow more effectively than transactional or conversational methods. Training issues, pedagogy, maintenance of knowledge are of growing and becoming paramount in the universities and businesses. Software development is therefore followed with great interest as an effective way to improve teaching and skill level. A considerable increase of the field before computer-assisted instruction with the development of artificial intelligence and expert systems. The aim of our intervention is to present a methodology considered friendly to the teaching of numerical control with input modules for programming and video sequences corresponding to the various difficulties of Computer Aided Manufacturing (CAM). INTRODUCTION Computer-assisted instruction (CAI) remains after several years of existence, very little known alternative and very widespread in our universities. Among the possible reasons for this situation include: the level of preparation of teachers in the use of microcomputers. These reasons can not explain everything but point, at least, a few tracks on which there is consensus. The aim in this article is to present a methodology to develop a tool to computer assisted instruction.

COMPUTER-ASSISTED TEACHING In general, the Computer-Assisted Teaching (CAT) includes various educational uses of the computer. For the person who forms, it is the situation in which it dialogue with a computer via communication instruments. To introduce its own messages to the computer (for example to answer a question or send orders ...), the learner uses a keyboard and / or object designation device (reticle or mouse). To receive information from the computer, view the working results of the computer, it has a display and possibly a printer. The above highlights two fundamental concepts CAT : individualization and interactivity. More practically, to the CAT is use hardware and software to provide all or part of a training process. - Using computer equipment Computer equipment is increasingly miniaturized (result of the evolution of electronic technology). The microcomputer is now the preferred tool for the CAT. Indeed, the limited number of operating systems has enabled a great portability CAT programs on different machine builders, facilitating a massive distribution of realized courses. Technological change tends to reduce weight and volume, resulting in increased memory-sizes, response times become faster, allows the use of increasingly diverse devices and increased graphical quality screens for cost more accessible. In this description of the material, it does not have to forget two other approaches:

Conference Paper 



The Minitel using specific standards (video text) is unsuitable ergonomics to an educational use, but provides access to important data banks. Large systems that were developed and operated the first tutorials.

The future will certainly combine the advantages of micro and large systems with interconnection making it possible to download the courses. - Software To function, the computer needs of software tools. There is basically software for creating applications (languages or systems-authors of application software or tutorials). - Training The hardware and software are designed to provide all or part of the training. How will we use this tutorial? What is the role of the computer in relation to other educational resources? USE APPROACHES Three types of approaches can be individualized:  The computer replaces instruction in one or more phases of the training process (sharing the knowledge, appropriation through examples and exercises control of these two phases by testing). This approach is often called self-service.  The computer is used as a teaching aid for teaching in a traditional training structure (practical work tool, experimentation).  The computer is in addition to other training (it is used as another medium for tests, as an evaluation tool, deepening or documentation). COMPUTER-ASSISTED TEACHING PERCEPTION For the one that forms the CAT means:  The inclusion of a personal project by building training tailored to the needs that will utilize and integrate the acquired staff. The user becomes an actor of his training.  An organization and more flexible management of training: • Choice of training times (interest in the night staff) • own pace of learning: the user can mark downtime or to be accelerated, skipping steps or return on some points,  A possible diversity of duration of training,  A constructive use from own mistakes and ongoing self-assessment,  The use of original tools, current and easy to handle. For those who form the CAT finally means:





 

A privileged position both in relation to the computer they use, as compared to the trained person with the opportunity for dialogue, monitoring and evaluating ongoing, Better quality training through prior and experimental determination of objectives and teaching strategies, a continuous updating of knowledge and critical examination of the content and progress of the course, A different organization of courses (modular) A reduction in repetitive administrative tasks.

For those that control the formation, the EAO finally means:  Easier organization and continuing progress,  High efficiency by bringing the training in places suitable for everyone,  A lowering training costs, be they direct costs (time, stakeholders) and indirect costs (training replacement staff, travel expenses, hotels ...)  A better control of the training. The computer can provide all necessary information to ensure the assessment and management of training,  Access to training for a larger population (the night staff at the hospital for example). IMPLEMENTATION OF A COMPUTER-ASSISTED TEACHING The study, design, implementation, validation, operation and evaluation of a tutorial can be committed by an individual. The success of a project EAO through the intervention at each step, one or more clearly identified partners. - Actors The actors concerned by the CAT project are:  The expert content It is the benchmark in the (s) subject (s) (s) concerned by the project. He speaks with (s) content (s). This is a caregiver.  The pedagogue He mastered the methods and means to format the contents defined by the expert. This is a teacher.  The Manager It manages training (Chief of Staff, in charge of training).  The institution It represents the framework within which the project takes place. It is the final authority in all operations involved in the projects.  The médiatiseur It is developing the project in its part "technical realization" (computer, graphic, audiovisual ...). It establishes the operational resources of realized products.  The hierarchy

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It is the operational manager of the public concerned by the project.  The learner It uses the courseware developed for the project. It is the final destination of the products developed. The usual training principles are also valid in CAT, especially that in general the student is alone in front of his tutorial, while in a master / student interaction is possible. - Implementation stages of a program • Preliminary study It concerns the development of the specifications. Its objective is to define globally for the project, all the teaching modules to be developed and their characteristics: cutting, global objectives, target population, prerequisites, current state of formalization of content, overall structure (architecture) and educational approach modules, funding and implementation schedule. • Overall analysis This is an intermediate step that gives an overview of what will be the tutorial. It goes through the decomposition of the overall objective in so-called intermediate objectives. Is already in the blank between the content by the objectives, which results in a structuring of the tutorial. This phase is indispensable starting specifications to arrive at detailed document that represents the model paper. • Detailed analysis The aim of the detailed analysis phase is to define in a precise way all components of the tutorial, to establish the details of screens, dialogues, sequences depending on the intended responses. It represents the tutorial paper form pedagogical model. At every stage, there validation by the author group. These steps are not specific to the CAT against products by documents, especially the pedagogical model are. • Technical realization The aim is to publicize the paper model described in the previous step by using several media if necessary. This is the programming phase or media which is a much broader view. • Testing and validation The objective is to define the experimental conditions and answer questions such as: What do we evaluate? which evaluates? Why evaluate? how to evaluate? • Distribution and evaluation The aim is to make the tutorial diffusible, he can go geographically in places where it will be operated and ensure the operating conditions of the products and their impact. APPLICATION The figures 1, 2, 3, 4 illustrate a programming support module NC machining instructions. Put body of the paper here. Put body of the paper here. Put body of the paper here. Put body of the paper here. Put body of

the paper here. Put body of the paper here. Put body of the paper here. Put body of the paper here. Put body of the paper

Figure 1: Block N001 Original Machine

Figure 2: Identification Of A G Code

Figure 3: Block N008 Cycle Roughing

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Figure 4: Block N001 Machine Original Position Milling Program CONCLUSION In this work, we presented a methodology for developing teaching modules using computer-assisted. An example application was given to the teaching of numerical control using modules contribution to programming and video sequences corresponding to the various difficulties of Computer Aided Manufacturing (CAM).

REFERENCES Fargette J.P., et Latge G,( 1985), EAO et formation professionnelle. Les éditions d'Organisation, Collection Micro EAO, 1985 ; 88 p. Moulay A.M., Pascal A,(1 989), l'EAO un moyen pédagogique Revue Recherche en Soins Infirmiers Publication ARSI. N° 17, juin 1989. Nicaud J.F., (1985) ,Les Didacticiels de demain - des systèmes experts pédagogues ? Le Monde Informatique ; 2 septembre 1985; pp 9-11. Pascal A., Pichon M.B, (1989), L'EAO et la transfusion sanguine. Revue de l'infirmière. Mai 1989. Schwartz B.. L'Informatique et l'Education. Paris .(1981), La Documentation Française. Agence de l'Informatique. Avril 1981; 97 p. Rahou.M ,sebaa.F ,cheikh.A ,(2008), développement d’une interface d’aide à l’enseignement technique , conférence internationale sur LMD , Oran ,Algérie Rahou ,sebaa ,cheikh (2008), développement d’une interface d’aide à l’enseignement technique , conférence nationale sur l’enseignement universitaire , Tizi-ouzou, ,Algérie.

ISTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

IMPACT OF WELDED JOINT DEFECTS ON PIPE LIFE EFFECTS OF MECHANICAL SHOCKS *Abdelhamid BENHAMEL ESSA Tlemcen, Algeria

Féthi HADJOUI University Abou Bekr Belkaid Tlemcen, Algeria

Keywords: Pipeline, Crushing, Scratching, Degradation, Lifetime * Corresponding author:, Phone: +213(0)771759826 , Fax: E-mail address: [email protected]

ABSTRACT AREAS OF FATIGUE CRACKING The majority of ruptures in pressure pipes are due to stress concentrations near a defect, especially in welded joints. These defects fall into five categories: corrosion craters, cracks, scratches, depressions and so-called combined defects (dents + scratches). These defects reduce the lifetime of pipelines. The resistance of the pipelines depends on several parameters of a metallurgical nature, mechanical properties, operating conditions characterized by the pressure applied and weld joints. In this work, defects analysis is presented. These analyzes show that the presence of these defects corresponds to the majority of the pipes. The numerical study shows that the application of a load on this type of pipes and at different grade creates depths of penetration, which cause failures on the structure. The geometry of the depression depends on the duration of application of the load, as a result of the constraints will be generated. INTRODUCTION The most economical and efficient way to route fuel is through pipelines. This in-service structure undergoes cyclic loadings of varying amplitude, which can cause fatigue damage. This occurs mainly at the level of the welded joints, which constitute the most stressed parts. The assembly operation by welding generates three zones. A zone forming the base metal, the second a zone of molten metal and a so-called thermally affected zone. The fatigue behavior in these last two zones changes with respect to the metal. This change is due to a thermal effect where residual stresses are introduced. The objective of this study is to determine the crack propagation at welded joints for an oil pipeline or the material is grade X60 steel and by comparing with STEEL X70 the fatigue life of welded joints

The fatigue failure is the phenomenon of a crack under cyclic loading passing through the stages of initiation and stable propagation). The understanding of this phenomenon lies in the study of the propagation speed crack by fatigue, in this framework the mechanics of the Rupture has strongly contributed to the study of many laws linking the rate of fatigue cracking to characteristic parameters determined analytically. In general, we can explain a semi - theoretical law "crack propagation law" If we consider a structure containing a crack of length "a", and we follow the behavior of this crack (the length as a function of the number of Cycle applied N) during a cracking test, under a load with constant amplitude, it is constant that this growth continues until the rupture

Figure 1. Evolution de la longueur de fissure en fonction du nombre de cycle THE PREDICTION OF THE FATIGUE BEHAVIOR DEPENDS ON SEVERAL PARAMETERS OF EFFECTS. Applied loading parameters (load ratio, load amplitude). For pipelines, the change in the load ratio is related to the change in the operating pressure. The environment characterized by the

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presence of hydrogen or nitrogen as well as the temperature strongly affects the cracking rates of such steels used for pipelines. Given the development of pipeline steels, several studies have focused on fatigue behavior taking into account laboratory-scale service conditions. The state of the art conducted on the fatigue cracking behavior of the X60 and X70 pipeline steels at a fixed charge ratio (R = 0.1) under hydrogen and nitrogen environment showed that the cracking rate for the API steel 5L X60 is superior to that of API 5L X70 steel. The presence of hydrogen exhibits significant damage compared with nitrogen. Cracking under the same type of environment (H2 or N2) is higher than API 5L X70 due to chemical composition, grain size... The resistance to fatigue cracking of the API 45L X60 steel decreases in the presence of hydrogen at the different positions of a welded joint (base metal, heat affected zone and melting zone) compared to the tests carried out K = 20 MPa (m1 / 2) is 2.10-4 mm / cycle) in the presence of hydrogen (6.9 MPa H2) ∆In the open air [1] the cracking rate for, The speed is of the order of 10-3mm / cycle. The same effect of hydrogen occurs during the cracking of API 5L X70 steel at R = 0.5 [1]. The increase in the charge ratio in the presence of hydrogen shows an increase in the rate of cracking (FIG. 2).

decreases with increasing amplitude of the stress intensity factor∆K. FIG 3. Cracking speed (a) Pipe steel in TL direction (b) Melting zone under the effect of load ratio [3].

Hadjoui et al. [4] investigated the study on the fatigue cracking of API 5 L X 60 and X70 steels in the welded zone. Under load at constant amplitude, the effect of the charge ratio over the lifetime was highlighted. The results showed the increase of the lifetime by the increase of the charge ratio. At the same load ratio (R = 0.2), the API 5L X70 steel has a better resistance to fatigue cracking compared to the X60 steel.

FIG. 2. Crack speed in a welded joint in PLC 5L X60 [1]. The investigation carried out by Neves [2] has shown that the cracking speed of the API 5L X60 steel is affected by the direction of the crack orientation (FIG. 2). The parameters of the propagation model were determined according to the Paris law and showed that the T-S direction had good resistance to fatigue cracking with respect to the T-L direction. Kim [3] studied the characterization of fatigue cracking of the X60 steel in the base metal (BM), the heat-affected zone (HAZ) and the welded zone (WM). The mechanical properties of the metal of the welded zone are superior to those of the base metal. The crack velocity and the threshold stress intensity factor of the X60 steel (base metal) in the TL direction are not sensitive to Effects of the charge ratio, on the other hand, for the rate of cracking in welded metal (WM), it increases with increasing load ratio at low values ∆K (FIG 3), of ∆K This effect

FIG 4. Effect of load ratio on the fatigue life of pipeline steels (a) API 5L X60 (b) API 5L X70 Given the variability of parameters affecting fatigue cracking (loading, residual stresses, harmful environment ...) and the nuances of the materials used for pipelines put into service, which led us to predict fatigue cracking behavior assuming the presence of defects And environment. The present investigation focuses on studying the effects of charging parameters characterized by the charge ratio, loading amplitude on various steels used for pipelines, based on experimental results of fatigue cracking.

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The assembly operation by welding generates three zones. A zone forming the base metal, the second a zone of molten metal and a so-called thermally affected zone. The fatigue behavior in these last two zones changes with respect to the metal. This change is due to a thermal effect where residual stresses are introduced. The evolution of the crack velocity in the weld joint [5] where the crack propagates in an area near the weld bead is shown in FIG. 5 and compared with the base metal taken away from the weld bead. This result shows that the rate of cracking for the metal near the weld bead is less than the cracking rate of the base metal. This results in the presence of residual compressive stresses. The evolution of the predicted residual lifetime for the two states is shown in FIG. 5 The evolution of the residual fatigue lifetime at a load ratio R = 0.1 and a maximum applied cyclic loading of 200 MPa is shown in FIG. 6. It is found that the residual fatigue life for the metal of Base of the API 5L X60 steel is much lower than the metal close to the molten zone. 105 cycles that represents a lifetime increase of about 5 times.×The difference in service life is of the order of 5.11.The presence of the residual compressive stresses due to the expansion of the tube justifies such an increase.

Figure 5. Comparison of cracking rates of base metal (T-L direction) and welded joint of API 5L X65 steel [6]

Length of the crack “a “(mm)

FATIGUE CRACKING OF WELDED JOINTS * X60_BM X60_WM

Number of Cycles "N" Figure 6. Prediction of residual fatigue life of steel API 5L X65 (base metal (T-L) / welded joint)

RESULTS AND DISCUSSIONS The study on the fatigue cracking of API 5L X60 and X70 steels in the welded zone, the results showed the increase of the lifetime by the increase of the load ratio. At the same load ratio (R = 0.2), the API 5L X70 steel has a better resistance to fatigue cracking compared to the X60 steel. The work presented on the API 5L X65 steel shows that the rate of cracking through the weld joint in the T-L direction is higher than the speed for the base metal in the same T-L (FIG. 5). The velocities approximate with the increase in the stress intensity factor. A, 10-8 m / cycle for the × rate of cracking for the base metal is 1.32 10-8 m /×metal of the bottom zone, the cracking rate has decreased to 4.5 cycle, this represents a Decrease of 3.40 times. This also justifies the presence of residual tensile stresses due to thermal effects. These residual tensile stresses affect fatigue life. The residual lifetimes for the base metal and the metal of the molten zone are predicted using the Walker model (FIG 6). A significant reduction in fatigue life is observed. CONCLUSION This study was conducted to predict the fatigue behavior of API 5L steels used for pipelines in welded joints. The loading effect characterized by the variation of the loading ratio and the loading amplitude was highlighted. The study was carried out on specimens of the SENT type (Single Edge Notch Tensile Specimen). The applied load is a voltage loading due to the internal pressure causing the opening mode I. The results have shown that the lifetime and rate of cracking depend primarily on a number of parameters, which summarizes the types of loading, environmental and metallurgical parameters. The result of this work shows that the rate of cracking for the metal near the weld bead is less than the cracking rate of the base metal. This results in the presence of residual compressive stresses.

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REFERENCES [1] Sandia National Laboratories. “Technical reference on hydrogen compatibility of materials”. [2] M. Augusto Neves, (2005). “Propagation de fissures par fatigue des tubes d'acier soudés longitudinales, grade API 5L X-70”. Université Fédérale de Rio de Janeiro, 2005 [3] Young Pyo Kim, Cheol Man Kim, Woo Sik Kim, KwangSeon Shin (2007). “Fatigue crack growth behavior in girth weld of natural gas transmission Pipelines”. Key Engineering Materials, Vols. 345-346, pp 303-306 [4] F. Hadjoui, M. Benachour, M. Benguediab (2012). “Fatigue crack growth on double butt weld with toe crack of pipelines steel”. Materials Sciences and Applications, Vol. 3, pp 596599 [5] C. Mokhdani (1995). “Amorçage et propagation de fissures de fatigue dans un acier pour tubes de transport de gaz”. Thèse de Doctorat, Ecole des Mines de Paris. France.

ISTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

VISCOMETRIC STUDY OF THE INTERACTION BETWEEN POLYELECTROLYTE COMPLEX AND SURFACTANT

*Tennouga Lahcene Laboratoire d’Application des Electrolytes et des Polyélectrolytes Organiques (LAEPO).Université de Tlemcen. Département de Chimie. B. P. 119 13000 Tlemcen. Algeria

Mansri Ali Laboratoire d’Application des Electrolytes et des Polyélectrolytes Organiques (LAEPO).Université de Tlemcen. Département de Chimie. B. P. 119 13000 Tlemcen. Algeria

Medjahed Kouider Laboratoire d’Application des Electrolytes et des Polyélectrolytes Organiques (LAEPO).Université de Tlemcen. Département de Chimie. B. P. 119 13000 Tlemcen. Algeria

Keywords: Polyelectrolyte, Viscosity , Surfactant , Interaction * Corresponding author: E-mail address: l14_tenyahoo.fr

ABSTRACT Using surfactants in combination with polyelectrolyte increases the width of the applications even further and mixtures of polymers-surfactants in aqueous solution have been used for colloidal stabilization or flocculation as well as rheology control. In this paper, the interaction of polyelectrolyte complex (hydrolyzed polyacrylamide AD37-poly(4vinylpyridine (P4VP)) with the anionic surfactant (sodium dodecyl sulfate (SDS) in aqueous media at T=25°C, was investigated using viscosity measurements. The measurements allowed the determination of the SDS concentration at which the polyelectrolyte complex –SDS interaction begins (CAC) and ends (X2). Between the CAC and X2, there is the area of interaction i.e. the binding of the SDS molecules to the complex. Thus, the interaction is therefore favored for low P4VP concentrations with a high hydrophobicity. The result shows that the values of viscosity system were influenced by the surfactant concentration, polymer concentration and neutralization degree. INTRODUCTION Aqueous polymer–surfactant systems offer a wide variety of possibilities for applications. This is a consequence of the fact that the association between surfactant and polymer can

be influenced by numerous factors, ranging from structural properties of the components to experimental conditions such as ionic strength, temperature, and pH. Of major significance for interactions in a particular polymer–surfactant pair are the presence and sign of charged groups on the polymer and/or on the surfactant. Many articles have appeared on this topic over the years, and extensive reviews of the field are available [1, 2]. The effects of polymer surfactant interactions are useful in practice to achieve emulsification, colloidal stability, viscosity enhancement, gel formation, solubilization, and phase separation [3, 4]. The properties and structure of surfactantpolymer complexes depend on the molecular characteristics of the polymer and surfactant [5-7] Interaction is most pronounced in the system consisting of the oppositely charged polymer and surfactant, often accompanied by phase separation. Then come the systems uncharged polymer-charged surfactant, and weakest interactions exist between uncharged polymer and surfactant [811]. There are two polymer surfactant interaction mechanisms of different intensity, viz. electrostatic and hydrophobic. Depending on the polymer surfactant system and surfactant concentration, the surfactant may adsorb onto the polymer in the form of individual molecules or small aggregates. Mixed micelles may be formed with surfactant molecules and hydrophobic polymer segments. At sufficiently high surfactant concentrations, only free surfactant micelles are formed in the

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highest P4VP concentrations interpreted by a linear variation of viscosity as a function of AD37 concentration. 120000

90000

ηred (ml/g)

solution. As the polymer-surfactant interaction takes place, the properties of the systems change, and they can be detected by various techniques: tensiometry, viscometry and rheometry etc [12]. In this study, interactions between sodium dodecyl sulfate (SDS) and polyelectrolyte complex 27% hydrolyzed polyacrylamide [AD37] / poly (4-vinylpyridine) [P4VP], in aqueous solution and at neutralization degree α=0,1 and 1, at 25°C were studied by viscometric measurements. RESULTS AND DISCUSSION Figure 1 shows the reduced viscosity variation of the system (AD37–P4VP–SDS), depending on the concentration of AD37, concentrations of P4VP and at fixed concentration of SDS equal to 1%. We note that the viscosity depending on the concentration of AD37 and increases when the concentration of P4VP decreases. Also, the highest value recorded is about 7.104ml g-1 corresponding to a low concentration of P4VP and a high concentration of AD37 (0.1 10-4 and 10-3 g ml-1, respectively) [14]. A salt effect is observed when P4VP concentrations exceed 10-4 g ml-1, the number of P4VP chains becomes more important than those of AD37, and electrostatic screening of AD37 charges by those of P4VP is favoured. 80000

30000

0 0,0000

0,0002

0,0004

0,0006

0,0008

0,0010

CAD37 (g/ml)

Figure 2: Reduced Viscosity Change Of The System ( AD37-P4VPSDS ) At T=25°C, As A Function Of C AD37, And With Different Concentrations Of P4VP (G/Ml) : (■) 0.1E-4 ; ( ●)0.2E-4 ; (▲)0.5E4 ; (▼)1.0E-4 ; (♦)2.0E-4 ; (+)4.0E-4 For α = 1 And C SDS =1%

The measurement of solution viscosity provides a simple way to monitor such conformational changes, and hence the occurrence of polymer-micelle association [15].

70000 60000 50000

η red(ml/g)

60000

5

40000 30000

4

CAC

20000

η(mpa.s)

10000 0 0,0000

0,0002

0,0004

0,0006

0,0008

3

0,0010

CAD37 (g/ml)

Figure 1: Reduced Viscosity Change Of The System ( AD37-P4VPSDS ) At T=25°C, As A Function Of C AD37, And With Different Concentrations Of P4VP (G/Ml) : (■) 0.1E-4 ; ( ●)0.2E-4 ; (▲)0.5E4 ; (▼)1.0E-4 ; (♦)2.0E-4 ; (+)4.0E-4 For α = 0,1 And C SDS =1%

Reduced viscosity change of the system (AD37-P4VP-SDS) at T=25°C (Figure 2), as function of C AD37, and with different concentrations of P4VP (g/ml) at α = 1 . With increasing of neutralization degree, the values of viscosity increases and the highest value is 100.103 ml.g-1 correspoding to a low concentration of P4VP and a high concentration of AD37 [14]. We note that the viscosimetric behaviour is the same as that observed in figure 1. A salt effect is observed for the

2

0,0

0,2

0,4

0,6

0,8

CSDS (g/100ml)

Figure 3: Viscosity Change Of The System ( AD37-P4VP-SDS ) At T=25°C, As A Function Of SDS Concentration And With Different Concentrations Of AD37 :(■)1.10-4g/Ml; ( ●)2 .10-4g/Ml; (▲)3 .104g/Ml; (▼)4.10-4g/Ml; (♦)5.10-4g/Ml For C -4 P4VP =2.10 g/Ml And

α =1

Figure 3 shows the variation of the viscosity versus concentrations of SDS, the different concentrations of AD37

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and at C P4VP =2.10-4g/ml. The viscosity change shows a maximum at the critical micelle concentration CMC of the surfactant (≈0.003 g/ml). Thus the critical aggregation concentration (CAC) for this system occurs at 0.002 g/m. The maximum of the viscosity suggests a change in the conformation of the polyelectrolyte complex [16]. The viscosity decreases beyond a SDS concentration equal to 0.003 g/ml, the system shows the typical polyelectrolyte character. The viscosity plots shows several variation according the SDS concentration. After the CAC, the viscosity increases gradually, the SDS molecule start to bind to complex of polymer by electrostatic interactions [17-21]. When the surfactant concentration (C SDS >0.005 g/ml), the viscosity shows a constant variation caused by the formation of free micelles [22]. CONCLUSION The interaction between the complex of polymer and the surfactant has been studied using viscosity measurements. The surfactant interacts strongly with the oppositely charged cationic complex of polymer. The result shows clearly the existence of strong electrostatic interactions in solution between the surfactant and the polyelectrolyte. The surfactant binds to the polyelectrolyte due to strong electrostatic interactions, after saturation of the binding sites of the copolymer at X2. It appeared that the X2 depends on this concentration. ACKNOWLEDGMENTS Authors thank the Agence Nationale pour le Développement de la Recherche Universitaire (ANDRU) in Algeria for its Financial support. NOMENCLATURE 27% hydrolyzed polyacrylamide: AD37 Poly (4-vinylpyridine): P4VP Neutralization degree α Sodium dodecyl sulfate: SDS Critical micelle concentration of the surfactant: CMC Critical aggregation concentration: CAC Concentration of saturation : X2 REFERENCES [1] J.C.T. Kwak (Ed.), Polymer–Surfactant Systems, Surfactant Science Series, vol. 77, Dekker, New York, 1998. [2] E.D. Goddard, K.P. Ananthapadmanabahn (Eds.), Interactions of Surfactants with Polymers and Proteins, CRC Press, Boca Raton, 1993. [3] Goddard, D. E. (1993a). Application of polymer–surfactant systems. In D. E. Goddard (Ed.), Interaction of surfactants with polymers and proteins (pp.395–413). Boca Raton, FL: CRC Press.

[4] Goddard, D. E. (2002). Polymer/surfactant interaction: Interfacial aspects. Journal of Colloid and Interface Science, 256, 228–235. [5] Lindman, B., Thalberg, K. (1993). Polymer - surfactant interactions-Recent developments. In E. D. Goddard (Ed.), Interaction of surfactants with polymers and proteins (pp. 203– 275). Boca Raton, FL: CRC Press. [6] Winnik, M. F., Regismond, A. T. S. (1996). Fluorescence methods in the study of the interaction of surfactants with polymers. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 118, 1–39. [7] Li, Y., Dubin, L. P. (1994). Polymer-surfactant complexes. In C. A. Herb, R.K. Prud’homme, Structure and flowin surfactant solutions.ACS symposium series 578 (pp. 320–336). Richland,WA: American Chemical Society. [8] Goddard, D. E. (1993b). Polymer–surfactant interaction. Part I. Uncharged water-soluble polymers and charged surfactants. In D. E. Goddard (Ed.), Interaction of surfactants with polymers and proteins (pp. 123–169). Boca Raton, FL: CRC Press. [9] Goddard, D. E. (1993c). Polymer–surfactant interaction. Part II. Polymer and surfactant of opposite charge. In D. E. Goddard (Ed.), Interaction of surfactants with polymers and proteins (pp. 171–201). Boca Raton, FL: CRC Press. [10] Wang, Y., Kimura, K., Huang, Q., Dubin, P., Jaeger, W. (1999). Effects of salt on polyelectrolyte-micelle coacervation. Macromolecules, 31, 7128–7134. [11] Ridell, A., Evertsson, H., & Nilsson, S. (2002). Influence of counterion on the interaction of dodecyl sulfates and cellulose ethers. Journal of Colloid and Interface Science, 247, 381–388. [12] Kulicke, M. W., Arendt, O., & Berger, M. (1998a). Rheological characterization of the dilatant flow behavior of highly substituted hydroxypropylmethylcellulose solutions in the presence of sodium lauryl sulfate. Colloid and Polymer Science, 276, 617–626. [13] Mansri A, Tennouga L, Desbrières J (2007) Viscosimetric behaviour of hydrolyzed polyacrylamidepoly(4-vinylpyridine) [AD37-P4VP] mixture in aqueous solution. Eur Polym J 43:540–549 [14] L. Tennouga, K. Medjahed, A. Mansri, J. desbrières, Polyelectrolyte complex–surfactant interactions: effect of neutralization degree on viscometric behavior in aqueous solution Polym. Bull., 70 (2013) 97-103. [15] R.C. Lu, A.N. Cao, L.H. Lai, B.Y. Zhu, G.X. Zhao, J.X. Xiao, Colloids and Surf. B, 41 (2005) 139-143. [16] P. Deo, S. Jockusch, M. F. Ottaviani, A. Moscatelli, N. J. Turro, P. Somasundaran, Langmuir 19 (2003) 10747-10752. [17] J. Verica Sovilj, B. Lidija Petrovic, Carbohydrate Polymers 64 (2006) 41-49. [18] E. Minatti, D. Zanette, Colloids and Surf. A: Physicochemical and Eng. Aspects, 113 (1996) 237-246. [19] J.A. Müller, Y. Garcés, M. Toress, B. Scharifker, A.E. Sáez, Progress in Colloid and Polymer Science, 122 (2003) 7381.

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[20] S. Nilsson, Macromolecules, 28 (1995) 7837-7844. [21] H.W. Jiang, J.S. Han, Journal of Colloid and Interface Science, 229 (2000) 1-5. [22] L. Tennouga, K. Medjahed, A. Mansri, Synthesis, characterization and study of copolymer/surfactant mixture in aqueous solution by conductivity and viscosity techniques, Mor. J. Chem.4 N°3 (2016) 651- 662

ISTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

HIGH PERFORMANCE FUZZY LOGIC CONTROL OF INDUCTION MOTOR DRIVES POWERED BY PHOTOVOLTAIC PANEL USING FUZZY MPPT CONTROLLER * Mohammed Omar Benaissa Intelligent Control and Electrical Power System Laboratory, Djillali Liabes University Sidi Bel-Abbes, Algeria

Samir Hadjeri Intelligent Control and Electrical Power System Laboratory, Djillali Liabes University Sidi Bel-Abbes, Algeria

Sid Ahmed Zidi Intelligent Control and Electrical Power System Laboratory, Djillali Liabes University Sidi Bel-Abbes, Algeria

Keywords: PV generator, MPPT, Fuzzy Logic control (FLC), DC/DC Boost converter, Induction Motor, Indirect Field-Oriented Control (IFOC). * Corresponding author: Mohammed Omar Benaissa, Phone: +213558481869. E-mail address: [email protected]

ABSTRACT

present a serious problem for its control. For this purpose, the vector control theory has long since been applied successfully for three phase induction motors [1]. However, the desired drive specifications still cannot be perfectly satisfied and/or their algorithms are too complex [2]. Therefore, the birth of fieldoriented control (FOC), as a standard of the industry for the AC drives that have the same dynamics as DC motors [3]. This control was included in the most significant inventions in AC motor drives that gave rise to the research and development programs, resulting in the ultimate enhancement of the control performance [4]. On the other hand, Photovoltaic power is widely used to supply isolated or unpopulated areas (lighting, pumping, etc.). Also another great advantage is that this source is inexhaustible, it offers great safety in use and it is clean. However PV module can generate the solar energy with very low efficiency. One of the techniques to improve the PV module efficiency is the MPPT controller. The P&O method is often used to control the MPPT. This method is very simple to be implemented. However, it has low efficiency in steady state condition caused the perturbation makes operation point of PV module is isolated around maximum power point (MPP) so wasting the energy [5]. These imperfections lead us to use Artificial Intelligent methods recently increase in usage of renewable energy system because of their flexibility nature of controlling. Among different intelligent controllers, fuzzy logic is the simplest to integrate with the system. Recently, fuzzy logic controller (FLC) has received an increasing attention from researchers for converter control, motor drives and other process control as it provides better responses than other conventional controllers [6,7]. The main advantage of fuzzy logic control as compared to conventional control resides in the

With the advent of the vector control methods, the induction motor can be operated like a separately excited dc motor for high performance applications. The authors has made an effort through this paper to develop a controller consisting of fuzzy logic controller (FLC) to put into indirect field oriented control of induction motor to achieve fast response of the motor with a high dynamic performances. It should be noted that we have subjected the system to several disturbances such as sudden load torque and reversal speed. Furthermore, photovoltaic (PV) system has a great potential compared to its counterparts of renewable energies, however it’s necessary to track the MPP of the PV array all the time in order to improve the system efficiency, for this reason we have proposed a controller that can adjust the duty cycle of the DC-DC boost converter switch to track the maximum power of a solar PV array. This paper gives raise the problem of speed control and estimation using indirect field oriented control based on fuzzy logic controller, the considered induction motor is powered by a photovoltaic panel, the power delivered by the PV generator is maximized by inserting MPPT based on fuzzy logic controller. Simulation results showed that the fuzzy logic controller can ensure the best dynamic performances. INTRODUCTION The electric motors of industrial systems operate generally at variable speed. Since, the induction motors are often used because they are unquestionably an advantage over to the DC machine. But, the coupling between the flux and torque of IM 1

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DC/DC BOOST CONVERTER

fact that no mathematical modeling is required for the controller design. In this paper, the MATLAB/Simulink software based model of a three-phase induction motor was derived using mathematical modeling principles. The controller will be designed, founded in the indirect field-oriented control principles, and would be implemented later in the model. It should be noted that the input voltage of the DC/AC inverter is obtained from a stand-alone PV panel that is becoming very popular when it comes to the energy production. As we now the output of solar panel is variable so we have inserted a DC-DC Boost converter which enhances variable DC into fixed DC, while ensuring the maximum power transfer.

To overcome the undesired effects on the power output of the PV and to extract its maximum, it is recommended that a DC/DC converter be inserted between the PV generator and the load, which can control the MPP [10]. The converter consists of a circuit topology and a control, where there will be an algorithm for MPP trackers. The role of MPPT is to ensure the operation of the PV generator at its optimum. The MPP trackers can be designed based on the boost or the buck topologies converters. The buck converter is generally used to reduce the output voltage and the boost converter is used to achieve higher output voltages. In this application, the voltage has to be increased. So the average value of the output voltage of the boost converter Vdc can be expressed in terms of the average value of the voltage input Vpv as:

SOLAR PV MODULE The equivalent circuit of a PV cell is shown in Fig. 1. An ideal solar cell is modeled by a current source in parallel with a single diode. However no solar cell is ideal there by series resistance which has a very small value and Rsh is the equivalent shunt resistance whose value is very high [8]. From the equivalent circuit the output current and power can be expressed as [9]:

  qV I  N p I ph  N p I sat exp    KTAN S

    1  

  qV   P  VI  N p I phV  N p I satV exp    1   KTAN S  

1 V pv 1

(3)

I dc  1    I pv

(4)

Vdc 

Where α is a duty cycle ratio determined by the conceived MPPT algorithm. Figure 2 demonstrates the block diagram of a boost converter.

(1)

(2)

Fig. 2. Block diagram of Boost Converter [10]

FUZZY LOGIC APPROACH In contrast to classical knowledge systems, fuzzy logic is aimed at a formalization of modes of reasoning that are approximate rather than exact [11]. Fuzzy logic is much closer in spirit to human thinking and natural language than the traditional logical systems. Basically, it provides an effective means of capturing the approximate, inexact nature of the world [12]. The success of this methodology has been demonstrated in a variety of fields. Several fuzzy logic based efficiency controller have been reported in literature. A fuzzy logic controller essentially embeds the experience and intuition of a human plant operator. The structure of such regulation is shown in Fig. 3.

Fig. 1. Equivalent circuit of solar cell [8].

Where I is output current of PV module V is output voltage of PV module Iph is light induced current of single PV cell Isat is diode saturation current of single PV cell Np is the number of PV cell in parallel Ns is the number of PV cell in series Q is elementary charge (1.6x10-19C) K is boltzmann constant (1.38x10-23 J/°K) T is surface temperature of PV module (°K) A is diode ideality factor

2

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Figure 5 shows the 3 D presentation of error and variation of error and variation of duty cycle.

Fig. 3. General structure of fuzzy controller [13]

Our fuzzy controller is characterized by:  Two inputs, the error e and its variation e and a single output dD (Fig. 3).  The universe of discourse divided into seven classes for input and output variables.  The membership functions of triangular and trapezoidal type.  The involvement of Mamdani for inference.  The center of gravity method for defuzzification. Where these inputs and output variables are expressed in terms of linguistic variables such as nb (negative big), nm (negative means), ns (negative small), zr (zero), ps (positive small), pm (positive means), pb (positive big). Membership functions used for the input variables and output variables are shown in Fig. 4.

Fig. 5. The input-output surface wave form of the FLC

SYSTEM DESCRIPTION The simulation block diagram of the indirect vector control based on the fuzzy logic controller is shown in Fig. 6, where the whole system is powered by a photovoltaic panel through a DC/DC Boost converter, the duty cycle of the last one is controlled by a second fuzzy controller whose role is ensuring the tracking of the maximum power delivered by the PV system.

Fig. 4. General diagram of fuzzy controller MPPT MATLAB

A fuzzy rule base is formulated for the present application and is given in table 1. Fig. 6. Schematic diagram of the proposed PV system feeding the Induction Motor

TABLE 1. Fuzzy rules table. De e nb nm ns zr ps pm pb

nb

nm

ns

zr

ps

pm

pb

bn bn bn bn mn sn zr

bn bn bn nm ns zr ps

nb nb nm ns zr ps pm

nb nm ns zr ps pm pb

nm ns zr ps pm pb pb

ns zr ps pm pb pb pb

zr ps pm pb pb pb pb

SIMULATION RESULTS AND DISCUSSION To illustrate the operation of the indirect field oriented control (IFOC) based on a Fuzzy logic controller and highlight its performances, a simulation model has been realized in Matlab/Simulink environment see Fig 7. Simulation results to be presented in this paper are drawn using the induction motor of 1.5 KW whose characteristics are given in the Appendix.

3

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[Vdc]

Régulateur Flou

O PI Id

F Ids R Qr Wsl

Flux estimé

Bloc NL

d e c o u p l i n g

Induction Motor

Va

I N s1 V E R Vb s2 T E R

dq PWM abc

Qdr

Uds

Ud

is1

Qqr

Qrq

Ce abc/dq

v +-

[Vdc]

Ce

Uqs M wr

A

PV Array 1

wr

Is

Vc

s3

a

g

PI Iq

C

Iqs Ce

Vdc Voltage Source

E

wref

Ws S

Display

is

ids

Calcul angle

Qr

iqs m t

Cr

wr1

Qr

Uref Pulses

Discrete PWM Generator1 Fuzzy Logic Controller1

wr2 Qr1

[Vdc]

Qr2 1

220 Constant2

z Unit Delay1

Fig. 7. Overall Simulink model

The control performances of the indirect vector control based on a fuzzy controller have been tasted from the simulation of the following modes:  Start under unloading condition followed by the introduction of the load torque.  With reversal of rotor rotation. The simulation system with the adopted control gave the results shown in the Figures below.

200

Rotor Speed Ref Speed

150

Speed (rad/sec)

100

50

0

-50

400

-100

350 -150 0

300

0.5

1

1.5

2

2.5

3

DC-Voltage (Volt)

time (sec) 250 200

Fig. 9. Rotor Speed (rad/sec)

150 100 50 0 -50 0

0.5

1

1.5

2 time (sec)

2.5

3

3.5

4

Fig. 8. Output Voltage of the Boost converter

4

3.5

4

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1.2 1

Fundamental (50Hz) = 0.8995 , THD= 51.12%

0.6

160

Qdr Qqr

140

0.4 Mag (% of Fundamental)

Rotor Flux (Web)

0.8

0.2 0 -0.2 0

0.5

1

1.5

2 time (sec)

2.5

3

3.5

4

Fig. 10. Rotor Flux Qdr, Qqr (Weber)

120 100 80 60 40 20 0

0

100

200

300

400

500

600

700

800

900

1000

Frequency (Hz) 25 Electromagnetic Torque Charge Torque

Electromagnetic Torque (N.m)

20

(c)

15

Fig. 12. IFOC control performances: (a) the simulated dqaxis current, (b) stator current, (c) Harmonic Spectrum of stator current along with THD

10

5

Figure 8 shows the output voltage of the DC/DC Boost converter which is constant and equals to 220 V. this voltage corresponds to the maximum power delivered by the PV panel, the fact that makes us say that the fuzzy MPPT designed has fulfilled its intended purpose.

0

-5 0

0.5

1

1.5

2 time (sec)

2.5

3

3.5

4

Fig. 11. Electromagnetic Torque (N.m)

To test the robustness of the control, we have simulated the start up under no load condition after a while the speed of the rotor stabilizes at 160 rad/sec, then a load torque of 10 N.m is applied at t=1sec followed by a change of the direction of rotation at t=2sec, in fact we notice that the actual speed follows perfectly the reference speed with a short settling time, and no overshooting was recorded (see Fig. 9), so the error caused by the disturbance of the load is compensated instantly. Furthermore we notice that the decoupling between the flux and the torque has been verified whether during the transient period or when the load torque has been applied, in fact the electromagnetic torque has taken a new value at t=1s (see Fig. 11), while the flux remained unchanged (see Fig. 10). Figure 12 (a) to 12 (c) show respectively the graphs of dq stator currents, stator current of one single phase, and the harmonic spectrum of the stator current. We notice that the current takes a sinusoidal form with a considerable THD of 51.12%. The results validate the static and dynamic quality control.

12 Ids Iqs

10

Stator current (A)

8 6 4 2 0 -2 0

0.5

1

1.5

2 time (sec)

2.5

3

3.5

4

(a) 10

5

0

-5

10 -10 1.5

1.55

1.6

1.65

1.7

Stator current (A)

5

CONCLUSION 0

Two conclusions can be drawn from the actual work; the first one is about the fuzzy logic technique applied to the squirrel cage induction motor. Simulations results have confirmed the efficiency and the precision of this proposed control during the sudden load torque and reversal speed. The second one is about the photovoltaic power generation system,

-5

-10

-15 0

0.5

1

1.5

2 time (sec)

2.5

3

3.5

4

(b)

5

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which applies fuzzy logic control, simulations results show that the proposed strategy doesn't add complexity to the system, it is easy to implement and can intelligently ensure the tracking of the maximum power point of photovoltaic solar array.

[4] Muawia A. Magzoub, Nordin B. Saad, Rosdiazli B. Ibrahim, “An Intelligent Speed Controller for Indirect Field-Oriented Controlled Induction Motor Drives”, Conference on Clean Energy and Technology (CEAT), pp. 327-331, 18-20 November 2013. [5] Anang Tjahjono et al, “Photovoltaic Module and Maximum Power Point Tracking Modeling Using Adaptive NeuroFuzzy Inference system”, Makassar International Conference on Electrical Engineering and Informatics (MICEEI), 26-30 November 2014. [6] M.F. Naguib, and L.A.C. Lopes, “Harmonics Reduction in Current Source Converters Using Fuzzy Logic”, IEEE Transactions on Power Electronics, Vol. 25, No. 1, 2010, pp. 158-167. [7] Ahmed H. El Khateb, Nasrudin Abd Rahim, Jeyraj Selvaraj, “Fuzzy Logic Control approach of a Maximum Power Point Employing SEPIC Converter for stand-alone photovoltaic system”, Procedia Environmental Sciences, 2013, pp. 529536. [8] Sonam Mishra et al, “Modeling and simulation of solar photovoltaic and PMSG Based wind Hybrid system”, IEEE Students' Conference on Electrical, Electronics and Computer Science, 2014. [9] Dogga Raveendhra et al, “Performance and Control System design for FPGA based CVMPPT Boost Converter for Remote SPV water pumping system applications”, Power and Energy Systems conference: Towards Sustainable Energy (PESTSE), 13-15 March 2014. [10] Najet R, Belgacem B G, Othman H, “Modeling and control of photovoltaic energy conversion connected to the grid”, Frontiers of Energy and Power Engineering in China, 2012, pp. 35-46. [11] C. C. Lee, “Fuzzy Logic in Control Systems: Fuzzy Logic Control-Part. II”, Transaction on Systems, Man and Cybernetics, Vol. 20, No. 2, 1990, pp.419-435. [12] Zineb Rouabah, Fatiha Zidani, Bachir Abdelhadi, “Fuzzy Efficiency Enhancement of Induction motor Drive”, 4th International Conference on Power Engineering, Energy and Electrical Drives, Turkey, Istanbul 13-17 May 2013. [13] Mohamed Ajaamoum et al, '”Fuzzy controller to extract the Maximum Power of a photovoltaic system”, International Renewable and Sustainable Energy Conference (IRSEC), Morocco, Ouarzazate, 7-9 March 2013.

APPENDIX TABLE 2. Induction Motor Nominal Parameters Power

1.5 KW

Nominal voltage

220 V (Δ) / 380 V (Y)

Nominal efficiency

0.78

Nominal power factor

0.8

Rated speed

157RAD/SEC

Nominal frequency

50 HZ

Nominal current

3.64 A (Y) ET 6.31 A (Δ)

Stator resistance

4.850 Ω

Rotor resistance

3.805 Ω

Stator inductance

0.2 74 H

Rotor inductance

0.274 H

Number of pairs of poles

2

Inertia constant

0.031 KG.M2

Friction factor

0.00114 N.M.S/RD

REFERENCES [1] S. Lekhchine et al, “Speed control of doubly fed induction motor”, Energy Procedia, 2015, pp. 575-586. [2] Minh Ta-Cao et al, “Fuzzy Logic Based Controller for Induction Motor Drives”, Electrical and Computer Engineering, Canadian Conference 26-29 May 1996. [3] S.M. Joachim Böcker, “State of the Art of Induction Motor Control”, IEEE Transaction, Control, 2007, pp. 1459-1464.

6

ISTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

THE IMPACTS OF UV DIRECT PHOTOLYSIS AND (UV/H 2 O 2 , UV/NaOCl) ADVANCED OXIDATION PROCESSES ON THE DEGRADATION OF MONOCHLORAMINE USING LOW PRESSURE (LP) LAMP * Ala Abdessemed1,2, 1 Biotechnology Research Centre, BPE 73, Ali Mendjeli, Nouvelle Ville, 25000 Constantine, Algeria

Kamel E. Djebbar2 2 Laboratory of Science and Technology of the Environment, University Mentouri Constantine, Chaabat Errassas, 25000 Constantine, Algeria.

2 Laboratory of Science and Technology of the Environment, University Mentouri Constantine, Chaabat Errassas, 25000 Constantine, Algeria.

Amer S. El-Kalliny3,4 3 National Research Centre, Water Pollution Research Department, Dokki, Giza, Egypt. 4 Product and Process Engineering, Delft University of Technology, ChemE, Julianalaan 136, 2628 BL Delft, the Netherlands.

T. Sehili2 2 Laboratory of Science and Technology of the Environment, University Mentouri Constantine, Chaabat Errassas, 25000 Constantine, Algeria.

Keywords: Monochloramine, ultraviolet (UV LP ) Low Pressure Hg lamp light, photolysis, photoluminescence, •OH radical, Cl• radical. * Corresponding author: 00213 669 48 19 94, Fax: 00213 31 77 50 44 E-mail address: [email protected] [email protected]

ABSTRACT The aim of this study was to investigate the use of photochimicals processes (photolysis, H 2 O 2 /UV LP and NaOCl/UV LP ) to eliminate monochloramine compound using a Low Pressure Hg lamp as an irradiation source (254 nm). First, it was found that the direct photolysis treatment might be considered as a suitable way to degrade this product (≈ 98 % rate of depletion under UV dose at 8000 mj/m2). Besides, this degradation was greatly improved by H 2 O 2 /UV LP thank’s to the high production of •OH from photolysis of H 2 O 2 . However, no big advantages were observed when we have employed NaOCl/UV LP comparatively to H 2 O 2 /UV LP . This fact would be attributed to the weak production of radicals •OH which was showed by a test conducted with a probe molecule: the terephthalic acid (TA). In addition the system NaOCl/UV LP

could generate also Cl• creating thus, a competition between these two species towards the target compound. In another site, kinetics data for the three systems were best represented by a pseudo-first-order and the photodecomposition of monochloramine has conducted to the formation of by-products like: nitrate and nitrite. No formation of ammonia was observed during this process. INTRODUCTION Chlorine has been used as an oxidant in water treatment over the last 100 years. Although many benefits have been gained from this treatment, there are also some disadvantages [1]. It is well known that chlorine could react with naturally occurring organic matter present in water to form halogenated disinfection by-products (DBPs) that might be dangerous for

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human health [2]. In 1974, Rook discovered that hypochlorous acid and hypobromous acid also react with naturally occurring organic matter to create many water disinfection by products [3]. Among chlorinated DBPs, inorganic chloramines (mono-, di- and trichloramine) are common in water and contain reduced nitrogen in the form of ammonia [4]. Chloramines have been used by water utilities for almost 90 years, and their use is closely regulated. More than one in five Americans uses drinking water treated with chloramines. Therefore, in several industrial processes using in general chlorinated municipal water, residuals of combined chlorine have to be removed because chloramines could damage reverse osmosis membranes and deionization resins [5]. They could also affect the taste, flavor and smell of drinks and liquids. Chloramine could also change the chemical properties of water leading consequently to an increase of the corrosion and thus to the metals leaching from pipes [6]. Dechlorination was used to remove free and combined chlorine residuals from disinfected wastewater and cooling water prior to discharge into the environment [5]. Among methods used before, we could list: activated carbon filtration and addition of a reducing agent like sulfur dioxide or a sulfite salt [7]. More recently, in swimming pools the dechloronation was achieved using photochemical processes in presence of UV irradiation [8], [9]. Under UV irradiation of HOCl and ClO-, various primary reactive intermediates are formed and are rapidly converted into secondary photooxidants like •OH and Cl• [10-16]. In addition, recombination rate of these radicals was relatively slow [17]. Therefore, the primary quantum yields for the formation of these species and the photodecomposition rates of free chlorine might depend on wavelength of light and on pH [10, 14, 16]. Recently Urs von Gunten et al found that UV dose of 2.2×104 j.m-2 gives 70% efficiency in the degradation of monochloramine [18]. Ormeci et al also showed that UV dose at (254 nm) at about 1.2×104 j.m-2 and 1.5×104 j.m-2 were needed to obtain a 50% decay of monochloramine in deionized and treated water, respectively [13]. Besides photodecomposition of monochloramine by direct photolysis in the same conditions has given essentially two by-products: nitrate (NO-3) and nitrite (NO-2) [19]. Photodecay mechanism of this compound was given first by Li and Blatchely and also by De Laat. These authors have demonstrated the role played by oxygen [5, 9]. The present study was undertaken in order to investigate and to compare the efficiency of three photochemical systems (at254 nm) in the monochloramine depletion. These are mainly: photolysis, H 2 O 2 /UV LP and NaOCl/UV LP (with constant concentration during the experiment). The effect of sodium bicarbonate used as scavenger for hydroxyl radicals, was examined during the photodecomposition of NH 2 Cl by NaOCl.

Additionally, experiments will be conducted with a probe molecule, terephthalic acid (TA) to compare the production of radicals •OH issued from H 2 O 2 /UV LP and NaOCl/UV LP . The kinetics of the degradation under different experimental conditions was also discussed.

MATERIALS AND METHODS Chemicals and reactor The basic chemicals used are 10-15% NaOCl (from Sigma Aldrich), 25% NH 4 OH (from Sigma Aldrich) and 30% H 2 O 2 (from Merck). Solutions of monochloramine ([NH 2 Cl] 0 ≈ 6 or 12 mg/l) were freshly prepared before each experiment by using a total nitrogen-to-chlorine molar ratios (N/Cl) = 1 and by a dropwise addition of sodium hypochlorite (NaOCl) into a wellstirred solution containing ammonia (NH 4 OH). The reaction time was about one hour at pH = 9.69. Under these conditions, the conversion of free chlorine into monochloramine was >98%. A stock solution of terephthalic acid (TA 98%) (5 × 10-2 M) (from Sigma Aldrich) was prepared in alkaline medium (pH = 9) . All solutions were prepared with demineralized water using “ISO 5 Milipore” water system. All experiments were conducted in a cylindrical photoreactor with an effective volume of 800 mL, a diameter of 90 mm, a height of 175 mm and a thickness of 6 mm. All the vessels coming from Heraeus Noblelight company, were made of glass. The total length and diameter of the cooling tube was 340 mm and 39 mm respectively, while the total length and diameter of immersion tube was 380 mm and 25 mm respectively. Both cooling and immersion tubes are made up of quartz which permit transfer of UV radiation through them. The free ozone lamp (GPH212T5L/4, 10 W) from Heraeus Noblelight was used as a UV light source. The temperature was kept constant at 20 ± 1 °C by water circulation using a (Julabo FL300 apparatus) thermostat. A continuous dosing pump from PHD 2000 Infusion (Harvard Apparatus) was used for continues supply of H2O2 (1000 mg/L or 0.029 M stock solution) and NaOCl (640 mg/L or 0.008 M) to keep the concentration constant during the time of the experience. Aliquot samples of 10 ml were taken from the vessel with a syringe. A magnetic stirrer (from IKA-WERKE) was used to keep the solution well mixed. Sample analysis Monochloramine, free chlorine and hydrogen peroxide were analyzed by using spectrometer (SPI Handmeter type D141) and the appropriate reagents. The detection limits for the different compounds are: (H 2 O 2 : 0-17 ppm ± 0.1 ppm; free chlorine: 0-12 mg/L ± 0.03 mg/L; Monochloramine 0-12 mg/L ± 0.03 mg/L). For H 2 O 2 determination, a molybdate reagent was used with a photometric detection wavelength at 350 nm. The hypochlorite (free chlorine) reacts immediately with DPD

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(N, N-diethyl-pphenylendiamine) reagent to yield a pink color; the total chlorine was also quantified. The bounded chlorine oxidizes the iodide present in the reagent to form iodine, this latter reacts with the DPD and the difference between the results of total and free chlorine yields the bounded chlorine. The photometric detection wavelength was 530 nm. A digital pHmeter (Hanna HI 3222) was used to measure all pH solutions. Nitrites (NO-2), nitrates (NO-3) and ammonium (NH+4) were analyzed with special reagents from Hach-Lange on (DR 5000) UV-Visible spectrophotometer. Experiments were conducted separately in presence of terephthalic acid (TA) with H 2 O 2 and NaOCl allowing the measure and the comparison of the amount of radicals •OH generated by both systems. However, it is clear that these species could react with (TA) to produce a highly florescence compound: 2-hydroxyterephthalic acid (2-OHTA) [20]. Therefore solution containing: 5×10-4 M of (TA) and (NaOCl 5 mg/L or 6.71 × 10-5 M) or (H 2 O 2 5 mg/L or 1.47 × 10-4 M) were prepared in distillated water at pH = 8.79. The irradiation time for both solutions was 10 min. The detection of these two species was made by photoluminescence PL (PIT Quanta Master Model QM-1) at 425 nm after an excitation at 315 nm.

Kinetics expressions For a solution containing a single absorbing compound (C) that is characterized by A = ελ.l. [C] (where A absorbance, ε λ molar absorptivity, [C] molar concentration of absorbing compound, l optical path length) it can be demonstrated that:

conjunction with linear regression to estimate rate constant (kpc) for photodecay of NH 2 Cl using only direct photolysis. To model the oxidation of monochloramine in water using UV radiation the direct photolysis as well as the advanced oxidation process based on •OH and/or Cl• radicals have to be taken into account. The following rate law can be used to describe the decay of a compound C [21]:

-

(Eq. 4)

For the NaOCl/UV system in the presence of sodium bicarbonate (•OH) scavenger:

-

(Eq. 5)

Where k pc is the first-order direct photolysis rate constant, k OH•,C is the rate constant for the oxidation by hydroxyl radicals, k Cl•,C is the rate constant for the oxidation by chlorine radicals, [C] is the concentration of the compound, [•OH] is the concentration of hydroxyl radicals, and [Cl•] is the concentration of chlorine radicals. Under the condition that the •OH radical or Cl• concentration is constant (steady state) due to the continuous dosing of the H 2 O 2 or NaOCl during the experiments time and the k pc the direct photolysis constant previously determined, Eq. (4) and Eq. (5) reduces to

-

(Eq. 6)

-

(Eq. 7)

(Eq. 1) Where, : intensity of incident radiation at wavelength λ (E.cm-2.s-1),

: molar absorptivity of the compound at wavelength λ (M1.cm-1 ), [C]: concentration of target compound (M), : quantum yield (mole.E-1). Eq. (1) can be solved to indicate the time-dependent behavior of the target compound:

(Eq. 2) (Eq.3) The rate of decomposition of [C] follows pseudo-first kinetics, measured values of [C] 0 , [C] t and time t were used in

This pseudo first-order rate law can be used to determine experimentally the overall reaction rate constant k app and k’ app .

RESULTS AND DISCUSSION

and

Actinometry using H 2 O 2 for UV fluence calculation lamp efficiency

Hydrogen peroxide actinometry experiments were performed to determine the fluence rate in the quartz tube for the Low Pressure (LP) lamp [22, 23]. For high values of optical density of the H 2 O 2 solution (concentrated medium, D > 2), the photonic fluxes of the lamps calculated from the general equation: (Eq.8)

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-

With: [C] 0 : concentration of compound C at time t = 0 (mol/L) [C]: concentration of compound C at time t (mol/L) Φ: quantum yield of the actinometry compound (Φ H2O2 = 0.5) P 0 : incident photonic flux (Einslein s-1) (1 Einslein = 1 mol photons) V: volume of the solution (L) t: time irradiation (min)

(a) ClO , (b) HOCl, (c) NaOCl, (d) NH2Cl, (e) H2O2, (f) NH4OH

Hence, the incident photon flux of (LP) lamp at 254 nm was 4.87 ×10-6 Einslein s-1. Consequently, the power of the lamp is 2.29 W (typical efficiency 22.9 %) which can be calculated using the following relation: (Eq.9) Where P is the power of the lamp, N is the Avogadro’s number (6.023 × 1023), h is Planck’s constant (6.63 × 10-34 J.s), c is the light velocity (2.99 × 108 m.s-1), p o is the photonic flux in Einstein.s-1, and 𝛌𝛌 is the maximum lamp wavelength (254 × 109 m). As far as the average fluence rate (UV Dose) is concerned, “Bolton UVCalc1B software” is used to estimate it. Actually, in the software both reflection and refraction are taken into account as the beam of UV radiation passes through an air/quartz/water interface [24]. The fluence rate is estimated according to the followed dimensions: 2.5 cm width (the distance between the quartz cooling jacket and the reactor wall) and 16 cm height (the height of the reaction medium in which the lamp is immersed). In addition the software was run to estimate also the average fluence rate for different transmittance values at 254 nm as the penetration of light through the reactor is changed with the concentration. UV-Visible spectra study The UV-visible study was carried out on hydrogen peroxide, sodium hypochlorite, monochloramine, and ammonium hydroxide using DR 5000 Hach-Lange spectrometer. The purpose of this section is to determine the maximum wavelength and the extinction molar coefficient (ε) for the different products used in this study. The molar extinction coefficient, ε, is a measurement of how strongly a chemical species absorbs light at a given wavelength. It is an intrinsic property of the species. The recorded spectra are presented in figure. 1.

Fig. 1 UV-visible spectra of: (a) NaOCl (ClO-) (10-2M ; pH=10.67); (b) NaOCl (HOCl) (10-2M ; pH=4.8); (c) NaOCl (50%HOCl , 50%ClO-) (10-2M ; pH=7.2 ≈ pKa=7.5); (d) NH 2 Cl (6mg/L ; pH=10.67); (e) H 2 O 2 (10-2M ; pH=6.20); (f) NH 4 OH (10-2M ; pH=10.70); T° = 20 ± 1 °C Hypochlorous acid and hypochlorite ion (HOCl/ClO-), which are the two forms of free chlorine at neutral pH, absorb UV radiation in the field of wavelengths between 200 and 360 nm (figure. 1. (a), (b), (c)). Additionally, the spectrum of HOCl presents two bands: one centred on 234 nm (ε ≈ 52.6 M-1.cm-1) and a second band around 300 nm (ε ≈ 15.3 M-1.cm-1); ClO- has a characteristic band centred at 292 nm (ε ≈ 211.7 M-1.cm-1). It should be noticed that monochloramine has an absorption band at 244 nm with a maximum extinction coefficient equal to 643.77 M-1.cm-1 (fig.1. (d)). The UV-absorption spectrum of monochloramine obtained in this work is very consistent with the spectra reported in literature [25, 26]. Hydrogen peroxide (H 2 O 2 ) and ammonium hydroxide (NH 4 OH) do not show any maximum band. In general all these absorb in the UV region. Hydroxyl radicals generation under H 2 O 2 /UV and NaOCl/UV Fig. 2 shows the changes of PL spectra of TA solution at pH equal to 8.78, in the presence of H 2 O 2 and NaOCl under dark and UV LP light irradiation for 10 minutes. No PL signal was observed in the absence of UV light irradiation. However, the highest PL intensity at about 425 nm was observed with H 2 O 2 /UV LP and the lowest one with NaOCl/UV LP . This can be explained by the dissociation of H 2 O 2 or NaOCl and the generation of the Terephthalic acid radical (TA•) which is easily formed by (•OH) than by (Cl•). From these results it can be said that the H 2 O 2 /UV LP system generates a greater amount of (•OH) comparatively to that of NaOCl/UV LP system. The concentrations used are: 5 mg/L or 1.47 × 10-4 M in H 2 O 2 and 5 mg/L or 6.71 × 10-5 M in NaOCl.

Conference Paper

Photolysis of monochloramine by UV LP lamp

Fig. 2 Photoluminescence (PL) spectral of 5 × 10-4 M terephthalic acid (TA) solution at pH 8.78 (excitation at 315 nm) in dark and after 10 min UV LP (254 nm) irradiation in the presence of (5 mg/L H 2 O 2 ) and (5 mg/L NaOCl); T° = 20 ± 1 °C

The photodecay monochloramine, taken at two different concentrations (6 mg/L or 1.16 × 10-4 M) and (12 mg/L or 2.33 × 10-4 M) was studied as a function of UV dose at pH 9.69 and with UV LP (254 nm). After each exposure period, samples were collected and the concentration was measured by the DPD (N, N-diethyl-phenylendiamine) method. The result depicted in figure (04), showed that monochloramine was susceptible to degrade by this process. Indeed, the rate of degradation in these conditions was equal to 98% for a UV dose 16000 mj/cm2 (figure 04). In another part we observed that only 2336.4 mj/cm2 was needed to obtain a 50% decay of the compound. During the process of direct photolysis, we observed a change in the spectra of monochloramine within the exposure time. Moreover, we noticed a decrease of the band located at 244 nm followed by the formation of a strong one around 200 nm which could be attributed to formation of two main by-products: Nitrate (NO-3) and Nitrite (NO-2). It was important to indicate that NH 2 Cl remained almost constant in dark conditions.

Once the radicals (Cl• and •OH) are liberated from these two species (H 2 O 2 and NaOCl) and by taking in to account the competitions toward the probe molecule (TA), they react with this compound to give Terephthalic acid radical (TA•) and finally with (•OH) to give a fluorescent product: 2hydroxyterephthalic acid (2-OHTA). The reactions (Eq.10 and Eq.11) and mechanism describing the processes are represented below (figure 3): H 2 O 2 + hʋ → 2 •OH (Eq. 10) NaOCl + hʋ → •OH + Cl •/OCl • (Eq. 11) The TA react either with •OH or Cl• to give in first step the radical TA which in turn react preferentially with •OH to give 2OHTA:

Fig. 4 UV Photodecay Of The Concentration Of Compound Chlorine As The Function Of UV Dose For 254 Nm Wavelength Of Exposure (Ph = 9.69 ± 0.5); T° = 20 ± 1 °C

Fig. 3 Schematic Reaction Mechanism Of TA With (•OH) And (Cl•) Free Radicals

Conference Paper

(a)

(b) Fig. 5 Spectrum Evolution Of NH 2 Cl (6 Mg/L) Photolysis With UV LP , Ph = 9.69 ± 0.5; T° = 20 ± 1 °C Monochloramine degradation by H 2 O 2 / UV LP The results on degradation of NH 2 Cl (6 mg/L or 1.16 × 10-4 M) and (12 mg/L or 2.33 × 10-4 M), under the UV LP lamp with continuous dosing to insure a constant concentration of H 2 O 2 (5 mg/L or 1.47 × 10-4 M) are plotted in figure (6). The results indicate that the degradation is faster and more effective in the presence of H 2 O 2 compared to those obtained in direct photolysis. The results can be interpreted by taking into account the absorption of H 2 O 2 at 254 nm where hydrogen peroxide is rapidly dissociated, producing thus radicals •OH, a nonselective and powerful oxidant, which decomposes the monochloramine very quickly [27-29].

Fig. 6 Relative Concentration Of Compound Chlorine As The Function Of UV Dose With Photolysis And UV LP /H 2 O 2 (5 Mg/L) Continuous Dosing, (A) [NH 2 Cl] 0 = (6 Mg/L) And (B) [NH 2 Cl] 0 = (12 Mg/L); Ph = 9.69 ± 0.5; T° = 20 ± 1 °C

H 2 O 2 + hʋ → 2 •OH (Φ=0.5) (Eq. 12) Where Φ is the quantum yield of the homolytic H 2 O 2 photodissociation, NH 2 Cl + •OH → degradation products (Eq. 13) As with photolysis, NH2Cl remained almost constant in dark conditions and in the presence of H 2 O 2 . The variation of the spectral absorbance of the monochloramine, show a sensitive decrease of the absorption band located at 244 nm, due to the action of •OH radicals (produced in situ from H 2 O 2 photolysis at 254 nm) and the formation of an isobestic point at 237 nm (figure 7). At this point, all the chemical species have the same molar absorptivity (ε) or -more generally- are linearly related [30].

Fig. 7 Spectrum Evolution Of NH 2 Cl (6 Mg/L) With UV LP /H 2 O 2 (5 mg/L) Continuous Dosing; Ph = 9.69 ± 0.5; T° = 20 ± 1 °C

Conference Paper

Monochloramine degradation by NaOCl/UV LP in the presence and in absence of •OH radical scavenger

(a)

As with direct photolysis and with H 2 O 2 , solutions of NH 2 Cl were stable in presence of NaOCl (5 mg/L or 6.71 × 10-5 M). Figure 08 depicted degradation process of NH 2 Cl (6 mg/L or 1.16 × 10-4 M and 12 mg/L or 2.33 × 10-4 M) by UV LP /NaOCl continuous dosing in absence and in the presence of the scavenger: NaHCO 3 (10-1 M). First, in its absence we have observed no significant difference in the efficiency rate for degradation by photolysis and NaOCl/ UV LP processes: Without scavenger: NaOCl + hʋ → •OH + Cl•/OCl • (Eq. 14) NH 2 Cl + •OH → degradation products (Eq. 15) NH 2 Cl + Cl•→ chloramines (Eq. 16) Chloramines + •OH → degradation products (Eq. 17) Chloramines+hʋ → degradation photoproducts (Eq. 18)

(b) By contrast, the degradation has become increasingly slow. These results indicated that •OH radicals were scavenged due to the formation of carbonate anion radical [31] and also inactive species as, CO 4 -2 and C 2 O 7 -2 [32, 33]: In the presence of scavenger: NaOCl + hʋ → •OH + Cl•/OCl • (Eq. 19) HCO-3 + •OH → CO•-3 + H 2 O (Eq. 20) CO•-3 + •OH → HOOCO-2 (Eq. 21) CO•-3 + CO•-3 C 2 O 6 -2 → CO 2 + O 2 COO-2 (Eq. 22) CO•-3 + CO 4 -2 → CO 4 •- + CO 3 -2 (Eq. 23) CO•-3 + CO 4 •- → C 2 O 7 -2 (Eq. 24) NH 2 Cl + Cl•→ chloramines (Eq. 25) Chloramines+ hʋ → degradation photoproducts (Eq. 26) It is interesting to mention that Cl• radicals may play an important role in the formation of chloramines which in turn could be degraded by direct photolysis. The spectral evolution of the monochloramine is similar for both systems: NaOCl/ UV LP and H 2 O 2 / UV LP . This fact may presume that we have the same final products with them. (figure. 09).

Fig. 8 Relative Concentration Of Compound Chlorine As The Function Of UV Dose With Photolysis, UV LP /Naocl (5 Mg/L) Continuous Dosing And UV LP /Naocl (5 Mg/L) Continuous Dosing / Nahco 3 (10-1 M), (A) [NH 2 Cl] 0 = (6 Mg/L) And (B) [NH 2 Cl] 0 = (12 Mg/L); Ph = 9.69 ± 0.5; T° = 20 ± 1 °C

Conference Paper

(b)

(c)

Fig. 9 Spectrum Evolution Of NH 2 Cl (6 Mg/L) With UV LP /Naocl (5 Mg/L) Continuous Dosing; Ph = 9.69 ± 0.5; T° = 20 ± 1 °C Degradation photoproducts of NH 2 Cl The degradation of NH 2 Cl (6 mg/L or 1.16 × 10-4 M) and (12 mg/L or 2.33 × 10-4 M) by the three processes, has led to the formation of photoproducts like: Nitrate (NO-3) and Nitrite (NO-2). Besides, no ammonia formation was observed during these processes (figure 10). These results were in agreement with those given by the literature [14]. Furthermore, some authors showed that Nitrite was the major product whereas Nitrate was the minor one during the photodecomposition of NH 2 Cl in presence of dissolved oxygen [5]. In addition, it is interesting to emphasize that the highest amount of (NO-2) was formed with NaOCl/UV LP and the lowest one with H 2 O 2 / UV LP . Other nitrogenous products like nitrogen gas (N 2 ) and/or nitrous oxide (N 2 O) could also be formed. These results were also in agreement with those related by the literature [34].

(a)

(d)

(e)

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(f)

Fig. 10 Degradation Photoproducts Of NH 2 Cl, Change In The Concentration Of NO-3, NO-2 And NH+4, (A) UV LP Photolysis [NH 2 Cl] 0 =(6 Mg/L), (B) UV LP Photolysis [NH 2 Cl] 0 =(12 Mg/L), (C), UV LP /H 2 O 2 [NH 2 Cl] 0 =(6 Mg/L), (D) UV LP /H 2 O 2 [NH 2 Cl] 0 =(12 Mg/L), (E) UV LP /Naocl [NH 2 Cl] 0 =(6 Mg/L), (F) UV LP /Naocl [NH 2 Cl] 0 =(12 Mg/L) Ph = 9.69 ± 0.5; T° = 20 ± 1 °C

Study of the pseudo-first order kinetics The logarithmic plot of (C/C 0 ) versus time has given straight lines for the tree systems. Therefore the experimental data could be best represented by a pseudo-first-order model (figure 11). As results the k app value for these processes might be deduced from the slopes of the curves (table 1). They showed also that the degradation at a constant concentration of H 2 O 2 (5 mg/L or 1.47 × 10-4 M) and under UV LP light was faster than that observed with photolysis and NaOCl (5 mg/L or 6.71 × 10-5 M) (continuous dosing) in presence and in absence of scavenger (NaHCO 3 ). This high efficiency could be attributed to radical •OH produced from photolysis of H 2 O 2 at 254 nm [27-29]. Additionally, the rate constant calculated from NaOCl/UV LP and direct photolysis was found to be very close in spite of the participation of Cl• radical, produced from the first system. This results could be explained essentially by competition of •OH and Cl• towards monochloramine. However, we should precise that •OH could degrade NH 2 Cl whereas Cl• could form chloramines in the same time making thus the degradation slow enough for both concentrations of our substrate. This fact was proved by addition of the scavenger (NaHCO 3 ). In this case we noticed a decrease in different values of the kapp (table 1).

Fig. 11 Graphical Estimation Of The Pseudo-First Order Rate Constant Of UV LP Direct Photolysis, UV LP /H 2 O 2 (5 Mg/L) Continuous Dosing, UV LP /Naocl (5 Mg/L) Continuous Dosing And UV LP /Naocl (5 Mg/L) Continuous Dosing / Nahco 3 (10-1 M), (A) [NH 2 Cl] 0 =(6 Mg/L), (B) [NH 2 Cl] 0 =(12 Mg/L); Ph = 9.69 ± 0.5; T° = 20 ± 1 °C Table 1: Pseudo First Rate Constants Obtained Of NH 2 Cl Degradation Experiment conditions UV LP direct photolysis UV LP /H 2 O 2 (5 mg/L) continuous dosing UV LP /NaOCl (5 mg/L) continuous dosing UV LP /NaOCl (5 mg/L) continuous dosing / NaHCO 3 (10-1 M)

6mg/L k app (min-1)

R2

12 mg/L k app (min-1)

R2

0.119

0.98

0.095

0.985

0.168

0.979

0.128

0.987

0.102

0.98

0.096

0.99

0.055

0.983

0.059

0.986

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CONCLUSION

[3] J.J. Rook. Formation of haloforms during chlorination of natural waters. Water Treatment Examination, 23 (1974), 234-243.

The results of this study indicate that: 1. Monochloramine absorbs photons at 254 nm and can be photolysed by UV light emitted by the lamp we used; 2. Monochloramine can be degraded more rapidly by H 2 O 2 / UV LP than by direct photolysis. This is due to the participation of radicals •OH; 3. The NaOCl/ UV LP process can form hydroxyl radicals simultaneously with chlorine radicals. The H 2 O 2 / UV LP system generates a greater amount of •OH radicals than the NaOCl/UV LP system. These results are obtained with basis of a probe molecule: TA and at pH = 8.78. The detection is made by PL; 4. NaOCl/ UV LP which is also an advanced oxidation process is less effective than H 2 O 2 / UV LP in the degradation of monochloramine. This fact can be due to the formation Cl• that can form combined chlorine during the time exposure to the UV light; 5. The decomposition of monochloramine leads to the formation of nitrate and nitrite whatever the system used; 6. The variation of the spectral absorbance show decrease in the peak at 244 nm (monochloramine peak absorbance) with time and formation of an isosbestic point at 237 nm; 7. The degradation kinetics of monochloramine can be adjusted to a pseudo-first order kinetic model with direct photolysis, NaOCl/ UV LP and H 2 O 2 / UV LP .

[4] C.T, Jafvert; R.L, Valentine. Reaction scheme for the chlorination of ammoniacal water. Environmental Science and Technology, 26 (1992), 577-586. [5] J, De Laat; N, Boudiaf, F, Dossier-Berne. Effect of dissolved oxygen on the photodecomposition of monochloramine and dichloramine in aqueous solution by UV irradiation at 253.7 nm. Water Research, 44 (2010), 3261-3269. [6] Technical note chloramines, the good & the bad, an evaluation of chloramine treatment for DBP reduction, (2009), V0308. [7] Ganesh R, Leong L, Tikkane M, Peterka G, Wang LK, Hung YT. Advanced physicochemical treatment processes, chapter 13. In: Wang LK, Hung YT, Shammas NK, editors. Dechlorination handbook of environmental engineering, vol. 4. Totowa, NJ: Humana Press, 4 (2006), 441-62. [8] D. Cassan ; B. Mercier., F. Castex; A. Rambaud. Effects of medium-pressure UV lamps radiation on water quality in a chlorinated indoor swimming pool. Chemosphere, 62 (2006), 1507-1513. [9] Li, J., Blatchley III. Combined application of UV radiation and chlorine. Implications with respect to DBP formation and destruction in recreational water applications. Conference presented at Disinfection: Water, Wastewater, Stormwater, Water Reuse and Biosolids. Pittsburgh, USA, (2007).

ACKNOWLEDGMENTS We are grateful to the Organization for the Prohibition of Chemical Weapons (OPCW) for financial support of this research. We would like to thank also Pr. Peter Appel and Dr. Henk Nugteren for the help, advice and support provided for the realization of this work.

REFERENCES [1] Mosteo, R. Mosteo, N.Miguel, S. Martin-Muniesa, Maria.P. Ormad, José L. Ovelleiro. Evaluation of trihalomethane formation potential in function of oxidation processes used during the drinking water production process. Journal of Hazardous Materials, 172 (2009), 661-666. [2] Richardson, S.D., Plewa, M.J., Wagner, E.D., Schoeny, R., DeMarini, D.M. Occurrence genotoxicity and carcinogenicity of regulated and emerging disinfection byproducts in drinking water: a review and roadmap for research. Mutation Research, 636 (2007), 178-242.

[10] G.V. Buxton; M.S. Subhani. Radiation chemistry and photochemistry of oxychlorine ions. II. Photodecomposition of aqueous solutions of hypochlorite ions. J. Chem. Soc., Faraday Trans, 68 (1972), 958-969. [11] M.J. Molina; T. Ishiwata; L.T Molina. Production of OH radical from photolysis of HOCl at 307-309 nm, J. Phys. Chem, 84 (1980), 821-826. [12] Lisa.H. Nowell; J. Hoigné. Photolysis of aqueous chlorine at sunlight and ultraviolet wavelengths e I. degradation rates. Water Research, 26 (1992), 593-598. [13] B. Ormeci; J.J. Ducoste; K.G. Linden. UV disinfection of chlorinated water: impact on chlorine concentration and UV dose delivery. Journal Water Supply Research and TechnologyAQUA, 54 (2005), 189-199. [14] M.J. Watts; K.G. Linden. Chlorine photolysis and subsequent OH radical production during UV treatment of chlorinated water. Water Research, 41 (2007), 2871-2878.

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[15] W.J. Cooper; A.C. Jones; R.F Whitehead; R.G. Zika. Sunlight-induced photochemical decay of oxidants in natural waters: implications in ballast water treatment. Environmental Science and Technology, 41 (2007), 3728-3733.

solution. ACS symposium series 82. In: Wang RG, editor. Water contamination and health. Integration of exposure assessment, toxicology and risk assessment, (1978), New York, NY: Marcel Dekker.

[16] Y. Feng; D.W. Smith; J.R. Bolton. Photolysis of aqueous free chlorine species (HOCl and ClO-) with 254 nm ultraviolet lamp. Journal of Environmental Engineering and Science, 6 (2007), 277-284.

[26] Z. Qiang; C.D. Adams. Determination of monochloramine formation rate constants with stopped flow spectrophotometry. Environmental Science and Technology, 38 (2004), 1435-1444.

[17] C.L. Thomsen; D. Madsen; J.A. Poulsen; J. Thogersen; S.J.K. Jensen; S.R. Keiding. Femtosecond photolysis of aqueous HOCl, J. Chem. Phys, 115 (2001), 9361– 9369.

[27] O. Legrini; E. Oliveros; A.M. Braun. Photochemical processes for water treatment. Chem. Rev, 93 (1993), 671-698.

[18] Fabian Soltermann, Tobias Widler, Silvio Canonica, Urs von Gunten. Photolysis of inorganic chloramines and efficiency of trichloramine abatement by UV treatment of swimming pool water. Water research, 56 (2014), 280-291. [19] Leung SW, Valentine RL. Chloramine loss and byproduct formation in chloraminated water, chapter 19. In: Minear RA, Amy GL, editors. Disinfection by-products in water treatment. The chemistry of their formation and control. Boca Raton, FL: CRC Press, 19 (1996), 363-70.

[20] J. Yu; B. Wang. Effect of calcination temperature on morphology and photoelectrochemical properties of anodized titanium dioxide nanotube arrays. Applied Catalysis BEnvironmental, 94 (2010), 295-302. [21] E.J. Rosenfeldt; K.G. Linden. The ROH,UV concept to characterize and the model UV/H2O2 process in natural waters. Environmental Science and Technology, 41 (2007), 2548-2553. [22] I. Nicole; J. De Laat; M. Dore; J. P. Duguet; C. Bonnel. Use of u.v. radiation in water treatment: measurement of photonic flux by hydrogen peroxide actinometry, Water Research, 24 (1990), 157-168. [23] H.J. Kuhn, S.E.B., R. Schmidt. Chemical actinometry, IUPAC technical report, Pure Appl. Chem, 76 (2004), 21052146. [24] James R. Bolton. Calculation of ultraviolet fluence rate distributions in an annular reactor: significance of refraction and reflection, Wat. Research, 34 (2000), 3315-3324. [25] Gray Jr ET, Margerum DW, Huffman RP Chloramine equilibria and the kinetics of disproportionation in aqueous

J.R. Bolton; S.R. Cater. Homogeneous [28] photodegradation of pollutants in contaminated water: an introduction. In: G.R. Helz; R.G. Zepp; D.G. Crosby (Eds.). Aquatic and Surface Photochemistry. EEUU, Lewis, Boca Raton, FL, 33 (1994), 467-490. [29] K.G. Bircher; W. Lem; K.M. Simms; B.W. Dussert. Combination of UV oxidation with other treatment technologies for remediation of contaminated water. J. Adv. Oxid. Technol, 2 (1997), 435-441. [30] Timberlake CF, Bridle P. Isosbestic points in the visible and ultra-violet spectra of three component systems. Spectrochim Acta Part A Mol Spectroscopy, 23 (1966), 313319.

[31] J.L.a.J.R. Weeks. The pulse radiolysis of deaerated carbonate solutions. 1. Transient optical spectrum and mechanism. II. pK for OH radicals. J. Phys. Chem, 70 (1996), 2100-2106. [32] Wu. Guozhong; Y. Katsumura; Yusa Muroya; Mingzhang Lin; Tomomi Morioka. Temperature Dependence of Carbonate Radical in NaHCO3 and Na2CO3 Solutions:  Is the Radical a Single Anion, J. Phys. Chem. A, 106 (2001), 24302437. [33] K.S. Haygarth; T.W. Marin; I. Janik; K. Kanjana; C.M. Stanisky; D.M. Bartels. Carbonate Radical Formation in Radiolysis of Sodium Carbonate and Bicarbonate Solutions up to 250 °C and the Mechanism of its Second Order Decay. J. Phys. Chem. A, 114 (2010), 2142-2150. [34] Jing Li., Ernest R. Blatchley III. UV photodegradation of inorganic chloramines. Environmental Science and Technology, 43 (2009), 60-65.

İSTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

NOISE POLLUTION IN THE METROPOLITAN CITY CENTER OF SAMSUN, TURKEY *Sevda Esma Akkaya Department of Environmental Engineering Faculty of Engineering Ondokuz Mayıs University, Samsun

Onur Yontar Department of Mechanical Engineering Faculty of Engineering Ondokuz Mayıs University, Samsun

Prof. Dr. Osman Nuri Ergun Department of Environmental Engineering Faculty of Engineering, Ondokuz Mayıs University, Samsun Keywords: Noise pollution, Samsun, Traffic noise pollution. * Corresponding author: ABSTRACT Outdoor noise pollution is one of the most important environmental issues in all over the world, particulary metropolitan and other large city centers where so many citizans live. The major factor for the outdoor noise pollution in the settlement units is traffic activities. The source of the noise derived from not only the road whicles, but also from the air and marine transport activities where maritime lines are active. In the city centers of Turkey the noise pollution is probably the most important environmental problem. The metropolitan city center of Samsun suffers from the noise pollution as in many metropolitan cities in Turkey. The aim of this research is to investigate the noise pollution levels in the metropolitan city center of Samsun. The central town centers of the metropolitan city Atakum province center has been chosen for the noise level investigation due to having various public transportation altenatives, namely bus, tram and collective taxi; beside that Atakum is a newly developing province amongst others in Samsun with the establishment of government facilities, dormitories, a shopping mall, many sightseeing points, restaurants and bars. More than 300 measurement stations were arranged for the investigation. All main roads of the settlement units examined for noise level together with traffic frequency and other city activities. According to the noise level data obtained in this research the noise level is very high in all main streets of the examined town center in the metropolitan city. Particulary during the rush hours, the noise levels exceed all of the national and international standarts for healty life. The noise levels are higher in winter seasons comparing with summer times. The reasons for this differences are probably holiday time, weather condition and student mobility. In this research more than 6000 measures examined together and numerically analyzed to determine the noise pollution of the Atakum province center of metropolitan city of Samsun. INTRODUCTION With the development of technology and industry, noise in big cities has become a problem for people. Along with these problems, noise is now a "pollution" concept. It has become a social and environmental problem that affects

living conditions and makes people nervous [1]. Noise can be defined as sound irregularity that does not have a clear structure and can affect the person physically and psychologically [2]. Conditions such as noise frequency, duration of presence in the environment, whether or not it is caused by a noise point, planar or linear source, the age, physical and mental condition of the person exposed to the noise, and time distribution in the environment where the noise is present are important factors for being perceived as discomfort by the noise receiver [3]. The effects on humans are physiological and psychological. Physiological effects, elevation of hearing threshold, permanent and temporary hearing loss, and headache. Psychological effects are distraction, stress, unhappiness and sleep disturbance. Hearing loss, especially caused by noise, is a health problem that can not be solved by medical and surgical methods. For this reason, it is necessary to reduce or prevent the effects by taking noisy protective measures [4]. The history of legal regulations on noise can not be said to be very old in the world. The first legal regulation in this regard was the OSHA, "Occupational Safety and Health Regulation" issued by the United States on 29 December 1970 [5]. In 1970 United States of America, in 1960 in England, in 1967 in Japan, in 1979 in Holland, in 1985 in France, laws on noise pollution were enacted and entered into force [6]. The first noise pollution control regulation in Turkey was put into practice on December 11, 1986. When we take a look at the types of noise sources, it could be seen that they are composed of basic sources such as industry, transportation, road and construction works at the settlement. While personal and social experiences differ, it is assumed that when the equivalent noise level exceeds 55 dBA the discomforts begin and exceeds 65 dBA, sleeping is seriously damaged and a vast majority of people are disturbed by noise [6]. Due to migration from the country to town, traffic problems are increasing in parallel with population growth, besides increasing traffic density is insurmountable. For this reason, the traffic noise is the biggest source of noise pollution in cities. In a study conducted, it was revealed that the road traffic noise can be reduced by 3.5 dBA with road speed reducers, road constrictions, road cuts and regulations and restrictions on traffic islands [7].

Conference Paper RESULTS AND DISCUSSION MATERIAL AND METHODS The study area Samsun is a province of Turkey and the sixteenth most populous city. According to 2015 records, it has a population of 1,279,884. It is located in the Black Sea Region and is the most populous city of the region. The Black Sea Region is the most developed city in terms of education, health, industry, trade, transportation and economy. Samsun is the city connecting the Black Sea Region to the Central Anatolia Region with the highways. [8] Atakum is a district of Samsun Metropolitan Municipality. Atakum is 5 km away from the city center on Samsun-Sinop highway. The sea is shallow and has a long beach. It is located in a flatter area than the other settlement areas of Samsun and is a newly built district. There is a more planned construction of urbanism since it is a newly constructed district. Population shows a rapid increase. According to 2015 data, Atakum population is 169,809 people. In Figure 1, the position of the Atakum is shown. [9].

When daily activities of the study area are considered, there are hospitals, schools and residences in Atatürk and Ismet Inönü boulevards. According to the regulation, schools, hospitals, nursing homes and places of worship are shown in sensitive areas. The measuring points are selected on the main access roads where traffic flow is intense. The measurement points were numbered and displayed for the 160 selected points on the atakum map. In Figure 2, certain decibel ranges on the map were shown on the color scale and a gradient map was generated by measurement data. The US department of housing and urban development gave the noise levels in the open air area as follows; • • • •

LAeq≤49 dBA absolutely acceptable. 49 < LAeq≤ 62 dBAcan be considered normal 62 < LAeq≤ 76 dBA can not be considered normal 76 < Laeq absolutely unacceptable. [10]

WHO (world health organization) recommends a limit of 55dBA for noise in open areas. According to the related regulation in Turkey, limit values are given in table 1. The average noise levels in the surveyed areas are 75 dBA for the Atatürk boulevard and 61 dBA for the Ismet İnönü boulevard. Adnan Menderes, which is a coastal strip where entertainment places are located, has an average noise level of 64 dBA. In the entertainment areas, the average sound level in the evening is 72 dBA, while in the daytime it decreases to 57 dBA. According to the regulation in Turkey, it should be done in the daytime in different noise levels; Table 1 Regulation Noise Limit Values Planned / Refurbished / Repaired ways Areas

Fig 1 Location of Atakum The research methodology Atakum was chosen as the research area. Samsun is a coastal town established on the interurban road of Sinop. Atatürk boulevard, İsmet İnönü boulevard and Adnan Menderes boulevard were chosen for the measurements. Ataturk boulevard is the main road which is the intercity road to Sinop. İsmet İnönü boulevard is a busy boulevard with tram and vehicle traffic. Adnan Menderes boulevard is with entertainment places on the beach side. 160 measurement points were selected on each boulevard, on both sides of the roads. Noise levels were measured 3 times a day between 08:00 and 10:00 in the morning, between 13:00 and 15:00 in the midday and between 18:00 and 20:00 in the evening. Three measurements were taken for each time and the average of these three was taken into account. Noise measurements were made with the Lutran SL-4001 sound level meter. The device has an LCD screen and a measurement range of 30-130dBA. The measurements were made the device would be 1 meter above the ground. In all measurements, air conditions were fine and the air temperature was above the average.

Areas where education, culture and health care, summer and camping sites are sensitive to noise Areas in which residential buildings are concentrated from areas where commercial buildings and noise sensitive uses coexist Areas where commercial establishments are sensitive to noisesensitive uses and places where workplaces are concentrated Industrial areas

L daytime (dBA)

Existing roads

L daytim L evening L night L evening L night e (dBA) (dBA) (dBA) (dBA) (dBA)

60

55

50

65

60

55

63

58

53

68

63

58

65

60

55

70

65

60

67

62

57

72

67

62

According to the regulation, what should be done according to the sound levels;

• • • •

Conference Paper Lg < 55 dBA not bother level, 55 < Lg ≤ 64 dBA take precautions, 65 < Lg ≤ 74 dBA background noise level should be reduced, 75 < Lg planning permission is not granted.

According to these values, almost all the points measured on Atatürk boulevard are unacceptable levels. The fact that the highest average is on Atatürk boulevard and the main reason is the intercity road and the heavy traffic. Ismet Inonu boulevard is a combination of tram and vehicle traffic. Although all the points that the tram passes through are silent, noise levels are quite high when coming to the intersections. The reason for the high level of noise in the intersections is that the vehicles do not have adequate waiting times, there are no parking restrictions and there are no traffic lights at all crossroads. As a solution to this situation; the use of traffic lights at intersections should not prevent traffic flow, vehicle intensity should be reduced by establishing parallel boulevards, overpasses should be built especially at the intersections to reduce vehicle intensity, the use of public transport should be encouraged. In terms of comfort inside the existing and new buildings, it is necessary to plan the sound insulation with a specialist.

REFERENCES [1] Aktürk N., Ünal Y., (1998) Gürültü, Gürültüyle Mücadele ve Trafik Gürültüsü, G.Ü. Fen Bilimleri Enst. Bülteni, no:3, 21-32. [2] Watts GR (1993) A Comparasion of Noise Measures for Assesing Vehicle Noisines. Journal of Sound and Vibration 180, 39, 493-512. [3] Downn CG, Stocks J (1978) Environmental Impact of Mining. Applied Science Publishers, London. [4] Fişek, NH. Halk Sağlığına Giriş. Hacettepe Üniversitesi Hizmet Araştırma ve Araştırıcı Yetiştirme Merkezi Yayını, No:2, Hacettepe Üniversitesi Basımevi, Ankara, 1983, S:3-6 [5] Occupational Safety and Healty Act, U.S. Department of Labor, 1970. [6] Morgul Ö., Dal H., (2012) A Preliminary Study on Noise Pollution of Sakarya Province City Center, SAÜ Fen Bilimleri Dergisi, s. 83-91. [7] Kohlhammer W., (1998) Bundesminisıer fiir Umwelt. Naturschutz und Reaktorsicherheit, Was sie schon immer über Utmıschutz wissen wollten. Verlag GmbH. McrcedcsDrack. Sluttgart. Berlin, Köln, Mainz. 247 s.ı. [8] https://tr.wikipedia.org/wiki/Samsun#N.C3.BCfus, 26.11.2016 [9] https://tr.wikipedia.org/wiki/Atakum, 28.11.2016 [10] Zannin PHT, Diniz FB, Barbosa WA (2002) Environmental Noise Pollution in the City of Curitiba Brazil. Applied Acoustics 63, 351-358.

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Fig 2 Noise Map Of Principal And Minor Thoroughfares İn Atakum

ISTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

TRIPLE DIFFERENTIAL CROSS SECTIONS FOR THE SINGLE IONIZATION OF METHANE MOLECULE (CH 4 ) BY ELECTRON IMPACT * Boumediene LASRI Theoretical Physics Laboratory, Physics Department, University of Tlemcen, Algeria. University Dr. MoulayTahar of Saïda, Algeria.

Fatima BOUASRIA University Dr. MoulayTahar of Saïda, Algeria.

Mohammed SAHLAOUI Superior School of Applied Sciences Science and Technology Preparatory School, Tlemcen, Algeria

Mammar Bouamoud Theoretical Physics Laboratory, University of Tlemcen, Algeria.

Mevlut DOGAN Afyon Kocatepe University, Science Faculty, Physics Department, 03200 Afyonkarahisar, Turkey.

Keywords: (e-2e), Born approximation, Triple differential cross section. * Corresponding author: Boumediene LASRI, Phone:00213552363727, E-mail address: [email protected]

ABSTRACT The ionization of atomic and molecular targets by electron impact called (e,2e) reaction is one of the complex and fundamental reactions in collision theory. In order to give a better description to this reaction, different theoretical and experimental methods have been developed. In this work, we present our analytical formalism developed to calculate the triple differential cross section (TDCS) for the ionization by electron impact of simple molecules with the chemical form XH n as for example Methane Molecule (CH 4 ), Ammonia Molecule (NH 3 ) and water molecule (H 2 O). A comparison between the theory and experiment allows for better understanding and improving the theoretical models. Our theoretical calculations (First Born, second Born for the ionization of Methane molecule CH 4 by electron impact stay in good agreement with experimental data. INTRODUCTION In recent decades, (e,2e) experiments for the ionization by electron impact have been performed for both atomic and molecular targets. In these experiments the triple-differential cross sections (TDCS) are measured. The investigated molecule in the present paper is methane.

Electron collisions with methane molecule are of particular interest in many fields of science and technology, ranging from astrophysics to bio-physics. Methane is the smallest hydrocarbon and the simplest molecule of all organic

composition. This molecule is also a primary constituent of the atmospheres of Jupiter, Saturn, Uranus and Neptune. Methane molecule is a good molecule to study from both experimental and theoretical aspects [4]. This molecule is relatively simple (as the water and ammonia [1,2,3,5]) with only one Carbone atom and four hydrogen atoms. This allows us to choose the collision framework centered on the Carbone atom. This choice helps us to reduce the complexity of this (e,2e) reaction. The CH 4 molecules interact with charged particles in atmosphere and electron-methane interactions are one of the most common and dominant processes in the nature. Our formalism [1-3] developed in the framework of the second Born approximation is employed to study the single ionization of the methane molecule by electron-impact. The exchange between the two outgoing electrons is considered only in the first Born term using the so-called Ochkur approximation, from the moment that this term represents the dominant part in the transition amplitude. In order to consider also the post-collision interaction between the outgoing electrons the final state is multiplied by the Gamow factor.

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THEORETICAL TREATEMENT:

RESULTS AND DISCUSSION

When the target is a molecule, the TDCS in the (e, 2e) reaction must be averaged over all the molecular orientations:

where 𝑑𝑑Ω means a molecular orientations given in the laboratory frame by the Euler angles (𝛼𝛼, 𝛽𝛽, 𝛾𝛾). 𝒌𝒌𝑖𝑖 , 𝒌𝒌𝑠𝑠 and 𝒌𝒌𝑒𝑒 are the momenta of the incident, scattered and ejected electrons, respectively. 𝑇𝑇 is an element of the transition matrix: (+)

Where |Ψ𝑖𝑖 ⟩ and �Ψ𝑓𝑓 � are the initial and final states. 𝐺𝐺0 and 𝑉𝑉 are the Green and interaction operators. In order to reduce the problem to two active electrons we have used the so-called frozen-core approximation. So, the interaction energy and the wave functions are reduced to the following forms:

The molecular orbital 𝜙𝜙𝑀𝑀𝑀𝑀 is expanded on a set of basis centered over the carbone atom [6]:

Figure 1: Triple Differential Cross Sections (TDCS) From The 1t 2 Molecular Orbital Of Methane (CH 4 ) In Coplanar Symmetric Geometry. Solid Circles: Experimental Data [4]. Green Dashed Line: Our Born-II Results. Blue Dashed Line: Our Born-I Results Without Gamow Factor, [3], Red Dashed Line Our Born-I Results With Gamow Factor. Red Solid Line: Results From The Molecular Three-Body Distorted Weave Approximation Nixon Et Al. [4].

�φ𝒌𝒌𝒊𝒊 � and �φ𝒌𝒌𝒔𝒔 � are plane wave describing the incident and scattered electrons. �ψ𝒌𝒌𝒆𝒆 � is a Coulomb wave function describe the transition to the continuum of the ejected electron:

After performing an analytically integration over the molecular orientations, the TDCS take the form

Where 𝑇𝑇𝜈𝜈𝑑𝑑 and 𝑇𝑇𝜈𝜈𝑒𝑒 are the direct and exchange amplitudes, respectively (for more detail the reader can see our papers [1-3]).

Figure 2: Same as Figure 1. The results given above for the ionization of the orbitals 1t 2 of the Methane (CH 4 ) molecule are derived in the coplanar symmetric geometry, for the scattering and ejecting energies E s = E e = 15 eV and 20 eV, and ejection angle varying from 0° to 180°. Our results are compared with the experimental and theoretical results of Nixon et al. [3]. We can see the good agreement of our results, given from the second born approximation, with the experiment in the binary region from θ =30° to θ =90°. In the recoil region from θ = 90° to θ = 180°

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the theory underestimates the experiment. When we compare the theoretical results of Nixon et al. with the experiment, we can observe, that the results given by the molecular three distorted wave (M3DW) model are in well agreement with the experience in the second recoil region. This is the consequences of the accurate description of the final wave function where the distortion effect of the molecular ion is taken into account in the two states describing the scattered and ejected electrons. We note that this effect become more important in the recoil region. This is the reason why our model underestimates the experiment in this region. However, the good agreement of our results with the experiment in the binary region shows that the transitions from the intermediate states of the initial to the final state are important and must be taken into account as in the second born approximation from our formalism. We note also that in the M3DW model each molecular orbital has been spherically averaged. however, the correct manner to consider all the molecular orientations is to average the TDCS over all these orientations as in our formalism. Like it has been awaited the first-Born approximation is far from describe the ionization problem in the low energies range. CONCLUSION In present study we left with two important results: To describe the (e,2e) reaction at low and intermediate energies, we must describe in the final state accurately the interaction of the outgoing electrons from the residual ion. At low and intermediate energies, the transition from the intermediate states of the initial to the final state are important and must be taken into account in each theoretical formalism.

REFERENCES 1. Sahlaoui M. ; Bouamoud M.. (2011), ″Cross sections for electron-impact ionization of water molecules″. Can. J. Phys., (89) 723 2. Sahlaoui. M., Bouamoud. M. (2012). ″Electron impact single ionization of the water molecule in the second Born approximation″. J. Phys. B: At. Mol. Opt. Phys. (45) 08520. 3. Sahlaoui. M., Bouamoud. M,, Lasri. B., Dogan. M., (2013). ″Ionization of a water molecule by electron impact in coplanar symmetric and asymmetric geometries″. J. Phys. B:At. Mol. Opt. Phys. (46) 115206. 4. Nixon. K. L., Murray. A. J., Chaluvadi. H., Ning. C., Colgan. J., Madison. D. H. (2013). ″Low energy (e2e) coincidence studies of NH 3 : Results from experiment and theory″. J. Chem. Phys., (138) 174304. 5. Murat Yavuz, Nimet Okumus, Zehra Nur Ozer, Melike Ulu, Mevlut Dogan, Mohammed Sahlaoui, Houda Benmansour, Mammar Bouamoud. Journal of Physics: Conference Series 488 (2014) 052031.

ISTANBUL INTERNATIONAL CONFERENCE ON PROGRESS IN APPLIED SCIENCE 2017 – ICPAS 2017 4 - 6 JANUARY 2017, Istanbul, Turkey

IINHIBITION OF CALCIUM CARBONATE DEPOSITION ON STAINLESS STEEL USING OLIVE LEAF EXTRACT AS A GREEN INHIBITOR of calcium carbonate Abdelkrim Kahoul*, Roumaissa Aidoud Laboratoire d’Energetique et d'Electrochimie du Solide, Université F. Abbas, Sétif-1, 19000-Sétif, Algeria.

Keywords : Calcium carbonate scale; olive leaf extract; antiscalant * Corresponding author:, Phone: 00213668626161, E-mail address:[email protected]

ABSTRACT Scale causes severe economic loss, since it limits heat exchange and can reduce tube diameter causing a significant decrease in water flow. In order to solve this problem many scale inhibitors have been used in cooling water systems. The used inhibitors were found to reduce the scale growth. Nevertheless, the use of chemical inhibitors has been limited because of the environmental threat. Recently, natural compounds such as herb plants are again employed as inhibitors in order to develop new cleaning chemicals for green environment. Several studies have been published on the use of natural products as antiscalants and corrosion inhibitors in different media. The drinking water network in Ain Kébira in the area of the city of Sétif knows some scaling problems as the deposit of calcium carbonate CaCO 3 on the pipe walls. This water is hard and naturally rich in minerals, such as calcium and magnesium. To reduce the CaCO 3 scale formation on the network, the aim of this study was to investigate the effect of olive leaf extract as a novel, environmentally friendly, antiscalant for the water of Ain kebira using chronoampérometry, electrochemical impedance spectroscopy (EIS) and microscopic examination techniques. It was found that the extract acts as a good antiscalant for the tested system. The inhibition efficiency increases with increasing extract concentration. A concentration of 100 ppm was found to be an optimal concentration for preventing completely the CaCO 3 deposit. The inhibitive action of the extract is discussed with a view of inhibtor

adsorption onto the steel surface, making a barrier to scale deposit. INTRODUCTION Scales cause severe economic loss, since it limit heat exchange and can reduce tube diameter causing a significant decrease in water flow [1–3]. In this paper, we are interested to study water scale found in water distribution system in the town of Ain Kébira. This town, located at a distance of 30 km far from the city of Sétif in the northeast region of Algeria, is supplied with drinking water from an underground water source called "Hammam water". This water, which is a scale-forming water, is transported from the Hammam source to a tower located at Ain Kebira town where it is used throughout the distribution network. In fact, changing the network pipes transporting water from time to time is necessary. Chemical analysis of the water revealed that this water has a scaling potential corresponding to a hardness of 34 French degrees (104 mg/L as Ca2+). The scale deposit, consisting essentially of calcium carbonate CaCO 3 , obstructs drinking water pipes leading to a decrease in flow rate. Hence, it is very important to investigate this scaling problem. In order to solve the problems many scale inhibitors have been used in cooling water systems [4, 5]. The inhibition efficiency of the used inhibitors was found to reduce the scale growth. Nevertheless, the use of chemical inhibitors has been limited because of the environmental threat. The hazardous effects of most synthetic scale inhibitors are the motivation for the use of natural products. A number of antiscalants are commercially available and new formulations are continuously being

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developed and tested for calcium carbonate CaCO 3 scaling such as gelatin, carboxymethyl cellulose and keratin [6]. Polymers with negatively charged groups can adsorb onto the surfaces of crystals and prevent agglomeration by keeping the CaCO 3 or CaSO 4 particles suspended in solution [7, 8]. Chaussemier et al. [9] focused on some antiscalants usually named “green inhibitors”, derived from petrochemicals and resumed the efforts done those last years to obtain these green inhibitors, either by using natural organic molecules or molecules extracted from plants. Recently, plant extracts have again become important as an environmentally acceptable, readily available and renewable source for a wide range of needed inhibitors. Plant extracts are viewed as an incredibly rich source of naturally synthesized chemical compounds that can be extracted by simple procedures with low cost. Various natural products were used as scale inhibitors in different applications. The obtained data showed that plant extracts could serve as effective environmentally friendly scale inhibitors. D.E. AbdEl-Khalek et al. investigated palm leaves [10]. Abdel-Gaber et al. investigated fig [11] leaves extracts as novel environmentally friendly antiscalants. Olive is one of the most important trees cultivated in the Mediterranean coastal zone, which grows well under calcareous soil conditions, and provides huge economic and dietetic benefits. The aqueous extract of olive leaf (Olea europaea L) consists of at least thirty natural phenolic compounds [12]. Among these, glycoside oleuropein 1, hydroxytyrosol 2 (3,4dihydroxyphenylethanol) (Fig.1) are found in highest concentration, together with tyrosol. Whereas hydroxytyrosol is the prevalent phenolic constituent of olive oil [13], oleuropein is the major polyphenol in the olive fruit, representing as much as 14% of the weight of the dried fruit.

. Figure 1. Chemical Structure Of Hydroxytyrosol And Oleuropein. The phenolic compounds adsorb on the steel surface through the lone pairs of electrons of the oxygen atoms forming a covering film. Inspection of the phenolic structures in Fig. 1 reveals that the oxygen atoms almost surround the aromatic rings of the phenolics. This arrangement of the oxygen atoms may lead to the conclusion that the phenolic compound is forced to be adsorbed horizontally onto the steel surface. This adsorption gives rise to a large covered surface area with a small number of adsorbed molecules. Therefore, high inhibition

efficiency could be obtained by relatively low concentrations of the extract. Using olive leaf (OL) extract as a scale inhibitor at different concentrations, for steel surface in brine solution of 0.7M NaCl, 0.0025M NaHCO 3 ,0.028M Na 2 SO 4 and 0.01M CaCl 2 , Abdel-Gaber et al. [14] reported a critical concentration of 50 ppm of the extract is required to obtain 83% of scale inhibition. It was reported that this inhibition may be attributed to complex forming of the extracted molecules together with the calcium ions present [15], but their scale preventing mechanism is not known in detail. Maciejewska et al. [16] synthesized and characterized a complex of caffeic acid, a constituent of olive leaf extract, with calcium ions. They demonstrated that the caffeic acid binds calcium ions through carboxylic groups and forms a nucleus of caffeate complex, which adsorbs on the surface at an early stage and poisons crystal nuclei around them. This study aims to gain some insight into the scaling of a stainless steel in a drinking water in the presence of OL extract as a scaling inhibitor. Our objective is to consider extracts from trees as scale inhibitors have large economic benefits and advantageously used in a situation where organic or mineral inhibitors would be limited by environmental regulation or difficulties of application. The inhibitive effect of this naturally extract on stainless steel scaling was investigated using chronoamerometry, electrochemical impedance spectroscopy and microscopic examination. To our knowledge, no study has so far been published about the scaling inhibitive effect, except that of Abdel-Gaber et al. [14] who investigated the inhibition properties of OL extract in alkaline brine solution which models natural seawater at relatively higher temperature. PREPARATION OF THE OL EXTRACT Fresh green olive leaves were collected from trees localized in the Sétif region. The leaves were then washed, dried inan oven and finally grinded to obtain a powder. A mixture of 5 g sample of the powder and 100 mL bidistilled water was placed in a round-bottom flask equipped with a condenser. The solution was heated to reflux for 1 h. The refluxed solution was filtered to remove any contamination. Theconcentration of the stock solution, expressed in terms of milligram per liter (ppm), was determined by evaporating 10 mL of the filtrate and weighing the residue. Diluted solutions were prepared by adding water to a volume of the stock solution.

RESULTS AND DISCUSSION (MANDATORY HEADER) A chronoamperometric curve, referring to Hammam raw water at 25°C, for the polarized SS electrode is presented in Fig. 2.

Conference Paper

250

tN

(1): 00 ppm (2): 5 ppm (3): 10 ppm (4): 20 ppm (5): 50 ppm (6): 100 ppm (7): 200 ppm

200 150 100 50 0

0

50

100 tS Time (min)

150

200

Figure 1. Chronoamperometric Curve Obtained At 25°C In Hammam Raw Water, Rotation Speed Of SS Electrode ω =500 Rpm, Applied Potential E= -1V/SCE. As seen, the plot can be separated into three regions: nucleation, crystalline growth and total coverage of the electrode surface. • During the first stage, an increase in the current is observed, when the potential is applied the system needs a few seconds to reach dynamic equilibrium to allow the diffusion layer which is related to the dissolved oxygen reduction to be established [15]. The scaling process is initialized by increasing the local pH near the electrode surface by means of reduction of the dissolved oxygen and water (reaction 1), then, the resulting hydroxide ions react with bicarbonates ions to give carbonates (reaction 2) which allow a few nuclei of CaCO 3 (reaction 3) to deposit on the electrode surface. The nucleation time t N, defined as the time between the creation of supersaturation and the first appearance of nuclei, is determined from the maximum of the chronoamperometric curve (see Fig. 2) • In the second stage, the current clearly decreased as the active electrode surface is progressively blocked by deposition of CaCO 3 . There is a continuation of nucleation and growth of the deposit crystals. • In the third stage, the current reached a very low value close to the residual current observed when the electrode was totally scaled. The scaling time t S at which total coverage of the electrode surface was obtained. by the intersection of the inflexion tangent with the time-axis. According to Lédion et al. [16], the index of scaling defined as I S =1000 / t S (min) makes possible to classify water as follows. • 100