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دراسة تاكل وتثبيط تاكل سبيكة الفولاذ المقاوم للصدا L 316 في اوساط ملحية مختلفة == Corrosion and Corrosion Inhibition Studies of Stainless Steel 316L Alloy in Different Saline Media

اسم المؤلف: مروة صباح حسين
اسم المشرف: وصال عبد العزيز عيسى | انتصار عليوي
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
الجامعة: جامعة بغداد
اللغة: الانكليزية
مكان الجامعة: بغداد
الصفحات الاولى:
المستخلص: تتضمن الرسالة دراسة كهروكيميائية لتاكل الفولاذ المقاوم للصدا نوع 316L في محاليل ملحية لكلوريد الصوديوم مختلفة التراكيز mol.〖dm〗^( - 3) (0.6و0.3و0.1) وفي قيم من الاس الهيدروجيني (pH) تضمنت (11و9و4و2) ومدى من درجات الحرارة من (293 - 308)K . وانجز العمل باستعمال جهاز المجهاد الساكن وخلية التاكل المكونة من ثلاثة اقطاب.وقد اوضحت النتائج العملية ما يلي : تزداد كثافة التيار(icorr) الزيادة الحامضية ودرجة الحرارة للوسط الاكال حيث تبلغ اعلى قيمة لها مساوية الى〖18.62 µA.cm〗^( - 2) عند pH=2 ودرجة حرارة= 308K. تزداد كثافة تيار التاكل (icorr) بزيادة تراكيز المحاليل الملحية في الوسط الحامضي (pH=2,4) وكانت اعلى قيمة لها = 〖18.62 µA.cm〗^( - 2)عند تركيز 0.6 mol.〖dm〗^( - 3) لمحلول كلوريد الصوديوم. تذبذب قيم جهود التاكل (Ecorr) والتي تعكس امكانية حصول عملية التاكل نتيجة لعدم تجانس مواقع الطاقة الكامنة على سطح السبيكة الفلزية. امكن حساب حركيات التاكل من قيم تيار التاكل واعتمادها على درجات الحرارة المختلفة. وقد خضعت حركيات (Kinetics) تفاعل التاكل بوجود وعدم وجود المثبط لمعادلة ارينيوس والتي تفترض وجود علاقة خطية بين قيم لوغارتم تيار التاكل (log icorr) ومقلوب قيم درجة الحرارة المطلقة (1/(T ) ) والتي منها امكن حساب طاقة التنشيط (E_a) وقيمة مسبوق المقدار الاسي (A) وانتروبي التنشيط (∆S^* ). وجد ان اعلى قيمة لطاقة تنشيط لتفاعل تاكل سبيكة الفولاذ المقاوم للصدا تقع عند (pH=11) واقل تركيز لمحلول كلوريد الصوديوم. ووجد بانها تساوي 39.59 kJ.mol - 1 عند pH=11وتركيز 0.1 〖mol.dm〗^( - 3) لمحلول كلوريد الصوديوم. وهذا يدل على ان عملية التاكل تحصل بشكل اكبر في الوسط الاكثر حامضية. وتبين قيم طاقة التنشيط (E_a) وقيم مسبوق المقدار الاسي (A) بوجود علاقة خطية بين قيم (log A) وقيم طاقة التنشيط (E_a) المناظرة لها ، وتدل هذه العلاقة بان تفاعل التاكل يحدث على مواقع متباينة على سطح السبيكة الفلزية المعرضة للتاكل وان تفاعل التاكل يبدا اولا بالمواقع التي تتمتع بطاقات تنشيط واطئة ثم ينتشر منها الى المواقع التي تتمتع بطاقات تنشيط اعلى. ويفسر هذا وفق عملية (compensation) للسلوك الحركي لتاكل السبيكة الفلزية. امكن دراسة الدينمية الحرارية للتاكل من قيم جهد التاكل ومدى اعتمادية تلك القيم على درجات الحرارة، وتم حساب الكميات الثرموديناميكية لتفاعل التاكل ∆G و∆H و∆S بدرجات حرارية مختلفة.وقد اظهرت الدراسة ان قيم ∆G و∆H و∆S كانت على التوالي مساوية الى 38214kJ.mol - 1 و98816kJ.mol - 1 و6768432kJ.mol - 1 مما يدل على تلقائية تفاعل التاكل وكونه تفاعل باعث للحرارة. ان قيم الفقدان بالوزن تزداد بزيادة درجة الحرارة، وزيادة الحامضية وتركيز المحلول الملحي اي انها تاخذ نفس منحى قيم تيار التاكل. كما اشتملت الدراسة على تاثير العامل المثبط (Adenine) بثلاث تراكيز تراوحت 〖mol.dm〗^( - 3) (10 - 2 - 10 - 3) على سبيكة فولاذ المقاوم للصدا نوع 316L في محلول كلوريد الصوديوم بتركيز 0.6 〖mol.dm〗^( - 3) وعند قيمتي pH=2 وpH=4 وعلى مدى من درجات الحرارة (298 - 308)K.واوضحت الدراسة ان المثبط (Adenine) قام بتثبيط عملية التاكل للسبيكة في الوسط حامضي حيث ازدادت قيم طاقة التنشيط عند وجود (Adenine) اي ان المثبط قام برفع (زيادة) الحاجز الطاقي لتفاعل التاكل حيث ان : Ea=5.90 kJ.mol - 1 بغياب المثبط واصبحتEa=20.5 kJ.mol - 1 بوجود المثبط عند pH=2 ، وعند pH=4 كانت Ea= 6.67 kJ.mol - 1 بغياب المثبط Ea= 18.59 kJ.mol - 1 بوجود المثبط.وكانت كفاءة التثبيط مساوية الى87% كحد اعلى عند تركيز 〖10〗^( - 2 ) 〖mol dm〗^( - 3) لل(Adenine) وقيمة pH=2 ودرجة حرارة 298K.ولم يكن بامكان المثبط (Adenine) ان يعمل في الوسط القاعدي لابطاء التاكل او اعاقته.ان ميكانيكية التثبيط لل (Adenine) في الوسط الحامضي تعتمد على عملية الامتزاز للمثبط على سطح الفلز، ووجد بانها تخضع لمتساوي درجة الحرارة للانكمير .تـم حــــــساب ومناقــــشة المعلمات الثرموديناميكية لعـــــملية الامتزاز(K_(ads.),∆G_(ads.),∆H_(ads.),∆S_ads )وكانت قيم∆G_(ads.) كلها سالبة مما تدل على تلقائية العملية وان قيم k_(ads.) كانت تمتلك قيم اكبر في الوسط الاكثر حامضية مما يؤكد ان عملية التثبيط عن طريق الامتزاز تكون اكبر.تم دراسة وفحص سطح الفلز بعد عملية التثبيط من خلال FTIR والمجهر الالكتروني الماسح (SEM) واتضح بان جزيئات المثبط قد صنعت فلما كطبقة واقية على سطح الفولاذ المقاوم للصدا نوع 316L. | The present work involves the investigation of the polarization behavior of 316L stainless steel corrosion in the presence of (0.1 - 0.6) mol.dm - 3 NaCl solution in four pH values (2,4,9 and 11) and over the temperature range (293 - 308)K .The work was performed using potentiostatic technique with three electrodes cell.The experimental results revealed that : 1. The corrosion current density increases with increasing the acidity and temperature of the corroded medium.It has a maximum value 18.62µA.cm - 2 in pH=2 and temperature=308K.2. The corrosion current density increases with increasing NaCl concentration in acidic medium, it was found to be 18.62µA.cm - 2 in 0.6 mol.dm - 3 NaCl .3. The variation of corrosion potential (Ecorr) reflects the heterogeneous nature of the corrosion process on 316L stainless steel surface.4. Kinetics of 316L stainless steel corrosion have been studied from the values of the corrosion current densities and their dependencies on temperature .The kinetics of 316L stainless steel corrosion followed Arrhenius type rate equation .A linear relationship has been existed between values of log (icorr) and (1/T) .Activation energy (Ea), pre - exponential factor (A) and entropy of activation (∆S*) can be determined. It was found that (Ea) has a higher value at the higher pH value (pH=11) and lower NaCl concentration, It was found to be equal to 39.59kJ.mol - 1 at pH=11 and 0.1mol.dm - 3 NaCl concentration .This indicates that the rate of corrosion process proceeds strongly in more acidic medium.A linear relationship was found for (Ea) which suggests the operation of a compensation effect of the stainless steel corrosion behavior .This may enable us to explain that corrosion reaction proceeds on surface sites which are associated with different energies of activation. The corrosion reaction is assumed to start on sites with lower (Ea) and (logA) values first, there after spreading to those sites on which (Ea) and (logA) are higher.5.The thermodynamic parameters ∆G, ∆S and ∆H were calculated at different NaCl concentrations and temperatures . The values of ∆G, ∆S and ∆H were - 38214 kJ.mol - 1, - 98816 kJ.mol - 1 and - 67684.32 kJ.mol - 1 respectively. These data indicate the spontaneous and exothermic reaction.6. The values of weight loss increase with increasing the temperature, these values agree with (icorr) values. The study involves also the inhibition effect of adenine (as inhibitor) on 316L stainless steel corrosion in acidic NaCl solution. It was studied with three concentration of adenine (10 - 3, 510 - 3 and 10 - 2) mol.dm - 3 in 0.6 mol.dm - 3 NaCl solution in two pH values of 2 and 4 over the temperature range (293 - 308)K. The study indicated that adenine acts as good inhibitor for 316L SS i.e. adenine raises the energy barrier for corrosion process, it was found to have a value of Ea= 20.5 kJ.mol - 1 in the presence of adenine which is clearly higher than in absence of adenine. The inhibitor efficiency was found to have a maximum value of ≈87% in pH=2 and 10 - 2 mol.dm - 3 adenine concentration. Adenine had no ability to inhibit corrosion in basic media. The mechanism of inhibition of adenine in acid medium depends on the adsorption of the inhibitor onto the metal surface and the adsorption was found to obey Langmuir adsorption isotherm. The thermodynamic parameters (Kads ,∆Gads , ∆Hads, and ∆Sads) of adsorption process were calculated and discussed. The values of ∆Gads were negative indicating spontaneous process, and Kads values of the adsorption /desorption process were found to have greater values in solutions of lower pH, i.e. adsorption of inhibitor is greater in more acidic medium.The surface examination studies including FTIR and SEM were done, they showed that the inhibitor molecules form a good protective film onto 316L.SS surface.

دراسة بعض الخواص الفيزيائية والميكانيكية للمتراكبات البوليمرية الجديدة المحضرة من الستايرين بيوتادين == Study of Some Physical and Mechanical Properties of New Polymeric Composition from prepared SBR

اسم المؤلف: حيدر عبد الواحد مهدي
اسم المشرف: عامر موسى جودة الشمري
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
اللغة: العربية
مكان الجامعة: النجف
الصفحات الاولى:
المستخلص: ان الاهمية المتزايدة لاستعمال المتراكبات البوليمرية جاءت نتيجة التطور الصناعي التكنولوجي الكبير الذي يشهده العالم بوصفة بديلا عن المواد الهندسية التقليدية التي ساد استخدامها في الصناعة لذا فان الدراسة الحالية تهدف الى تحضير متراكبات بوليمرية ذات مواصفات ميكانيكية جيدة من مادة الستايرين بيوتاداين مع مالئات من السيليكا والكاولين العراقي بنسب وزنية مختلفة (1%,5.2 %,5%,5.7%,10%,5.12%,15%) ان اضافة السيليكا والكاولين العراقي كان الهدف منة تحسين الخواص الفيزيائية والميكانيكية وكذلك خواص الفلكنة لمطاط الستايرين بيوتاداين اذ تم قياس خواص الشد(الاستطالة ,المرونة) وكذلك الصلابة والكثافة النسبية ومعدل سرعة الفلكنة والاحتكاك الخارجي للاطار. اظهرت النتائج ان جميع الصفات الفيزيائية والميكانيكية وكذلك خواص الفلكنة قد تحسنت بنسب عالية عند زيادة النسب الوزنية للمالئات وان افضل نسبة وزنية لتحسين الخواص هي (5.7%) حيث بلغت قيمة الشد عند هذة النسبة (16.81Mpa) عند اضافة السيليكا و(19.97Mpa)عند اضافة الكاولين بينما كانت (8.69Mpa) بدون اي اضافة, الاستطالة (441%) عند اضافة السيليكا و(417.078%) عند اضافة الكاولين, المرونة ((9.5Mpa عند اضافة السيلكيا و(14.12 Mpa)عند اضافة الكاولين بينما كانت ((7.69 Mpa بدون اي اضافة , الصلابة (68 IRHD) عند اضافة السيليكا و(65 IRHD) عند اضافة الكاولين بينما كانت (57 IRHD) بدون اي اضافة, معدل سرعة الفلكنة (74.07min (للسيليكا و(54.34min) للكاولين , الكثافة النسبية (1.156) عند اضافة السيليكا و(1.183)عند اضافة الكاولين بينما كانت (1.133) بدون اي اضافة اما للاحتكاك الخارجي للاطار (0.18 gm) عند اضافة السيليكا و(0.54 gm) عند اضافة الكاولين بينما كانت (0.75 gm) بدون اي اضافة,اما الجانب الاخر فقد تم دراسة الخواص الفيزيائية والميكانيكة وكذلك خواص الفلكنة ولكن هذة المرة تم مزج نسب وزنية مختلفة من السيليكا والكاولين وبينت نتائج المزج ايضا تحسين الخواص المذكورة اعلاه, | The important increasing for using polymeric composites came from result of industrial large to chronology development which it was seeing in world and sbstitute from traditional engineering materials which used in industry. the present research aim to preparation of new polymeric composites with good mechanical properties to Substance Styrene - Butadiene Rubber (SBR) with filler Silica and Iraqi Kaolin with different perceentage (1%,2.5%, 5%,7.5%, 10%,12.5%,15%).Addition of Silica and Iraqi Kaolin aim to improvement physical and mechanical properties also Cure characteristics to Substance Styrene - Butadiene Rubber (SBR) as it was measured tensile properties (tensile strength, elongation at break and modulus), also Hardness, Specific gravity ,Cure rate index and abrasion. The result had shown all physical and mechanical properties also Cure characteristics by improved high with increase of percentage of filler. The best ratio by weight to improve properties (7.5%). As the value of tensile strength(16.81 Mpa) when addition Silica and (19.97 Mpa) when addition Kaolin While the (8.69 Mpa) with any addition, elongation (441%) when addition Silica and (417.078%) when addition Kaolin, Modulus (9.5 Mpa) when addition Silica and (14.12 Mpa) when addition Kaolin While the (7.69 Mpa) with any addition , hardness (68 IRHD) when addition Silica and (65 IRHD) when addition Kaolin While the (57 IRHD) with any addition, Cure rate index (74.07 mint) when addition Silica and (54.34 mint) when addition Kaolin, specific gravity (1.156) when addition Silica and (1.183) when addition Kaolin While the (1.133) with any addition ,abrasion (0.18 gm) when addition Silica and (0.54 gm) when addition Kaolin While the (0.75 gm) with any additon. On the other hand Study the physical and mechanical properties also cure characteristics but this time was mix different percentage from Silica & Kaolin the results of blending increase properties the above - mentioned.

تحضير مركبات عضوية جديدة ذات صفات بلورية سائلة == Preparing of New Organic Compounds With Liquid Crystalline Properties

اسم المؤلف: محمود عبد الستار يحيى القزاز
اسم المشرف: ابتسام خليفة جاسم
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
الجامعة: جامعة بغداد
اللغة: الانكليزية
مكان الجامعة: بغداد
الصفحات الاولى:
المستخلص: يهدف هذا العمل لدراسة امكانية طلاء سطوح بعض المعادن مثل الفولاذ المقاوم للصدا 316، الحديد الكربوني، النحاس، الالمنيوم والزنك، بالمواد النانوية لتحسين مقاومة التاكل وذلك باستخدام اثنين من التقنيات، الاولى بواسطة الطلاء بالالياف النانوية لمادة متعدد الانيلي | This work aims to study the possibility of coating the surfaces of some metals such as stainless steel 316, carbon steel, copper, aluminum, zinc, with nanomaterials to improve the corrosion resistance using two techniques, first by coating with polyaniline nanofiber using electropolymerization of aniline monomer and the second technique by TiO2 nanoparticles via sol - gel process starting from titanium isopropoxide. The work focused on getting thin and homogeneous layer to cover the entire surface of the metal and protect it from corrosion in artificial seawater solution (3.5% NaCl) at 293, 303, 313, and 323 K.Atomic Force Microscope (AFM), Scanning Electron Microscope (SEM), Energy dispersive x - ray (EDX), x - ray photoelectronic spectroscopy (XPS), and x - ray diffraction (XRD) were used to diagnose and describe the structure and morphology of the layers that cover the surface of the metals under investigation, and finally the corrosion parameters ;corrosion potential (Ecorr), corrosion current (Icorr), protection efficiency (PE%), polarization resistance (Rp) and the effect of temperature on the inhibition efficiency in the absence and presence of polyaniline (PANI) or TiO2 coating at temperature ranging from 293 to 323 K were obtained and expressed as; Ea , ?H*, ?S*, and ?G* of all samples were estimated from Tafel plots using potentiostatic technique.The SEM and AFM images of PANI films reflect nanofibers (diameter from 50 to 70 nm); the thicknesses were measured by special AFM scans. They showed values between )700 to 1564 nm(, which may be attributed to the differences in oxidation - reduction potentials of the metals. The XRD patterns of the deposited PANI showed duplicate broad scattering peaks around 2? of 20? and 25?.The AFM images of TiO2 nanoparticles deposited on specimens revealed that the layer was extremely smooth, the particles are small spherical and the average diameter between 26 and 38 nm.The shifts in Ecorr of the uncoated with comparison of the PANI or TiO2 coated samples were small for; S.S316, C.S, Cu, Al, and Zn which means that the anodic and cathodic reactions affected by the same extent.The Rp of the PANI and TiO2 coated substrate was always more than the uncoated ones that attributed to the weak conductivity of PANI and the semiconducting properties of the Titania. All coated metals with PANI or TiO2 exhibited good degree of corrosion protectiveness. For PANI the PE ranged between 56 and 92 % and the best results was achieved for Zn metal this may attributed to the high corrosion values of the bared Zn, while TiO2 coating showed PE at the range of 68 and 93% and the best was for Al metal. The protection efficiencies showed small changes by increasing the temperature but for TiO2 in some cases the PE somehow increased with increasing the temperature. The data showed that the thermodynamic activation functions (Ea and ?H*) of the corrosion of the coated samples are higher than those of the uncoated ones indicating more energy barrier. The entropy of activation ?S* for the uncoated and coated samples are always negative ,this indicates that the activated complex in the rate determining step represents an association rather than a dissociation step, the measured ?G* values takes positive values and showed almost small change with increasing temperature, indicating that the activated complex was not stable and the probability of its formation decreased somehow with rise in temperature and the ?G* values for coated samples reveal that in the activated corrosion complex becomes less stable as compared to the uncoated specimens.Single cyclic potentiostatic tests conducted at 293 K to follow up the pitting probabilities of each metal in seawater before and after coating. The I - V plots indicated that only SS316 and Aluminium specimens suffer from pitting corrosion and the two types of coating reduces the pitting area of the hysterias loop with pushing the pitting potentials for more positive values

تحضير وتشخيص المركبات الحلقية غير المتجانسة الجديدة والمشتقة من الجالكونات == Synthesis And Characterization of New Heterocyclic Compounds Derived From Chalcones

اسم المؤلف: نبراس مظفر جميل
اسم المشرف: جمبد هرمز توما | ضحى فاروق حسين
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
الجامعة: جامعة بغداد
اللغة: الانكليزية
مكان الجامعة: بغداد
الصفحات الاولى:
المستخلص: يتقصى البحث امكانية الحصول على طبقة طلاء رقيقة ومتجانسة لبوليمر البايرول على بعض السبائك مثل الفولاذ المقاوم للصدا 316 والفولاذ الكربوني بواسطة البلمرة الكهروكيميائية لمونمر البايرول ودراسة امكانية تحسين مقاومة التاكل في مختلف الاوساط البيئية مثل المياه ا | This research focuses on getting thin and homogeneous polypyrrole (PPy) layer on carbon steel (45) and stainless steel (316) alloys by electropolymeriztion procedure of pyrrole monomer, and study the possibility of improving the corrosion resistance in different medias; saline water (3.5% NaCl), acidic media (1M H2SO4) and basic media (1M NaOH) at different temperature of 293, 303, 313 and 323 K. The deposited PPy layer on samples under investigation were examined by Atomic Force Microscope (AFM), Scanning Electron Microscope (SEM), Visible and Ultraviolet Spectroscopy (UV - Vis), Fourier Transform Infrared Spectroscopy (FT - IR), Thermogravimetric Analysis (TGA) and X - Ray Diffraction (XRD).The corrosion parameters are including corrosion potential (Ecorr), corrosion current (icorr), protection efficiency (%PE), polarization resistance (Rp) and the effect of temperature on the inhibition efficiency in the absence and in the presence of PPy coating at temperature ranging from 293 to 323K were obtained and expressed as; Ea, ?H*, ?S*, and ?G* of all samples were estimated from Tafel plots using potentiostatic technique.The SEM and AFM images of PPy films revealed a nanofiber like structure; diameter from 20 to 120 nm, the thicknesses were measured by gravimetric and special AFM scans, they showed values between 1300 to 1450 nm. UV - Vis studies showed that the PPy films exhibit weaker absorption peak at 477 nm and stronger absorption peak at 906 nm and the XRD patterns of the deposited PPy show two peaks around 2? of (43o) and (50o).The shift in Ecorr of the uncoated and of the PPy coated samples are between ( - 600 to - 200 mV) and ( - 200 to 100mV) for CS and SS316 respectively.The protection effectiveness of all PPy coated specimens showed remarkable degree of enhancement, and the %PE ranged between (30 to 80%) for CS and (78 to 96%) for SS316 in all medias.The values of Ea and ?H* of the coated PPy metals are always higher than the uncoated ones which indicate more energy barrier. The negative entropy ?S* for the uncoated and coated samples indicates that the activated complex in the rate determining step represents an association rather than a dissociation step, the measured ?G* values takes positive values and showed almost small change with increasing temperature, indicating that the activated complex was not stable and the probability of its formation decreased somehow with rise in temperature and the ?G* values for coated samples reveal that in the activated corrosion complex becomes less stable as compared to the uncoated specimens.Single cyclic potentiodynamic tests conducted at 293 K to follow up the pitting probabilities of each alloy in all medias before and after coating, the I - V plots indicated that only SS316 in salty media specimens suffer from pitting corrosion and the PPy coating reduces the pitting area of the hysterias loop with pushing the pitting potentials for more positive values

التقدير الطيفي لبعض المركبات العضوية المعوضة والمستحضرات الصيدلانية من خلال الاكسدة بايون السيريوم الرباعي باستخدام المحلل الطيفي الدقيق للتحليل بالحقن الجرياني المستمر (Ayah 3S BGR x3 -3D solar cell) == Spectrophotometric Determination of Some Substituted Organic Compounds And Pharmaceuticals Formulation Via Their Oxidation With Ce(IV) Ion Using Ayah 3SBGRx3 - 3D Solar Cell CFIA Microphotometer

اسم المؤلف: مالك حسين علي العلوش العامري
اسم المشرف: نغم شاكر تركي العوادي
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: دكتوراه
الجامعة: جامعة بغداد
اللغة: الانكليزية
مكان الجامعة: بغداد
الصفحات الاولى:
المستخلص: تم استخدام حسابات ميكانيك الكم التقريبية شبه التجريبية وفق نموذج الحساب PM3)) وحسابات ميكانيك الكم الاساسية التامة غير التقريبية وفق نظرية دوال الكثافة (DFT) وباسلوب B3LYP وعناصر قاعدة 6 - 311G لحساب جزيئة الفلرين التي امتلكت التماثل Ih مع وحدات بناءها (5 | Semi - empirical quantum mechanical methods (PM3) and Density Functional theory calculations (DFT/ B3LYP/ 6 - 311G) were executed to evaluate the fullerene molecule ,the internal coordinates (bond length and angles) and some physical and energetic properties.Calculations of the geometrical Parameters (bond lengths and bond angles), have shown that the (C=C) bond length is increased with increasing the size of the molecule that increased elasticity especially to fullerene to be like a ball. The (C - C) bond length is decreased with increasing the size of molecule, that means fullerene will be more stable than the other molecules.The energetic values (heat of formation) is found to be increased with the increasing of the size of molecule. The total energy is decreased with increasing size of molecule that means the stability will increase with the increasing of the size of unit construction of fullerene molecule , on the other hand , the energetic difference (E HOMO - LUMO) between the higher level of orbital and the lower level of orbital are decreased with the increasing of the size of molecule ' unit construction reaching to the fullerene molecule. So, this property will increase the significance of fullerene in the industrial and the electrical purposes.The vibrational modes frequencies with ( 3N - 6) whereas N is represented by number of molecule atoms which are evaluated with the absorption intensities of infrared frequencies. symmetrical and coordinated modes were discussed at the equilibrium geometric formation by using the programs MOPAC & Gaussian 05.It is worthy to say that it was not mentioned before that the complementary classification for the vibrated motion modes for such molecules , so our evaluations may considered unique. It is noted , as well , that CH stretching frequency has had fluctuations that means increasing and decreasing in the values of frequencies. In connected with the bending vibrated modes which taking place out of plane of the molecule are decreased with the increasing size of the unit constructions of molecule but it is increased only at the fullerene molecule. Conversely, the bending vibrated modes which are taken place in the plane of molecule are increased with the increasing the size of unit construction of molecule but are decreased at the fullerene molecule.The distribution of the electronic charges density on the atoms of unit construction of fullerene molecule were studied, the results shown the absence of the electronic charge on the atoms of Fullerene molecule and its concentrated at atoms of the outer circumferential edges C - Cc for the aromatic rings in its own unit construction. Semi - empirical methods (PM3) and Density Functional theory calculations (DFT/ B3LYP/ 6 - 311G) were carried out to evaluate the vibration frequencies and infra - red (IR) absorption intensities for equilibrium geometries of construction units of (6,0) zigzag (Mono (D6h), Di (D6d), Tri(D6h), Tetra (D6d)) ring layers SWCNTs and the internal coordinates ( bond length & angles ) at the equilibrium geometric formation symmetrically according to group theory were evaluated. The most important notes were axial bond length C - Ca which is decreased with the increasing of the tube length whether odd or even number of ring layers. The length of these mentioned axial bonds will be longer in the outer layers than the middle layers that means the increasing of stability of the tube with its length increasing , with the ability of replacing the external atoms of the tube because they are connected with longer and weaker bonds. The reverse was found with the circumferential bond lengths C - Cc was as they were increased with the increasing length of the tube whether the tube was odd or even in number of ring layers. Moreover , the lengths of these bonds are decreased in the middle side to the outer one for the odd and even ring layers. This will confirm the stability of the tube with its length increasing. The lengths of outer bonds C - H which are situated on the edges of the tube which were approximately fixed , with exception of the bond length of CH bonds in Mono ring layers which were longer because the large negative charge on carbon to which it is bonded and the large positive charge on it compared with the positive charge on hydrogen atoms of the multi - layers tubes. The heat of formation which was found to be increased with the increasing of the length of the tube , that means increasing of the stability and the aromatic properties , with the increasing of number of tube' layers. This property will increase the importance in the uses of these tubes for the industrial and electrical purposes as semi - conductors.The vibrational modes frequencies with 3N - 6 with the absorption intensities of infrared frequencies were evaluated and classified. These modes were discussed in symmetrical and coordinating manners at the equilibrium geometric formation, by using the programs of MOPAC and Gaussian 05 , with confirming on unavailability of bounded specification for such modes with 3N - 6 in the literature. We have a through our studies that the stretching vibration modes of symmetric and anti - symmetric Carbon - Carbon axial bond (C - Ca) increased with the increasing length of tube , and this will increase the physical properties for electrical conductivity with confirming on the significance of nanotube industrially. For the vibrational bending frequencies which are taking place in plane and out of plane of molecule surface as well as the vibrational stretching for odd number of ring layers (Mono and Tri) fluctuation will be happening in the relations , as all of them will be decreased with the increasing of tube ' length except (C - Caasym, C - Casym , ? CHsciss. , ? ringasym , ? ringsym and ? ringsym ) which be increased with the increasing the length of tube. The vibrational bending frequencies which are taking place in plane and out of plane of molecule surface for the even number of ring layers ( Di and Tetra layers ) will be decreased with the increasing of tube' length except (? CHsciss.) which is increased with the increasing of tube' length. Furthermore , all vibrational modes which are related to the puckering , breathing and bending movements of clockwise and anti - clockwise according to "group theory" were determined in accurate manner to which deformations are related , which are happened in the tubes , as a result of vibration, that may prevent the flow of electrons' movements and their transitions. The numerical values for the vibrational frequencies which are resulted from Semi - empirical methods (PM3) were acceptable in comparing with the strict calculations , hopping to achieve best values and to be close to the values obtained for the strict calculations (DFT) method to be suited with the basis and standards that are depended internationally. Some of these values were corrected by multiplied by constant scaling factors for such molecules. The results of scaling were good and very close to the experimental and calculated values.The distribution of charges' density on units of construction atoms of (6,0) zigzag nanotube SWCNTs also were studied. The results were consistent with the physical and experimental conductivity properties for such calculated tubes , as the intensity of the electronic charge was concentrated on the outer circumferential edges of atoms C - Cc for the aromatic molecules as well as for nanotubes with its disappearing form outer side towards the middle side of multi - ring layers ( Mono , Di , Tri and Tetra ).

تحضير وتشخيص الدقائق النانوية لاوكسيد النحاسوز بواسطة الكتروليتات مختلفة == Preparation And Characterization of Cuprous Oxide Nanoparticles By Different Electrolytic Media

اسم المؤلف: حيدر خضير خطار
اسم المشرف: فؤاد عبد الامير السعدي | سامي وحيد راضي الحسناوي
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
اللغة: الانكليزية
مكان الجامعة: النجف
الصفحات الاولى:
المستخلص: في الواقع، لم تلقي عملية فصل واستخلاص الكميات الضئيلة من الادوية في العينات الحيوية وكذلك في المستحضرات الصيدلانية اهتماما واسعا وكبيرا باستعمال مايسمى الاستخلاص بنقطة الغيمة. وفي هذا الصدد، نعتقد ان العمل البحثي الحالي سوف يسهم في فتح افاق جديدة في تصم | The separation and extraction of trace amounts of medicaments in biological specimens, as well as in pharmaceutical formulations have not received much attention by using the so - called cloud - point extraction (CPE). In this context, we think that the present research work will contribute to opening new prospects in designing procedural steps and expands the applications of the cloud point extraction methodology in most important areas, including pharmaceutical sciences, forensic and environmental analyses. The present work concentrates on the developing of new eco - friendly procedures for determination of two selected antibiotic medicaments namely cirprofloxacin chloride (CIPRO) and norfloxacin (NOR) using iron (III) ion in human serums and pharmaceutical formulations, as well as the exploitation of these two drugs in chemical analysis as chelating agents for the detection of iron in pharmaceutical formulations via using cloud point extraction coupled with molecular spectrophometry. Generally, these methods implicate the use of a nonionic surfactant (Triton X - 114) as an extracting medium which entrap the hydrophobic colored complex formed between one of these drugs and iron (III) ion in acidic medium as a reaction system for designing the CPE procedures.This thesis includes three main chapters as follows;Chapter One summarizes some theoretical and practical principles of cloud point extraction (CPE) methods and then highlights the knowledge of the target analytes (CIPRO, NOR and iron) in term of their structures, pharmacological importance besides a concise chemical literature review for the estimation of these analytes by different analytical techniques. Chapter Two consists of an outline of instrumental techniques , general apparatus and chemicals used in the present work. The full analytical procedures for CPE which have been designed for the determination of the target analytes under study are made in this thesis.Chapter Three covers a detailed study for the discussion of the analytical data obtained throughout this work which can be summed up as follows;A. Formation of chelates between CIPRO or NOR and Fe(III) in acidic medium , where the drugs have individually been estimated in the resulting complex by spectrophotometry after the cloud point extraction at each respective ?max, and the use of developed method so that to determine any of the interested drug in human serum and pharmaceuticals. At first, the study was conducted to pinpoint the optimum conditions for the formation of complexes by CPE and the results were as follows; 1. The optimum experimental conditions for Fe - CIPRO and Fe - NOR complex for the determination of CIPRO and NOR respectively : H2SO4 concentration (5x10 - 4 M and 2.5x10 - 4M; Fe(III) concentration ( 6 ?g mL - 1 and 10 ?g mL - 1); Triton X - 114 amount ( 1%) for both drugs; temperature and time ( 75 °C at 25 min and 65 °C at 20 min).2. The achieved analytical figures of merit on applying the developed methods for CIPRO and NOR are : linear range (2.5 - 120 ?g mL - 1 ) for drugs, limit of detection (0.770 and 0.204 ?g mL - 1), Enrichment factor (143 and 280 fold), extraction efficiency (96.46 and 96.62%) and mean recovery percentage (98.89±0.87% and 98.95±1.09). 3. The newly established procedures have been applied for the determination of CIPRO and NOR in human blood serum and pharmaceuticals. For the determination of these medicaments in serum samples , the statistical paired t - test was used to test the significance of the proposed method comparing with the conventional UV - spectrophotometry, while in pharmaceuticals, the findings were compared statistically with quoted values that stated by the manufactures. B. Iron (III) ion was also determined in the pharmaceutical formulations based on the above reaction system in (A) via formation of yellow colored complexes with each medicament which extracted by micelles generated by CPE and subsequently detected spectrophotometrically at the same ?max of the above mentioned complexes. The optimum established conditions and the analytical data obtained could be summarized as follows : 1. The same optimum conditions were used in (A) except that the concentration of CIPRO or NOR here was of 7x10 - 5 M and Triton X - 114 amount of 0.6% in final solutions.2. The analytical figures of merit obtained on applying the developed methods for iron using CIPRO and NOR respectively; linear range (5 - 150 ng mL - 1); limit of detection (2.67 and 3.42 ng mL - 1); preconcentration factor (71 and 83 fold); mean recovery percentage (99.78±0.53% and 98.77±2.29); extraction efficiency (99 and 98.7%). 3. The effect of some additives of the pharmaceutical formulations was also studied and the iron determined in three selected formulations collected from local drugstores. The results were compared statistically with quoted values and shown not to be significant at 95% confidence level.

دراسة التاكل والحماية من التاكل لسبائك من حديد الفولاذ في ماء البحر باستخدام دقائق اوكسيد الزركونيوم وكربيد السليكون واوكسيد الالمنيوم النانوية == Corrosion And Corrosion Protection Studies of Carbon Steel Alloy In Seawater Using; Zirconia, Silicon Carbide And Alumina Nanoparticles

اسم المؤلف: حيدر عبد الكريم يوسف
اسم المشرف: خلود عبد صالح السعدي
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
الجامعة: جامعة بغداد
اللغة: الانكليزية
مكان الجامعة: بغداد
الصفحات الاولى:
المستخلص: يعتبر اوكسيد النحاسوز واحدا من المواد ذات الاستخدامات العلمية المتعددة الاغراض وذات الاهمية الصناعية الكبيرة ,ومنها استخدامه كمتحسس للغازات وفي العوامل المساعدة وكذلك في انتاج الواح الطاقة الشمسية ويدخل وبصورة كبيرة كمحطم للصبغات العضوية في مجال الكيمياء | Cuprous oxide (Cu2O) has been extensively studied because of its potential use in several electronic applications, which include solar cells and gas sensors. This Thesis is devoted to the synthesis, characterization of nano - structured cuprous oxide by using a simple electrochemical cell with a potassium chloride solution as an electrolyte, the electro cell contains a two high purity copper electrodes as a sheet form in different areas at varying sizes the area of the cathode was twice of the area of anode , the two electrodes zone were separated using a fine diameter silica diaphragm,Within this broad scope , the Thesis focuses on : • Production of different shape nano - crystals (Cu2O) and investigation of the correlation between experimental parameters and resulting microstructure.• Production of highly purity nano - crystalline Cu2O powder, with the estimation it’s by the available investigation instruments.• Study the different parameters, current density, bath temperature, KCl concentration , types of additives , time of precipitation, and there’s effects on the shape ,quantity ,surface roughness, powder color, on the Cu2O powder. Models have been proposed for the nano - crystal formation validated by several techniques uses such as X - ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM), and Fourier Transform Infra - Red spectroscopy (FTIR). The produced nanocrystals show good crystallinity with Cu2O purity and Copper oxide semiconductor nanoparticles were prepared by electrochemistry using galvanostatic and potentiostatic approaches. The optimum deposition conditions ( electrolyte composition , medium pH , type of additives, electrodes area ,current density , temperature of the electrolyte and applied potential of the cell) , to prepare the Cu2O nano particles have been identified; in particular the conditions that allow getting this product by using KCl ,(PVA ,SDS ,and glycerin as emulsifying agent) have been well identified for the first time. The configuration of deposited Cu2O , purity and amounts. These values depend on the electro deposition conditions such as the pH of the solution, the deposition potential and temperature. Where the study results showed that there is direct effect of these factors, it has been observed that the sizes of the precipitate crystalline decreased with increasing current density and especially at high bath temperatures its ranged about 10 - 20 nm , in addition to the effect of the percentage of additives emulsifier agents the best results at poly vinyl alcohol.. The X - ray diffraction pattern and 2? values reflect that the high purity of the deposit where obtained, without any of the other undesirable products like CuO, CuCl2 and CuCl. Also the FTIR analysis was considered. the effect of additives of the type of emulsifier on the crystalline form of the deposit, the PVA produced of the Star (Branches) crystals shape, the addition of the SDS compound leads to the form of the cubic , and the glycerin product the binary pyramid crystals shape.. Finally the conditions effect on the surface roughness of the precipitated powder also discussed. Depending of the electro - deposition conditions, different surface morphologies with various preferential crystal orientations were obtained for the temperatures of the electro - deposition of 80 °C , pH = 8 - 9 , The influence of several deposition parameters of the Cu2O, such as applied potential, pH, the temperature of the bath , the chemical composition, grain size and orientation parameters of the sample was systematically studied using X - Ray Diffraction , Atomic Force Microscopy, Transmission Electron Microscopy ,Fourier Transmission Infra - Red, and scanning electron microscopy.

تحضير وتشخيص وتقييم انواع جديدة من البولي يورثان القابلة للتفكك الاحيائي ودراسة تطبيقاتها الحيوية في اطلاق الدواء == Preparation , Identification And Evaluation of New Types of Biodegradable Polyurethane And Study Their Application In Drug Delivery

اسم المؤلف: صابرين فرحان جواد
اسم المشرف: محمد علي مطر
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
اللغة: الانكليزية
مكان الجامعة: القادسية
الصفحات الاولى:
المستخلص: Corrosion and corrosion protection of carbon steel (C.S) alloy in seawater (3.5% NaCl) was achieved in this thesis. Three types of nanoparticles (NPs) were used to protect C.S the first silicon carbide (SiC), second alumina (Al2O3) and the third zirconium oxide (ZrO2) nanoparticles (NPs). Electrophoretic deposition (EPD) technique was applied to coating the C.S surface. Different polyacrylic acid (PAA) percentage (0.1 - 1)% were added to the suspension solution of coating by the three types of NPs, to improve the protection efficiency (PE%) for the coated C.S surfaces.The corrosion rate with respect to uncoated and coated C.S with the three above NPs were measured. Different corrosion parameters were obtained; corrosion current density (icorr), corrosion potential (Ecorr), cathodic and anodic Tafel slopes (bc,ba), protection efficiency (PE%), polarization resistance (Rp) and the surface porosity (P%). The effect of temperatures (298 - 328)K on the corrosion of uncoated and coated C.S by the three NPs in presence and absence of PAA were also investigated and therefore activation energy (Ea) and preexponential factor (A) were calculated. Thermodynamic parameters ?G, ?H and ?S for all corrosion processes were obtained. Coated C.S were analysed using atomic force microscopy (AFM) to detect the morphology of surface and the particles size of coat layers which range from 60 - 103 nm, which greater than thestarting particles.The corrosion current densities (icorr) were increased generally with increasing temperatures for all cases and icorr reduced after coated C.S by different NPs in absence and presence PAA, therefore icorr reduced from 168.88 ?A.cm - 2 to 19.45, 28.71 and 30.2 ?A.cm - 2 for C.S coated by SiC, ZrO2 and Al2O3 respectively at 298K.While the Ecorr shifted to more active potential after coated by different NPs excepting when C.S coated by SiC in presence of (0.25%) PAA in coating solution suspension where Ecorr shifted to noble direction. The protection efficiency (PE%) of all coated C.S in absence and presence of PAA showed noteworthy degree of enhancement and the PE% ranged between (85 to 99.65)% for SiC , (69 to 91)% for ZrO2 and (77 to 87.9)% for Al2O3. The surface porosity (P%) were increased with increasing temperatures for all cases. The activation energy (Ea) values for the corrosion of coated C.S by different NPs lead to higher values than Ea for uncoated C.S and the highest value was (71.936) kJ.mol - 1 obtained when C.S coated by SiC in presence of (0.25%) PAA. The free energy (?G) Values for the corrosion of coated C.S generally more negatively than uncoated and the values of enthalpy (?H) for the corrosion of coated C.S by ZrO2 and Al2O3 were less negatively than uncoated C.S while coated C.S by SiC lead to more negatively ?H values.

دراسة ارتباط بعض العناصر مع حامض الاسكوربيك باستخدام البولاروغرافي النبضي التفاضلي == Studies of the Binding between Elements and Ascorbic Acid Using Differential Pulse Polarography

اسم المؤلف: محمد عبد الخالق حسين
اسم المشرف: الهام مجيد الرفيعي
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
الجامعة: جامعة بغداد
اللغة: الانكليزية
مكان الجامعة: بغداد
الصفحات الاولى:

دراسات طيفية وفيزياوية لمعقدات انتقال - الشحنة لبعض مركبات الامين والكاربونيل الاروماتية ومشتقاتها == Spectral and physical Studies of Charge Transfer Complexes of Some Aromatic Amine and Carbonyl Compounds and Their Derivatives

اسم المؤلف: محمد محمود مسعود الصالحي
اسم المشرف: انور ذيب محمود الذيب
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
الجامعة: جامعة بغداد
اللغة: العربية
مكان الجامعة: بغداد
الصفحات الاولى:

دراسة الاستقرارية الضوئية لبوليمر كلوريد الفينيل بوجود بعض مركبات قواعد شيف == Photostabilization Studies Of Poly(Vinyl Chloride)Polymer In Presence Of Some Schiff’s Bases Compounds

اسم المؤلف: زينب علاء حسين
اسم المشرف: علي سلمان الطائي | عماد عبد الحسين يوسف
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: ماجستير
اللغة: الانكليزية
مكان الجامعة: بغداد
الصفحات الاولى:

تحضير وتشخيص والخواص الامتزازية لمواد ذات اساس سيليكوني == Synthesis, Characterization And Adsorptive Properties Of Silicone Based Materials

اسم المؤلف: انعام حسين علي محمد الموسوي
اسم المشرف: سمير حكيم كريم | مؤيد كاصد جلهوم
الموضوع العام: علوم الكيمياء
السنة: 2014
الموضوع الدقيق: الكيمياء الفيزيائية
الدرجة: دكتوراه
اللغة: الانكليزية
مكان الجامعة: بغداد
الصفحات الاولى: