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Associative and Surface Active Properties of Block Copolymers and Their Interactions With Surfactants

Thesis Info

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Author

Khan, Abbas

Program

PhD

Institute

Quaid-I-Azam University

City

Islamabad

Province

Islamabad.

Country

Pakistan

Thesis Completing Year

2010

Thesis Completion Status

Completed

Subject

Chemistry

Language

English

Link

http://prr.hec.gov.pk/jspui/handle/123456789/1525

Added

2021-02-17 19:49:13

Modified

2024-03-24 20:25:49

ARI ID

1676725559399

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The associative, micellar and surface active properties of various EmBn, EmBnEm and of some tip-modified, oxyethylene-oxybutylene block copolymers in aqueous media under varying solution conditions and their interactions with conventional surfactants are reported in this thesis. The tipped block copolymers (Me2N(CH2)2OEmBn denoted as DEmBn and I-Me3N+(CH2)2OEmBn denoted as TEmBn) have dimethylamino and trimethylammonium groups at the end of their hydrophilic blocks respectively. For all copolymers, E represents an oxyethylene (-[CH2CH2O]-) unit and B an oxybutylene (-[CH(C2H5)CH2O]-) unit while the subscripts denote the number average block length. This work is mainly divided in two parts; the first part is related to the associative/micellar, thermodynamic and surface active/adsorptive properties of various E/B block copolymers in aqueous and salt added solutions at various temperatures. While in the second part, the interactions of these polymers with conventional surfactants (anionic, cationic and non-ionic) have been reported. The first part of this study is based on applying some fundamental techniques like surface tensiometry, viscometry, densimetry along with some advance techniques such as laser light scattering (DLS and SLS), mT-jump stopped flow technique and quartz crystal microbalance with dissipation (QCM-D). Surface tension measurements were used to estimate various fundamental parameters such as, surface excess concentrations (Γm), area per molecule (as1) at air/water interface, critical micelle concentration (CMC) and various thermodynamic parameters like; standard Gibbs free energy change (DG0), standard enthalpy change (DH0) and standard entropy change (DS0) for both adsorption at air/water interface and micellization at several temperatures. Density and viscosity measurements were implied to investigate the effect of various internal as well as external parameters on the micellar/associative properties for the aqueous solution of E/B block copolymers. To calculate the intrinsic viscosities [h] and inter-micellar interaction parameter (KH), viscosity measurements were made. Partial specific volume (n mic) and density of the micelle (ρmic) were obtained from the density measurements at various temperatures. Besides that the hydration value (Wh) of micelle plus shape factor (υ) of aggregates were evaluated by combining the results of density and viscosity. Viscosities and densities data also support the temperature dependent micellization/aggregation and change in the shape of aggregates with temperature. Dynamic light scattering was used to investigate the hydrodynamic radius of micelle (rh), hydrodynamic volume (Vh) and hydrodynamic expansion factor (dh). Likewise static laser light scattering technique was used to determine apparent micellar molar mass (Mw), association number (Nw), thermodynamic volume (Vt), thermodynamic radius (rt) and thermodynamic expansion factor (dt). The effect of E/B- blocks length, variation in the hydrophilic end group, addition of NaCl and changing the solution temperature on various parameters deduced from light scattering (DLS and SLS) are also discussed in detail. The kinetics of micellar aggregation was also studied by using mT-jump stopped-flow technique in the temperature range 20 to 50oC. Most of the temperature jump stopped-flow kinetics results show that mainly three relaxation processes are involved in our micellar dynamic system. The first one (τ1) involves the growth of small micelle and increase in aggregation number within short time upon jumping to higher temperature. The second relaxation process (τ2) is associated with micelle formation/breakup and rearrangement, resulting in micelle with larger aggregation numbers and hence lower number density of micelles. The final process (τ3) is related to further rearrangement of the micelle size, shape etc and also to the clustering of micelle. Similarly, the adsorption of poly(ethylene oxide)-b-poly(butylene oxide) diblock copolymers at the solid-liquid interface was studied using a quartz crystal microbalance with dissipation monitoring (QCM-D). The effect of modifying the end- group of the hydrophilic block was investigated by comparing the behavior of TEmBn and DEmBn respectively. For EmBn block copolymer, the effect of E/B block ratio and nature of the substrate (gold-coated and silica-coated surfaces) was also investigated. In the second part, we have discussed the interactions of some EmBn and tip-modified TEmBn and DEmBn block copolymers with conventional surfactants (anionic, cationic and nonionic surfactants). In this work we have tried to highlight the type and strength of such interactions by using the some of the experimental techniques such as surface tensiometry, conductometry, LLS and quartz crystal microbalence. Surface tension and conductivity measurements of the copolymer-surfactant mixture were used to estimate the critical aggregation concentration (CAC) and the polymer saturation point (PSP). DLS has been used to estimate the size and types of the mixed aggregates present in the mixed system. We have studied the effect of polymers block length, end group, nature of surfactants, and also the impact of adding NaCl. To know the influence of the nature and size head group of surfactant we have used anionic (SDS), cationic (CTAB) and non-ionic (TX-100) surfactants for our system. DLS results show that there are different types of mixed species depending upon the amount of surfactant added to the copolymers solution. Quartz crystal microbalance with dissipation monitoring (QCM-D) has also been used to study the adsorption and interaction behaviour of block copolymers- surfactants complexes at the solid-liquid interface. Changes in adsorption/desorption phenomenon and conformational behaviour of block copolymers in presence of SDS and CTAB are discussed in detail. The changes in frequency and dissipation responses indicate that different copolymer-surfactant mixed structures depend on the amount of added surfactants to the mixed system.
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مولانا عبدالرزاق ملیح آبادی

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مرحوم اردو اورعربی دونوں زبانوں کے نامور ادیب، صحافی اورانشاء پرداز تھے۔عربی کی تعلیم مصر میں پائی تھی اورسید رشید رضا مرحوم جواپنے عہد کے اکابر علماء اورمحققین اورمصنفین میں سے تھے ان کے تلمیذ رشید تھے، اس لیے مرحوم عربی زبان بالکل مادری زبان کی طرح بولتے اورلکھتے تھے۔ مصر سے واپس آکر کلکتہ سے عربی کاایک جریدہ’’الجامعہ‘‘کے نام سے نکالا جو عربی کے اساتذہ اورطلباء میں بڑا مقبول ہوالیکن یہاں مولانا ابوالکلام کے دامان دولت سے وابستہ ہونے کے بعد انھوں نے اردواخبار نویسی کواپنا مستقل نصب العین زندگی بنا لیا اور بڑی محنت کاوش اورمشق ومزاولت کے بعد اس میں بھی اپنا خاص ایک ایسا اسلوب پیدا کیا کہ اردو زبان کے بھی صاحب طرزادیب بن گئے۔ اُن کی تحریر صاف سپاٹ،بہت سلیس وعام فہم مگرساتھ ہی ولولہ انگیز اور پُرجوش ہوتی تھی۔اس سلسلہ میں وہ اوّلاً ’الہلال‘ اور’البلاغ‘ کی ادارت میں مولانا ابوالکلام کے رفیق رہے اور پھر کلکتہ سے ہی متعدد اخبار خوداپنے نکالے، تقسیم کے بعدا پنا اخبار روزانہ ’آزاد ہند‘ اپنے لایق فرزند احمد سعید صاحب ملیح آبادی کے حوالہ کرکے دہلی چلے گئے اور انڈین کونسل فارکلچرل ریلیشنزکے سہ ماہی عربی مجلہ ’ثقافۃ الہند‘ کوبڑی قابلیت سے ایڈٹ کرتے رہے۔ اس کے علاوہ آل انڈیا ریڈیو اسٹیشن دہلی کے عربی پروگرام کے بھی ڈائریکٹر رہے۔ اخبارات و رسائل کی اڈیٹری کے باوجودتصنیف وتالیف اورترجمہ کا مشغلہ بھی رکھتے تھے چنانچہ متعدد کتابیں ترجمہ کیں اور کئی کتابیں تالیف کیں جن میں آخری ضخیم کتاب وہ ہے جومولاناابوالکلام آزاد پرہے اورغیر مطبوعہ ہے۔
ذاتی اخلاق واوصاف کے اعتبار سے مرحوم بڑے باوضع، بامروت،...

Pengaruh Ekspektasi Kinerja Dan Risiko Yang Diterima Terhadap Niat Perilaku Menggunakan Mobile Banking Pada Nasabah Bank Syariah Indonesia Cabang Rantauprapat

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Tunneling or Propping: Evidence from Family Business Groups of Pakistan

Corporate governance has two types of agency issues with respect to ownership and control of firms. The Type I agency issue is related to conflict of interest between shareholders and firm’s managers (i.e., principal-agent conflict); whereas, the Type II agency issue (i.e., principal-principal conflict) is between controlling (majority) shareholders and minority shareholders. The tunneling and propping in business group firms are examples of Type II agency issue. Tunneling is the process of expropriation or transfer of business resources by controlling shareholders from low cash-flow rights (CFR) firms to high CFR firms in a business group. Tunneling is carried out through certain transactions at the cost of minority shareholders in group firms. Whereas, propping is the opposite process through which resources are provided by controlling shareholders to firms under financial distress in a business group. This thesis examines these Type II agency issues between controlling and minority shareholders of firms related to family business groups of Pakistan. A family business group is a combination of two, or more firms under the control of a particular family. In this regard, the study examines whether tunneling, or propping is carried out in family business group firms, how it occurs and what impact it has on minority shareholders of these firms? The thesis has three major parts: first, this study explores regulatory and corporate environments in Pakistan; develops the pyramid ownership structures of family business groups; and examines the cash flow leverage, cash-flow rights and voting (control) rights of ultimate owners in family business group firms. The study finds that corporations in Pakistan have high degree of ownership concentration. Controlling shareholders own about 87% of firms with equal to or greater than 10% shareholding and 60% of firms with equal to or greater than 20% shareholding. Moreover, most of the businesses in Pakistan are controlled by families. In 62% of business group firms, families own about 20% or more top shareholdings. The study also finds considerable difference in voting, and cash-flow rights in family business group firms, which provides incentives for expropriation of resources. Secondly, the thesis focuses on finding the empirical evidence of tunneling, or propping in family business groups firms of Pakistan by taking a sample of 326 non-financial firms listed on Pakistan Stock Exchange (PSX) for the period 2004-17. The study finds that majority or controlling shareholders expropriate minority shareholders by tunneling or transferring resources from group affiliated firms containing low CFR of majority owners. While measuring the sensitivities of firms to the industry earnings shocks through indirect methodology; the empirical results elucidate that about 31% resources are tunneled from low to high CFR group firms. The study further finds that equity held by directors (representing majority shareholders) has negative relationship with earnings of minority shareholders of low CFR group firms. Thirdly, the thesis examines different categories of four thousand five hundred Related Party Transactions (RPTs) taken place among sample firms during the period 2008-2013. Using the direct methodology, the study categorizes, classifies, describes and analyses the RPTs. The study finds that group affiliated firms extensively involve in RPTs as compared to non-group, foreign and state-owned firms. The controlling shareholders significantly use various RPTs for both, tunneling and propping depending upon the characteristics of firms, and corporate governance. Moreover, the study finds that considerable amount of intra-group loans is outstanding on firms’ financial statements. Besides, direct cash payments, cash receipts, assets sales and trade of goods & services have been observed as major RPTs, and sources of Type II agency issues. The study further finds that market assigns lower multiple of reported earnings for the top other receivable balance firms and vice versa. The study finally finds that firms are less likely to reduce their outstanding other receivables balances despite qualified audit opinions and lower returns. Overall, the results show that business interests of dispersed minority shareholders are xi significantly affected by crafty operations of majority shareholders in family business group firms mainly because of pyramid ownership structure and inadequate enforcement mechanism of corporate governance.These findings have certain implications for regulatory institutions, firm management, shareholders, and researchers.