• Journal of the Korean Applied Science and Technology
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• v.19 no.4
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• pp.339-348
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• 2002

Self-diffusion coefficients of colloidal ass9Ciation structures in the aqueous solutions of anionic ammonium dodecyl sulfate (ADS) and cationic octadecyltrimethylammonium chloride (OTAC) surfactants were measured by pulsed-gradient spin echo NMR. The results were interpreted on the basis of the ADS/OTAC/water phase diagram. Crossing the phase boundaries, significant changes in self diffusion coefficients were observed and well correlated to the phase diagram. For the micelles their apparent radii were obtained from Stokes-Einstein equation. Their values were 15 for the ADS micelles and 54 ${{\AA}}$ for the OTAC micelles, respectively. For vesicles which were formed spontaneously at different relative amounts of the surfactants and total surfactant concentrations, the radius was measured as 50 to 200 nm. This result is in fair agreement with those by TEM and light scattering.

• Macromolecular Research
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• v.11 no.6
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• pp.444-450
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• 2003

Hydrophobically End-capped polyethylene oxide Urethane Resin(HEUR)-associating polymers, HEUR 35(8), HEUR 35(12), and HEUR 35(18), comprise a polyethylene oxide (PEO) having a molecular weight of 35,000 that is end capped with two C$\_$8/H$\_$17/, C$\_$12/H$\_$25/, and C$\_$18/H$\_$37/ alkyl chains, respectively. These associating polymers were synthesized by condensation reactions with polyethylene oxides and alkyl isocyanates. The self-diffusion coefficients of HEUR-associating polymers were measured in aqueous solution by pulsed-gradient spin-echo (PGSE) nuclear magnetic resonance (NMR) spectroscopy. All polymers underwent a decrease in their mean diffusion coefficients as the concentration was increased. However, the dispersion of the diffusion coefficients, ${\beta}$, about the mean fluctuated with changes in concentration. The large dispersion at low concentrations of HEUR 35(8) and HEUR 35(12) is related to the interaction between hydrophobic end groups, and the large dispersion at high concentrations of HEUR 35(18) is correlated with transient network formation. These results are valuable for predicting the associating mechanism of the large aggregates before and after their critical micelle concentration.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1970-1974
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• 2011

The effects of convection on the measurement of the diffusion coefficients of liquids by the pulsed gradient spin echo (PGSE) NMR method at low temperature are discussed. To examine the generation of convective flows, we used four different types of sample tubes in the diffusion measurements with temperature variation; a normal 5 mm NMR tube, a Shigemi tube, an ELISE type tube, and a capillary tube. Below room temperature, the calculated diffusion coefficients of chloroform in 5 mm o.d. type tubes increased with decreasing temperature, while those in the capillary tube decreased linearly. The convective flow was found to be significant even at low temperature and it seemed to be mainly induced by the transverse temperature gradient. It was also found that the capillary tube was most appropriate to measure the diffusion coefficients, since its small diameter is effective in suppressing the convective flows at both high and low temperatures.

• Bulletin of the Korean Chemical Society
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• v.25 no.3
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• pp.382-388
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• 2004

The sizes and structures of micelles formed in aqueous solutions of cationic octadecyl trimethyl ammonium chloride (OTAC) and anionic ammonium dodecyl sulfate (ADS) surfactants were investigated using smallangle neutron scattering (SANS), self-diffusion coefficients by pulsed-gradient spin-echo (PGSE) NMR, and dynamic light scattering (DLS) methods. SANS and DLS data indicate that their structures are spherical at concentrations as high as 300 mM. As the total surfactant concentration increases, the peaks of SANS spectra shift to higher scattering vector and become sharper, indicating that the intermicellar distance decreases and its distribution becomes narrower. This is due to more compact packing of surfactant molecules at high concentrations. The intermicellar distance of around 100 ${\AA}$ above 200 mM corresponds approximately to the diameter of one micelle. The sizes of spherical micelles are 61 ${\AA}$ and 41 ${\AA}$ for 9 mM OTAC and 10 mM ADS, respectively. Also the self-diffusion coefficients by PGSE-NMR yield the apparent sizes 96 ${\AA}$ and 31 ${\AA}$ for micelles of 1 mM OTAC and 10 mM ADS, respectively. For ADS solutions of high concentrations (100-300 mM), DLS data show that the micelle size remains constant at $25{\pm}2{\AA}$. This indicates that the transition in micellar shape does not take place up to 300 mM, which is consistent with the SANS results.

• Journal of the Korean Applied Science and Technology
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• v.16 no.1
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• pp.1-14
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• 1999

계면활성제는 수용액에서 미셀을 형성함에 있어서 자기확산이 분자 운동과 상변화에 대하여 자세한 정보를 제공하고 공업적으로 응용할 수 있는 기술이 점차 증가하고 있다. 계면활성제가 미셀을 형성함에 있어 자기확산 정도는 화학구조의 변화성과 상호 결합 및 회합현상에 매우 민감한 것은 사실이다. 특히 계면활성제 용액의 넓은 범위의 분자 시스템과 콜로이드 상태의 변화성은 다향한 물리, 화학적 성질에 기여됨이 많다. 더욱이 미셀 형성에서 자기확산 계수는 분자 치환에 직간접적으로 상호관계가 있어 NMR 분광학에서 스핀 이완속도의 해석과 분자의 재배열, 스핀 이완에 대한 모델선정 등에 많은 관심을 갖는다. 그중 미셀형성에 있어서 자기확산에 대한 측정 방법중 가장 많이 이용되고 있는 Fourier Transform Pulsed Gradient Spin Echo(FT-PGSE) 측정법은 계면활성제의 미셀형성에 대한 상변화성 및 물리, 화학적 성질을 다루는데 새로운 도구로 제공되고 있다. 이는 이 계통의 기술적 측정방법에 있어서 적절한 개선과 새로운 응용분야를 확장하는데 있어서 많은 가능성을 갖고있다. 그리하여 이들에 대한 역사적 배경과 기초적인 이론을 가지고 미셀 형성에 있어 자기확산에 대한 개념을 말하고 그에 대한 응용성을 계통적으로 설명하고자 한다.

• Applied Chemistry for Engineering
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• v.10 no.6
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• pp.876-880
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• 1999

The surfactant self-diffusion coefficients of mixed micellar solutions of ionic and nonionic surfactants have been measured by the NMR pulsed field gradient spin echo(FT-PGSE) method. In addition, the line widths of $^1H$ NMR signal have been monitored. The system investgated are $C_{12}EO_5/SDS/D_2O$, $C_{12}EO_5/DTAC/D_2O$, and $C_{12}EO_8/SDS/D_2O$. In the sample series, the molar ratios of $D_2O$ to surfactant(ionic+nonionic) were kept constant while the surfactant mixing ratio was varied. For the $C_{12}EO_5$ system, the surfactant self-diffusion coefficient indicates minimum when the surfactant mixing ratio is about 20% ionic surfactant. The observed decrease in self-diffusion coefficients as nonionic surfactant was replaced by ionic surfactant is interpreted to mainly be due to an increased micelle-micelle repulsion. The increase in self-diffusion coefficients occurring at higher fraction of ionic surfactant is shown to be due to a decrease in micelle size. For the $C_{12}EO_8$ system, the effect of the surfactant mixing ratio is much weaker which can be understood by considering the molecular geometry and large headgroup area. The proton NMR line widths correlate well with the self-diffusion coefficients and broadening of the alkyl chain methylene signals is found when the self-diffusion coefficients is low.

• Applied Chemistry for Engineering
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• v.9 no.6
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• pp.822-828
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• 1998

Binary system of water and polyoxyethylene dodecyl ether, $C_{12}H_{25}(OCH_2CH_2)nOH$, have been studied by $^1H$ NMR techniques. For n=5($C_{12}EO_5$) and n=8($C_{12}EO_8$), the self-diffusion coefficients of nonionic surfactants in the isotropic phase($L_1$) have been measured by using pulsed field gradient technique for a range of temperature and concentrations. In addition the line widths of the different proton signals have been monitored, and samples of some liquid crystalline characteristic were also studied. Dramatic Broadening of the methylene signals of the alkyl($C_{12}H_{25}$) chain is observed as the hexagonal liquid crystalline phase is approached in the $C_{12}EO_5-$water system, while only small broadening is observed in the $C_{12}EO_8-$water system. It was shown that there was a growth of $C_{12}EO_5$ micelles to rods with increasing concentrations, while the $C_{12}EO_8-$ micelles at low temperature remain small in the concentration range. The self-diffusion coefficients of the surfactants decrease rapidly with increasing concentration until a minimum is reached after which there is slow increase. The location of the minimum point occurs at lower concentrations the temperature is close to the cloud point, where the system separate into two isotropic phase. In the line width studies, broadening is found at a certain temperature interval when the concentration is increased in the $C_{12}EO_5$ system. The results indicate that the surfactant aggregates grow in size at the cloud point is approached. The aggregates seem to be flexible and probably not to be of a definite shape close to the cloud point. In the $C_{12}EO_8$ system, the micelles are much less affected by an increase in temperature and micellar growth can't be unambiguously established. The methylene signals of the ethylene oxide moieties consistantly show narrower $^1H$ signals, showing that in the aggregates they are less ordered than the chain methylenes. The various changes in aggregate size and shape are correlated with the stability ranges of the isotropic and liquid crystalline phases according to phase diagrams from the literature. Both aggregate size and phase structure are in qualitative agreement with concentration based on the effective shape of the molecules at different temperature and concentration.