폴리옥시에틸렌(POE) 계열에서 두 번째로 작은 화합물인 양친매 분자 2-(2-hexyloxyethoxy) ethanol (C6E2) 수용액의 밀도를 측정하였다. 밀도 측정은 진통 튜브 밀도계를 이용하여 279.15 K와 282.15 K에서 이루어졌다. 측정된 밀도로부터 2성분 계 C6E2 (1)/H2O (2)의 과잉 부피와 부분 몰 부피를 결정하였다. 과잉 부피는 음의 편차를 나타내었으며, C6E2의 몰 분율 χ ≃ 0.45에서 최소 값을 나타내었다. C6E2 와 물 분자 사이에 끌어당기는 작용이 상대적으로 우월하지만, χ ≃ 0.45 에서 이 작용이 가장 크다는 사실을 말해준다. 2성분 계 C6E2 (1)/H2O (2)에서 부분 몰 부피 V1 는 몰 분율 χ 에 따라서 단조 증가하였으며, V2 는 감소하였다. V1 과 V2 에서 C6E2 분자들의 회합을 암시하는 특이점은 관찰되지 않았다.
Garment skin leather 표면 코팅에 사용된 폴리우레탄 수지는 polyethylene glycole(PEG)의 함유를 [NCO]/[OH] mole % 비로 달리하면서 합성하였으며, 합성된 폴리우레탄 수지의 기계적 특성은 SEM, FT-IR, UTM 등을 이용하여 측정하였다. 비이온성을 띄고 있는 PEG(poly ethylene glycol)의 [NCO]/[OH] mole % 비가 증가함에 따라 내굴곡성(건식, 습식)의 변화는 없었으며, 내마모도, 인장강 도수치가 낮아짐을 알 수 있었다. 반대로 연신율 물성은 증가함을 알 수 있었다. 점도 변화 측정 결과에 는 PEG의 [NCO]/[OH] mole % 증가에 따라 점도가 묽어짐을 알 수 있었다.
Detergency and surface active properties of mixed anionic surfactants with amphoteric and nonionic were investigated. Sodium dodecyl sulfate (SDS) and ammonium dodecyl sulfate (ADS) as anionic surfactants and cocamidopropyl betaine (CAPB) as an amphoteric surfactant were used. Nonionic surfactants, which are butyl glucoside (BG), octyl glucoside (OG), decyl glucoside (DG), lauryl dimethylamine oxide (AO) and saponin were also used. To study the synergy effects of mixed SDS/ADS anionic surfactant systems, amphoteric and nonionic surfactants were added into the mixed anionic surfactants. Investigated properties of surfactant mixtures were critical micelle concentration (CMC), surface tension (γ), wettability. In addition, based on these properties, detergency of each sample was examined. Surfactant mixtures are anionics (SDS/ADS), anionic/amphoteric/nonionic (SDS/ADS/CAPB/ saponin), and anionic/nonionic (SDS/ADS/BG/saponin, SDS/ADS/OG/saponin, SDS/ADS/ DG/saponin, and SDS/ADS/AO/saponin). With the addition of amphoteric and nonionic to mixed anionic surfactants, CMC and γ were decreased. Addition of CAPB, which is amphoteric, showed the best property at CMC and γ. Furthermore, as the chain length of hydrocarbon in alkyl glucosides was increased, the CMC and γ were enhanced. However, the wettability did not exactly match up with CMC and γ. The surfactant mixture, which contained DG, showed the best performance at wetting time. Detergency was measured at various temperatures (15 oC, 30 oC, 50 oC). The cleaning performance was enhanced by increasing washing temperature. Moreover, detergency was influenced by not only CMC and γ but also wettability. Although CMC and γ were not minimum at surfactant mixture that included DG, the best cleaning performance showed in that sample.
여러 종류의 양이온성, 비이온성 및 혼합성 계면활성제 수용액에서 4-클로로벤조산의 가용화현상을 UV/Vis 분광광도법을 이용하여 연구하였다. 또한 온도의 변화에 따른 가용화상수값(Ks)의 변화를 측정함으로써 열역학적 함수값들을 계산하고 분석하였다. 그 결과 모든 계면활성제의 용액에서 4-클로로벤조산의 가용화에 대한 △Gos 값은 측정범위 내에서 모두 음의 값을 나타내었으며, △Hos 값과 △Sos 값은 모두 양의 값을 나타내었다. 계면활성제 종류와 계면활성제분자의 알킬-그룹 길이에 따라 Ks값이 큰 폭으로 변하였으며, 그런 결과로부터 4-클로로벤조산이 미셀 내에서 가용화되는 위치와 미셀과의 상호작용의 정도를 예측할 수 있었다.
4-클로로벤조산의 가용화현상을 이용하여 순수양이온성 계면활성제(DTAB, TTAB, CTAB), 비이온성 계면활성제(Tween-20, Tween-40, Tween-80) 및 이들 혼합계면활성제(TTAB/Tween-20, TTAB/Tween-40, TTAB/Tween-80)의 임계미셀농도(CMC)값과 반대이온 결합상수값(B)를 온도 284 K에서 312 K 까지 변화를 주면서 UV/Vis 분광광도법과 전도도법으로 측정하였다. 온도에 따른 CMC와 B값의 변화를 측정하여 미셀화현상에 대한 여러 가지 열역학 함수값(△G˚m, △H˚m, 및 △S˚m)을 계산하고 분석 하였다. 그 결과 측정범위 내에서 △G˚m 값은 모두 음의 값을 나타내었다. 그러나 △H˚m 과 △S˚m값은 계면활성제의 종류와 계면활성제분자에서 탄소사슬의 길이에 따라 양의 값 혹은 음의 값을 나타내었다.
본 연구에서는 계면활성제 분석법의 개발을 위하여 High performance liquid chromatography-evaporative light scattering detection(HPLC-ELSD) 기기를 이용하여 음이온 및 비이온 계면활성제 중 다소비 계면활성제인 Alkyl polyglucoside(APG)와 Alpha olefin sulfonate(AOS)를 분석하였다. 실험 결과 APG와 AOS 모두 직선성의 상관관계 계수(R2)가 0.99 이상으로 직선성이 양호하였으며, 검출한계는 APG가 2.29 mg/L, AOS가 16.55 mg/L로 나타났고, 정량한계는 APG가 7.63 mg/L, AOS가 55.16 mg/L로 나타났다. 또한, 회수율 검증을 실시한 결과 APG는 99.29%, AOS는 96.11%로 나타나 회수율 100±10% 이내의 검증기준을 모두 만족하였다. 정밀성 및 정확성을 판단한 결과 APG의 정밀성은 상대표준편차 0.30%, 정확성은 0.26-0.52%로 분석되었으며, AOS의 정밀성은 상대표준편차 0.10%, 정확성은 0.01-0.52%로 분석되어 모두 상대표준편차 1.0% 이하의 검증기준에 적합하였다. 확립된 분석법을 주방세제에 적용하여 분석한 결과 샘플 3종 모두에서 APG와 AOS가 각각 검출되었으며, 표준사용량을 기준으로 APG, AOS의 평균 함유량은 각각의 LD50에 크게 미치지 못하는 것으로 나타났다. 따라서 본 연구를 통하여 확립된 음이온 및 비이온 계면활성제의 분석법은 모든 성분에 대해 감응함으로 한가지 검출기를 이용하여 여러성분을 동시에 측정할 수 있어 식기 등의 잔류물질 혹은 식품 중 혼입되어 있는 다양한 계면활성제 함유량 분석에 적용하여 계면활성제의 관리를 위한 기초자료로 활용될 것으로 본다.
The transformation of the liquid crystal complex made by binding of anionic surfactant, sodium dodecyl sulfate (SDS), into high charge density cationic polymer, the homopolymer of diallyldimethylammonium chloride (PDADMAC) was induced by adding of nonionic surfactants and investigated by means of microscopy and FE.SEM. Among nonionic surfactants in this experiments polyethylene glycol (3 mol) ether of lauryl alcohol (laureth-3) made variation in the complex. The laureth-3 transformed the complex into spherulite vesicle with the size of ca.100μm. This change increased the viscosity and the turbidity of the solution phase separated originally. Microscope showed that they are spherulite particles and polarized microscope suggested they are multi.lamellar liquid crystals. FE-SEM also proved that explicitly.
The rheological properties and surface tensions of polymer solutions and polymer-surfactant mixed solutions were investigated. The polymers used in this study were a homopolymer of acrylic acid crosslinked with an allyl ether of pentaerythritol, an allyl ether of sucrose, or an allyl ether of propylene (CARBOMER), acylate/C10-30 alkyl acylate crosspolymer (AAAC), and ammonium acryloydimethyltaurate/VP copolymer (ADTV). A solubilizing agent PEG-40 hydrogenated castor oil (HCO-40) and an emulsifying agent polyoxyethylene (20) sorbitan monostearate (POLYSORBATE 60) made the micelles intervening between AAAC polymers, resulting in the increase of viscosity. However, HCO-40 made this behavior over the wider range of surfactant concentration than POLYSORBATE 60. From the view point of surface tensions in the same range of surfactant concentration, AAAC/HCO-40 solution showed the area of increasing surface tension with surfactant concentration in contrast to the AAAC/POLYSORBATE 60 solution showing no increasing area.
Monodispersed and nano-sized Ni powders were synthesized from aqueous nickel sulfate hexahydrate inside nonionic polymer network by using wet chemical reduction process. The sucrose was used as a nonionic polymer network source. The effect of reaction conditions such as the amount of sucrose and a various reaction temperature, nickel sulfate hexahydrate molarity. The influence of a nonionic polymer network on the particle size of the prepared Ni powders was characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and particle size analysis (PSA). The results showed that the obtained Ni powders were strong by dependent of the reaction conditions. In particular, the Ni powders prepared inside a nonionic polymer network had smooth spherical shape and narrow particle size distribution.
A proposed method of determining the composition of mixed micelles in equilibrium with monomer of known composition is described. The systems were sodium α-sulfonated dodecanoyl ethyl esther (α-SR12Et) or sodium dodecyl sulfate(SDS)-polyoxyethylene 23 lauryl ether (Brij 35) un water and in 0.1M sodium chloride solution at 25℃. This technique applies the Gibbs-Duhem equation to the mixed micelles, which is treated as a pseudophase. This proposed methodology, which needs only critical micelle concentration data as a function of monomer composition, is applied to an anionic/nonionic surfactant pair. The calculated monomer-micelle equilibrium is found to be very similar to the much-used regular solution for nonideal systems.
Excess enthalpies (HE) were measured by isothermal flow calorimetry for the nonionic amphiphile 2-butoxyethanol/water mixtures at 10 different temperatures (48.5 to 70℃) around and above the lower consolute solution temperature, Tlc. HE exhibits U-shape for the binary mixtures, and is large and negative which reflects substantial interaction between two chemical species. When the commonly used, semi-empirical Redlich-Kister (RK) polynomials were fitted to the measured HE, plots of HE vs. weight fraction provided more accurate fitting with fewer parameters than conventionally drawn HE vs. mole fraction plots. This was due to the enhanced symmetry of HE vs. weight fraction plots. Using the fitted Redlich-Kister polynomials and the Gibbs-Helmholtz relation, temperature dependence of the activity coefficients were found and compared to the values determined from vapor-liquid equilibria. The activity coefficients were in the range of one to three, indicating that the binary system deviates from ideality but not substantially. They slightly depended on temperature and the temperature effect was equivalent to 10 % change in the activity coefficients.
To prepare a O/W type nonionic durable softner(ANSA), synthesized 1, 3-dihexadanoyl-2, 7-dioxy-6, 8-di(2-hexadecanoyloxyethyl)-1, 3, 6, 8-tetraazacyclodecane as the main component of softner, was blended with beef tallow, anhydrous lanolin, polyoxyethylene(20) oleyl ether, sorbitan sesquioleate, and polyoxyethylene(7) stearyl ether in various compositions. Emulsion stability of ANSA was good, and the mixed HLB value was 9.8. After the treatment of ANSA to all cotton fabrics, the physical properties such as tear strength, crease recovery, and flexing abrasion resistance were measured, respectively. As a result of the measurement, ANSA was proved to be durable softner with good softness.
1, 3-Di(dodecanoyl)-2, 7-dioxy-6, 8-di(2-hydroxyethyl)-1, 3, 6, 8-tetraazacyclodecane(DDDT) and pentaerythritol monostearate(PMS) were synthesized as a main component for softner. O/W type softner(DPSA) was prepared by blending DDDT and PMS with polyoxyethylene(10) castor oil, polyoxyethylene(20) oleyl ether, and polyoxyethylene(10) monolaurate. After treatment of DPSA to all cotton fabrics, the physical properties such as tear strength, crease recovery, and flexing abrasion resistance were measured. As a result of the measurement, DPSA was proved to be durable softner with good softness.
The synthesis and solution properties of polyglycerol alkyl ether(R12Gn) are described. The phase behavior, surface tension, cloud point and HLB value of polyglycerol dodecyl ether in aqueous solution and in mixed solution of surfactant /water /oil have been investigated and compared with values of polyoxyethylene dodecyl ether. The surface tension showed that R12Gn have sufficiently low values of surface tension and cmc to serve as useful polyoxyethylene alkyl ether. The mesophases appearing in the R12Gn systems were more stable in a high temperature range than the mesophases of polyoxyethylene alkyl ether systems. The cloud point and HLB data indicated that addition of one glycerol group was equivalent to the addition of three oxyethylene group units, as far as the hydrophilic property was concerned. The phase diagrams of the polyglycerol alkyl ether /dodecane /water systems showed that the solubilizing and emulsifying powers of R12Gn were greater than those of polyoxyethylene alkyl ether. It is concluded that the polyglycerol chain can be even more useful as hydrophilic group of nonionic surfactants than the polyoxyethylene chain.
Properties of aqueous solution, that is, the viscosities and solubilities of benzene were observed in relation to critical micelle concentration of each alkyl aldehyde polyoxyethylene glycol acetal type surfactant. These showed that the mininum points in specific viscosity/concentration-concentration curves were corresponded with the critical micelle concentration obtained by surface tension and appeared the remarkable increase of non-Newtonics according to the increase of the number of carbon in hydrophobic groups. The fluidity of non-Newtonics is not observed by a little increase of the degree of polymerization in polyoxyethylene glycol groups.
Aliphatic aldehyde polyoxyethylene glycol acetals were synthesised through the reaction of aliphatic aldehydes such as caproic aldehyde, capryl aldehyde, capric aldehyde and lauric aldehyde with excess diethylene glycol, triethylene glycol and tetraethylene glycol, respectively. The acetal formation, in which water was azeotropically distilled by adding benzene to the reaction system, was gained a good yield of acetal type compounds. This reaction is found pseudo first order reaction at various temperatures such 70, 80, 90 and 97℃. Also these activation energies of reaction of acetal type products such as caproic aldehyde diethylene glycol acetal, capryl aldehyde diethylene glycol acetal, capric aldehyde diethylene glycol acetal, lauric aldehyde diethylene glycol acetal, caproic aldehyde triethylene glycol acetal and caproic aldehyde tetraethylene acetal were 17.3, 19.6, 21.2, 21.6, 15.5 and 14.7 Kcal/mole.
Agricultural soils around springwaters heavily affected by pesticide run-off and around wells considering the regional characteristics were collected at 24 stations in Jeju Island, and the physicochemical properties and adsorption and leaching characteristics of four nonionic pesticides (diazinon, fenitrothion, alachlor, and metalaxyl) were investigated. The values of the major soil factors affecting the adsorption and leaching of pesticides, namely, soil pH(H2O), organic matter content, and cation exchange capacity (CEC), were in the range of 4.64 ∼ 8.30, 0.9 ∼ 13.1% and 12.7 ∼ 31.7 meq/100 g, respectively. The Freundlich constant, KF value, which gives a measure of the adsorption capacity, decreased in the order of fenitrothion > diazinon > alachlor > metalaxyl, which was identical to their lower water solubility. Among the collected soils, the KF value was very highly correlated with organic matter content (r2 = 0.800 ∼ 0.876) and CEC (r2 = 0.715 ∼ 0.825) and showed a high correlation with clay content (r2 = 0.473 ∼ 0.575) and soil pH(H2O) (r2 = 0.401 ∼ 0.452). The leaching of pesticides in the soil column showed a reverse relationhip with their adsorption in soils, i.e., the pesticides leached more quickly for the soils with lower values of organic matter content and CEC among the soils and for the pesticides with higher water solubility.
본 연구에서는 인지질-비이온계면활성제의 혼합계면활성제를 이용하여 옥틸도데실미리스테이트를 조성상전이 유화법으로 O/W 타입 나노에멀젼을 제조하였다. 혼합 계면활성제와 오일의 농도 비가 1 : 1 정도의 매우 좁은 영역에서 나노에멀젼이 형성되었다. 비이온계면활성제로만 제조된 나노에멀젼과는 달리 전상점 이후에 수용액상을 첨가함에 따라 에멀젼의 입자 크기가 감소하였다. 제조된 나노에멀젼은 실온에서 한 달 이상 안정하였다. 인지질을 함유하고 저에너지 유화법으로 제조된 나노에멀젼 제형은 화장품의 기재로서 널리 사용될 수 있다.
The environmental behaviors of polycyclic aromatic hydrocarbons (PAHs) are mainly governed by their solubility and partitioning properties on soil media in a subsurface system. In surfactant-enhanced remediation (SER) systems, surfactant plays a critical role in remediation. In this study, sorptive behaviors and partitioning of naphthalene in soils in the presence of surfactants were investigated. Silica and kaolin with low organic carbon contents and a natural soil with relatively higher organic carbon content were used as model sorbents. A nonionic surfactant, Triton X-100, was used to enhance dissolution of naphthalene. Sorption kinetics of naphthalene onto silica, kaolin and natural soil were investigated and analyzed using several kinetic models. The two compartment first-order kinetic model (TCFOKM) was fitted better than the other models. From the results of TCFOKM, the fast sorption coefficient of naphthalene (k1) was in the order of silica > kaolin > natural soil, whereas the slow sorbing fraction (k2) was in the reverse order. Sorption isotherms of naphthalene were linear with organic carbon content (foc) in soils, while those of Triton X-100 were nonlinear and correlated with CEC and BET surface area. Sorption of Triton X-100 was higher than that of naphthalene in all soils. The effectiveness of a SER system depends on the distribution coefficient (KD) of naphthalene between mobile and immobile phases. In surfactant-sorbed soils, naphthalene was adsorbed onto the soil surface and also partitioned onto the sorbed surfactant. The partition coefficient (KD) of naphthalene increased with surfactant concentration. However, the KD decreased as the surfactant concentration increased above CMC in all soils. This indicates that naphthalene was partitioned competitively onto both sorbed surfactants (immobile phase) and micelles (mobile phase). For the mineral soils such as silica and kaolin, naphthalene removal by mobile phase would be better than that by immobile phase because the distribution of naphthalene onto the micelles (Kmic) increased with the nonionic surfactant concentration (Triton X-100). For the natural soil with relatively higher organic carbon content, however, the naphthalene removal by immobile phase would be better than that by mobile phase, because a high amount of Triton X-100 could be sorbed onto the natural soil and the sorbed surfactant also could sorb the relatively higher amount of naphthalene.