The microbeam X-ray diffraction study for the crystallization process of oil phase in oil-in-water emulsion

水包油乳液中油相结晶过程的微束X射线衍射研究

• 批准号: 15540314
• 负责人: UENO Satoru
• 金额: $ 2.5万
• 依托单位: HIROSHIMA UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2003
• 资助国家: 日本
• 起止时间: 2003 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-15540314/
• 关键词: syncrotron radiation; microbeam; interfacial heterogeneous nucleation; alkane; rotator phase; emulsion; crystallization; emulsifier; マクロビーム; 界面

In this research subject, the following results have been obtained ;(1)Results for macro-beam (synchrotron X-ray beam of mm-sized diameter)1-1.In the oil-in-water (O/W) emulsion whose oil phase consisted of even-numbered n-alkanes, when high-melting -point surfactants were added to the droplets, pseudohexagonal and orthorhombic crystals were nucleated. In contrast, triclinic crystals formed in the droplets without the additive, and in bulk liquid both with and without the additives. It is suggested that interfacial heterogeneous nucleation occurred at the oil-water interface by freezing of the adsorbed films of the additive molecules. These results indicate that emulsion can be used to form a new crystalline polymorphic structure by using suitable additives that modify interfacial heterogeneous nucleation behavior.1-2.On the large sized O/W emulsion, without additives, whose oil phase consisted of n-hexadecane, a transient rotator phase was observed. Thus we confirmed the existence of rotator phase in n-hexadecane that was observed in bulk samples. It is suggested that the rotator phase at the oil-water interface plays a precursor role for bulk crystallization.(2)Results for micro-beam (synchrotron X-ray beam of μm-sized diameter)2-1.When microbeam X-ray passed through the edge of an oil droplet which was the O/W emulsion with additives under crystallization temperature, two kinds of diffraction peak appeared; pseudohexagonal and triclinic. In contrast, only a diffraction peak from triclinic polymorph appeared when the microbeam passed through the center of an oil droplet of the same sample. These results suggest that the template film exists at the oil-water interface and n-hexadecane near the interface is crystallized as a pseudohexagonal polymorph in the influence of the teplate film.2-2.A lot of crystals exist in an oil droplet whose diameter is more than 10 μm. Each crystal size was estimated less than 3 μm by scanning the microbeam.

（1）宏观光束（mm直径同步辐射X射线）的结果1- 1.在油相为偶数正构烷烃的O/W乳状液中，当向液滴中加入高熔点表面活性剂时，假六方晶和正交晶均成核。相比之下，在没有添加剂的液滴中以及在有和没有添加剂的本体液体中形成三斜晶体。这表明，界面异相成核发生在油-水界面上的添加剂分子的吸附膜的冻结。这些结果表明，通过使用合适的添加剂来改变界面非均质成核行为，乳液可以形成新的结晶多晶型结构。1 - 2.在不含添加剂的大尺寸O/W乳液上，其油相由正十六烷组成，观察到瞬态旋转相。因此，我们证实了在正十六烷中存在的旋转相，在散装样品中观察到。这表明，在油-水界面的旋转相起着先驱体的作用，为本体结晶。（2）微束（直径为μ m的同步辐射X射线束）的实验结果2- 1.微束X射线通过含添加剂的O/W乳状液在结晶温度下的油滴边缘时，出现了两种衍射峰：准六方衍射峰和三斜衍射峰。相比之下，当微束通过同一样品的油滴中心时，仅出现来自三斜晶型多晶型物的衍射峰。这些结果表明，模板膜存在于油水界面处，界面附近的正十六烷在模板膜的影响下结晶为假六方晶型。2 - 2.直径大于10 μm的油滴中存在大量的晶体。通过微束扫描，估计每个晶体的尺寸小于3 μm。

项目成果

DSC and synchrotron-radiation X-ray diffraction studies on crystallization and polymorphic behavior of palm stearin in bulk and oil-in-water emulsion states

DSC 和同步辐射 X 射线衍射研究散装和水包油乳液状态棕榈硬脂的结晶和多晶型行为

• 发表时间: 2004
• 期刊: J.Am.Oil Chem.Soc. 81
• 作者: Y.Shinohara;Y.Shinohara;Yuya Shinohara;M.Sakamoto;T.Sonoda
• 通讯作者: T.Sonoda

Simultaneous synchrotron radiation X-ray diffraction-DSC analysis of melting and crystallization behavior of trilauroylglycerol in nanoparticles of oil-in-water emulsion

同步辐射X射线衍射-DSC分析水包油乳液纳米粒子中三月桂酰甘油的熔融和结晶行为

• 发表时间: 2003
• 期刊: J.Am.Oil Chem.Soc. 80
• 作者: Y.Shinohara;Y.Shinohara;Yuya Shinohara;M.Sakamoto;T.Sonoda;Y.Nozue;Y.Nozue;Mitsuhiro Sakamoto;Tomoyuki Sonoda;M.Takeuchi;S.Ueno;M.Higami
• 通讯作者: M.Higami

Observation of the Transient Rotator Phase of n-Hexadecane in Emulsified Droplets with Time-Resolved Two-Dimensional Small- and Wide-Angle A-ray Scattering

用时间分辨二维小角和广角 A 射线散射观察乳化液滴中正十六烷的瞬态旋转相

• 发表时间: 2005
• 期刊: Phys.Rev.Letters 94(In press)
• 作者: Y.Shinohara

Spatial distribution of lamella structure in PCL/PVB band spherulite investigated with microbeam small- and wide-angle X-ray scattering

• DOI: 10.1016/s0032-3861(03)00591-3
• 发表时间: 2003-09-01
• 期刊: POLYMER
• 影响因子: 4.6
• 作者: Nozue, Y;Kurita, R;Amemiya, Y
• 通讯作者: Amemiya, Y

In-situ studies of ultrasound-stimulated fat crystallisation using synchrotron radiation

使用同步加速器辐射进行超声刺激脂肪结晶的原位研究

• 发表时间: 2003
• 期刊: J.Phys.Chem.B. 107
• 作者: Y.Shinohara;Y.Shinohara;Yuya Shinohara;M.Sakamoto;T.Sonoda;Y.Nozue;Y.Nozue;Mitsuhiro Sakamoto;Tomoyuki Sonoda;M.Takeuchi;S.Ueno
• 通讯作者: S.Ueno