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1.
Molecules ; 28(17)2023 Aug 29.
Article in English | MEDLINE | ID: mdl-37687150

ABSTRACT

This study examines the structures of soft surfactant-based biomaterials which can be tuned by temperature. More precisely, investigated here is the behavior of stearic acid (SA) and 12-hydroxystearic acid (12-HSA) aqueous mixtures as a function of temperature and the 12-HSA/SA molar ratio (R). Whatever R is, the system exhibits a morphological transition at a given threshold temperature, from multilamellar self-assemblies at low temperature to small micelles at high temperature, as shown by a combination of transmittance measurements, Wide Angle X-ray diffraction (WAXS), small angle neutron scattering (SANS), and differential scanning calorimetry (DSC) experiments. The precise determination of the threshold temperature, which ranges between 20 °C and 50 °C depending on R, allows for the construction of the whole phase diagram of the system as a function of R. At high temperature, the micelles that are formed are oblate for pure SA solutions (R = 0) and prolate for pure 12-HSA solutions (R = 1). In the case of mixtures, there is a progressive continuous transition from oblate to prolate shapes when increasing R, with micelles that are almost purely spherical for R = 0.33.

2.
Molecules ; 28(11)2023 May 25.
Article in English | MEDLINE | ID: mdl-37298812

ABSTRACT

Here, we describe the behavior of mixtures of stearic acid (SA) and its hydroxylated counterpart 12-hydroxystearic acid (12-HSA) in aqueous mixtures at room temperature as a function of the 12-HSA/SA mole ratio R. The morphologies of the self-assembled aggregates are obtained through a multi-structural approach that combines confocal and cryo-TEM microscopies with small-angle neutron scattering (SANS) and wide-angle X-ray scattering (WAXS) measurements, coupled with rheology measurements. Fatty acids are solubilized by an excess of ethanolamine counterions, so that their heads are negatively charged. A clear trend towards partitioning between the two types of fatty acids is observed, presumably driven by the favorable formation of a H-bond network between hydroxyl OH function on the 12th carbon. For all R, the self-assembled structures are locally lamellar, with bilayers composed of crystallized and strongly interdigitated fatty acids. At high R, multilamellar tubes are formed. The doping via a low amount of SA molecules slightly modifies the dimensions of the tubes and decreases the bilayer rigidity. The solutions have a gel-like behavior. At intermediate R, tubes coexist in solution with helical ribbons. At low R, local partitioning also occurs, and the architecture of the self-assemblies associates the two morphologies of the pure fatty acids systems: they are faceted objects with planar domains enriched in SA molecules, capped with curved domains enriched in 12-HSA molecules. The rigidity of the bilayers is strongly increased, as well their storage modulus. The solutions remain, however, viscous fluids in this regime.


Subject(s)
Fatty Acids , Stearic Acids , Temperature , Stearic Acids/chemistry , Fatty Acids/chemistry , Microscopy , Micelles
3.
Micromachines (Basel) ; 13(7)2022 Jul 07.
Article in English | MEDLINE | ID: mdl-35888896

ABSTRACT

Micromachining allows the production of micro-components with complex geometries in various materials. However, it presents several scientific issues due to scale reduction compared to conventional machining. These issues are called size effects. At this level, micromachining experiments raise technical difficulties and significant costs. In this context, numerical modeling is widely used in order to study these different size effects. This article presents four different numerical models of micro-cutting of hardened steel, a Smooth Particle Hydrodynamics (SPH) model and three finite element (FE) models using three different formulations: Lagrangian, Arbitrary Eulerian-Lagrangian (ALE) and Coupled Eulerian-Lagrangian (CEL). The objective is to study the effect of tool edge radius on the micro-cutting process through the evolution of cutting forces, chip morphology and stress distribution in different areas and to compare the relevance of the different models. First, results obtained from two models using FE (Lagrangian) and SPH method were compared with experimental data obtained in previous work. It shows that the different numerical methods are relevant for studying geometrical size effects because cutting force and stress distribution correlate with experimental data. However, they present limits due to the calculation approaches. For a second time, this paper presents a comparison between the four different numerical models cited previously in order to choose which method of modeling can present the micro-cutting process.

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