Surface Science and Adhesion in Cosmetics. Группа авторов
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The crystallization and melting enthalpies of 15% PE wax in various HPIB oil blend ratios were obtained from the areas under the crystallization and melting peaks in DSC. Increasing the viscosity of the oil blend increases the enthalpy of crystallization of the wax-oil system, hence the % relative crystallinity of PE wax (determined from equation (2.1)) increases (Figure 2.8). The low relative crystallinity of PE wax in low viscosity HPIB might be from a portion of wax crystals dissolved in low viscosity oil. The relative crystallinity is higher in high viscosity HPIB. In the heating cycle, the melting peak temperature Tm of wax-oil gels also shows a strong viscosity dependence as shown in Figure 2.9.
Figure 2.5 Hardness of lipstick structure (containing 15% PE wax) as a function of hydrogenated polyisobutene (HPIB) oil viscosity.
Figure 2.6 DSC thermograms of 15% PE wax in low viscosity (LV) HPIB and high viscosity (HV) HPIB and their blends during (a) cooling and (b) heating.
The % relative crystallinity Xc of PE wax in the HPIB oil during melting was calculated from equation (2.2) using the melting enthalpy ΔHm obtained under melting peak and ΔHm0 of pure PE (230.5 J/g). It is observed that the hardness of lipstick increases with an increase of relative crystallinity Xc (from melting) (Figure 2.10). However, two samples c and e with lower relative crystallinity in the oil blend have higher hardness. This behavior might be due to the size and shape of wax crystals developed in the oil blends and influencing the hardness of lipstick. In addition, the relative wax crystallinity in the melting cycle is observed to increase after being annealed at low temperature. Therefore, the strong dependence of lipstick hardness on oil viscosity cannot be explained by crystal density alone.
Figure 2.7 Effect of oil viscosity on the initial crystallization temperature Tc,i (blue circles) and final melting temperature Tm,f (red circles) of 15% PE wax in HPIB oils.
Figure 2.8 Effect of HPIB oil viscosity on the relative crystallinity Xc during cooling.
Figure 2.9 Effect of HPIB oil viscosity on the melting peak temperature Tm of 15% PE wax.
The SEM micrographs for the wax- HPIB oil systems reveal that the crystal size of PE wax reduces when oil viscosity increases (Figure 2.11). Low viscosity of HPIB (ɳ = 15 mPa.s) creates large wax crystals (sample a) while high viscosity HPIB (ɳ = 8.9x104 mPa.s) creates small crystals (sample b). Depending on the oil blend viscosity, different wax crystal sizes and densities are observed. The sample c is wax structure crystallized in 3 to 1 ratio of low to high HPIB oil viscosity, having large crystal size and more contact points than sample a. Therefore, the sample c has harder structure compared to sample a, and even the relative crystallinity is a little lower as seen in Figure 2.10. Sample e is a wax structure crystallized in 1 to 3 ratio of low to high oil viscosity, having a smaller crystal size and higher hardness than sample d. Thus, the reduction of crystal size will increase the contact points of each crystal, enhancing the strength of lipstick [16]. For the wax crystal sample d (in the blend of 1 to 1 ratio of low and high viscosity HPIB), the crystal size is largest and open cell, which contributes to the weaker structure. Therefore, the hardness of the lipsticks is influenced by the densities, sizes, shapes and contact points of wax crystals as reported for wax-oil gels [10, 19, 29, 36, 38].
Figure 2.10 Effect of the % relative crystallinity Xc (from wax melting) on the hardness of the lipsticks containing 15% PE wax in HPIB oils.
Figure 2.11 SEM micrographs of PE wax-oil lipsticks at fixed 15% PE wax in hydrogenated polyisobutene (HPIB) with oil viscosity (a) ɳ HPIB = 15 mPa.s, (b) ɳ HPIB = 89,960 mPa.s, and with oil blend viscosity (c) ɳ HPIB blend = 72 mPa.s, (d) ɳ HPIB blend = 900 mPa.s and (e) ɳ HPIB blend = 9,200 mPa.s.
From these results, the viscosity of the oil-wax system during cooling has a strong effect on the crystal nucleation and growth. When the temperature is reduced during the cooling process, the viscosity of oil-wax