4.2 Article

Rheological stability of carbomer in hydroalcoholic gels: Influence of alcohol type

Journal

INTERNATIONAL JOURNAL OF COSMETIC SCIENCE
Volume 43, Issue 6, Pages 748-763

Publisher

WILEY
DOI: 10.1111/ics.12750

Keywords

Carbopol NF 980; flow behaviour; hydroalcoholic gels; intrinsic viscosities; stability

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This paper aims to analyze the rheological changes and dynamics of Carbopol gel systems over time, specifically neutralized by triethanol amine, to understand the time stabilities and ageing effects. The study observed significant differences in viscosity and modulus values among water-based, ethanol-based, and isopropyl alcohol-based gels, shedding light on the microstructural evolution of such gel systems. The results indicated that ethanol and water-based gels showed relatively stable rheological behavior over 30 days, while the isopropyl alcohol-based gel exhibited a significant increase in viscosity, suggesting different ageing mechanisms in these systems.
Objective The main objective of this paper is to analyse and attempt to understand the nature of rheological changes observed and the dynamics of Carbopol NF 980 hydroalcoholic gels neutralized specifically by triethanol amine (TEA), both as a function of time and alcohol type to probe time stabilities and ageing effects in such carbopol gel systems. The rheological changes and dynamics of 3 carbopol gel systems were observed; the gels included a water-based, ethanol-based, and isopropyl alcohol-based gel. It is hoped that this study shall shed light on the dynamical nature and the microstructural evolution of such networked gel systems, which were maintained under closed isothermal conditions and left completely unperturbed. The experimental results can provide the information necessary to understand and proposes plausible mechanisms guiding this dynamical behaviour in hydroalcoholic carbopol gels. Methods A TA instrument mechanical rheometer was used to measure the viscosity and storage and loss modulus, and a pH meter was utilized to determine the changes in each sample over the period. Results Studying the differences in the gel structures upon initial preparation illustrated that the ethanol and isopropyl alcohol (IPA) gels differed from the water-based gel in terms of viscosity, G ', and G '', with the IPA gel displaying the lowest viscosity and moduli values across all shear rates. All the three gel systems exhibited strong shear thinning characteristics and were reminiscent of yield stress type found in colloidal gels. The water-based gel compared to the hydroalcoholic gels was strongly G ' dominated, with the magnitude of the difference between G ' and G '' observed to be much higher. This reflects that initial formation of the water-based gel structure possesses a much more rigid structure with a high elastic modulus component dominating. This also suggests that the water-based gel structure displayed stronger interactions between the carbopol particles when compared to those of the hydroalcoholic gels. Over the 30-day period, it was observed that the ethanol and water-based gels did not reveal any appreciable viscosity changes, with only an approximate 12% and 7% change from day 1 to 30, respectively. It was observed that the IPA systems' viscosity drastically increased over the period, with an approximately 77% change from day 1 to 30. The water and ethanol-based gels also exhibited very similar rheological behaviour over the entire time period with G ' dominating G ''. The G '' values of the water and ethanol-based gels decreased slightly at the end of day 30 by 10% and 16%, respectively, while the G ' values for each sample remained essentially unchanged, increasing only 0.06% for the water-based gel, and increasing 1.4% for the ethanol-based gel. This further confirms the relatively stable gel structures attained. For the isopropyl gel system, the storage modulus of the system exhibited an average percent increase of approximately 16% from day 1 to day 30, but interestingly the loss modulus varied the least amongst all the gel systems, with only a 3% increase. The increase in G ' reflects upon the evolution of a more rigid structure by day 30 for the IPA gel. This observation is clearly consistent with the corresponding increase in viscosity observed in the IPA gel. None of the gels tested displayed a consistent pH over the period. The pH of the hydroalcoholic gels was higher than that of the water-based gel for a majority of the period. The greatest fluctuations in pH were observed for the water and IPA gels, even though the water-based gel had one of the most stable rheological profiles out of the samples tested. The water, ethanol, and IPA gels' pH increased approximately 25%, 6%, and 5%, respectively, from day 1 to day 30. Conclusion The rheological and pH study of the 3 hand sanitizer systems over a 30-day period allowed for rational insights into the plausible reasons responsible for driving the observed rheological changes in these unperturbed systems. For the water-based gel, we hypothesize that the changes observed are due to physical ageing, where the gel structure has evolved over time to eventually progress towards a more stabilized framework structure. The pH of the gel upon formation was on the lower side. Such a lower pH influences the formation of a gel, which is comparatively less swollen and occupies a slightly lesser volume, and thereby points to a much less compacted gel network structure or alternatively, a more fluid structure. If the particles moved around more, the system was not initially in a state of low energy, causing increased particle movement, and in turn, physical ageing. This could be responsible for the development of a physically altered structure over time. The gel structure dynamically attempts to minimize its free energy by becoming more rigid, which has been observed as being manifested in the decrease of both the viscosity and the G ''. For the hydroalcoholic gels, we conjecture that ageing observed was a result of chemical ageing, and the alcohol type employed in the preparation is primarily responsible for exhibiting this effect. The polarities of ethyl alcohol and isopropyl alcohol are key to the stabilization of such resultant network structures which get formed because of neutralization. It has been observed in previous studies that with decreasing polarity, there was an increase in the neutralization needed to obtain the development of a structure half as well developed as the final resultant structure. Isopropyl alcohol is a much less polar solvent compared to ethanol and water, and therefore required higher levels of TEA as the base to neutralize the system. We conjecture that the charged TEA cationic species had a greater propensity to get exchanged with bulk solution in the vicinity of the polymer into the bulk solution, and that the pH fluctuation observed indicated a kinetic exchange process over time, causing the viscosity and moduli profiles to increase along with the pH. At this time though, further investigations need to be carried out to truly understand the underlying instability, and thus dynamics for gel systems of this type.

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