This paper examines the effect of mechanical activation on the amorphization of starch having different types of crystalline structure (A-type corn starch; B-type potato starch; and C-type tapioca starch). Structural properties of the starches were studied by X-ray diffraction analysis. Mechanical activation in a planetary ball mill reduces the degree of crystallinity in proportion to pretreatment duration. C-type tapioca starch was found to have the highest degree of crystallinity. Energy consumed to achieve complete amorphization of the starches having different types of crystalline structure was measured. The kinetic parameters of the process (the effective rate constants) were determined. The rate constant and the strongest decline in the crystallinity degree after mechanical activation change in the following series: C-type starch, A-type starch, and B-type starch.

At present, “mechanochemistry” is synonymous with “grinding,” according to the views of a significant number of scientists and technologists. Often, one comes across the opinion that “the less the particle size, the better.” The cases of considering chemical reactions occurring during pretreatment, as well as considering changes in the ultrastructure of cell walls are extremely rare. Also, the wrong choice of the type of mechanical impact and the equipment used in most cases leads to excessive consumption of electrical energy and reduce economic efficiency. The review presents the currently available published data on mechanically activated processes for the pretreatment of plant materials and shows that when using mechanical treatment, it is necessary to look more closely at the phenomena occurring, rather than reducing everything to the production of fine and ultrafine powders. As a result of mechanical action, active surface radicals can form, hydrothermal chemical processes can occur, and mechanocomposites can form. The role of interphase processes, changes in surface chemistry, related dimensional effects, and the disordering of the crystal structure and amorphization should be taken into account. In addition, the physicochemical insights in mechanical pretreatment make it possible to more efficiently use the energy delivered to the material, and, consequently, increase the economic efficiency of the activation process.

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As a heterogeneous process, enzymatic hydrolysis depends on the contact area between enzymes and the cellulose substrate. The surface area of a substrate is typically evaluated through the sorption of gases (nitrogen, argon, or water vapor) or sorption of high-molecular-weight pigments or proteins. However, lignocellulosic biomass uninvolved in the reaction because of inefficient binding or even the complete inhibition of the enzymes on the surface consisting of lignin or inorganic compounds is erroneously taken into account under these conditions. The initial rate of enzymatic hydrolysis will directly depend on the number of enzymes efficiently sorbed onto cellulose. In this study, the sorption of cellulolytic enzymes was used to evaluate the surface accessibility of the cellulose substrate and its changes during mechanical pretreatment. It was demonstrated that for pure cellulose, mechanical activation did not alter the chemical composition of the surface and the initial rate of hydrolysis increased, which was inconsistent with the data on the thermal desorption of nitrogen. New active cellulose sorption sites were shown to be formed upon. the mechanical activation of plant biomass (wheat straw), and the ultimate initial rate of hydrolysis corresponding to saturation of the accessible surface area with enzyme molecules was determined.

Mechanical amorphization of three chitosan samples with high, medium, and low molecular weight was studied. It is shown that there are no significant differences between the course of amorphization process in a planetary ball mill of chitosan with different molecular weights, and the maximum degree of amorphization was achieved in 600 s of high intensity mechanical action. Specific energy consumption was 28 kJ/g, being comparable to power consumption for amorphization of cellulose determined previously (29 kJ/g) and 5–7-fold higher than that for amorphization of starch (4–6 kJ/g). Different techniques for determining the crystallinity index (CrI) of chitosan (analysis of the X-ray diffraction (XRD) data, the peak height method, the amorphous standard method, peak deconvolution, and full-profile Rietveld analysis) were compared. The peak height method is characterized by a broader working range but provides deviated CrI values. The peak deconvolution method (with the amorphous Voigt function) makes it possible to calculate the crystallinity index of chitosan with greater accuracy, but the analysis becomes more difficult with samples subjected to mechanical processing. In order to refine the structure and calculation of CrI by the Rietveld method, an attempt to optimize the structure file by the density functional theory (DFT) method was performed. The averaged profile of amorphous chitosan approximated by an eighth-order Fourier model improved the correctness of the description of the amorphous contribution for XRD data processing. The proposed equation may be used as a universal standard model of amorphous chitosan to determine the crystallinity index both for the amorphous standard method and for peak deconvolution of XRD patterns for arbitrary chitosan samples.