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dc.contributor.authorDincer, Tuna
dc.contributor.supervisorProf. Gordon Parkinson
dc.contributor.supervisorDr. Mark Ogden

Lactose is the major carbohydrate in milk. The presence of lactose in whey constitutes a significant pollution problem for dairy factories. At the same time, there is an increasing market for high quality crystalline lactose. The main problem of lactose crystallisation, compared to sucrose, which is also a disaccharide, is that it is very slow, unpredictable and cannot easily be controlled. Compared to sucrose crystallisation, which has been extensively studied, lactose crystallisation lacks the fundamental research to identify the mechanisms of growth and effect of additives. An important difference from most other crystal growth systems is that ([alpha]-lactose hydrate crystals never grow from a pure environment; their growth environment always contains beta lactose. [alpha]-lactose monohydrate crystallises much more slowly because of the presence of [beta]- lactose in all solutions. Although there have been some studies on growth rates and the effect of additives, there has not been any reported work on the fundamentals of lactose crystallisation and the mechanisms that operate on the molecular level. The aim of this thesis is to gain a greater understanding at the fundamental processes, which occur at the molecular level during the crystallisation of lactose, in order to improve control at a macroscopic level.The growth rates of the dominant crystallographic faces have been measured in situ, at three temperatures and over a wide range of supersaturation. The mean growth rates of faces were proportional to the power of between 2.5-3.1 of the relative supersaturation. The rate constants and the activation energies were calculated for four faces. The [alpha]-lactose monohydrate crystals grown in aqueous solutions exhibited growth rate dispersion. Crystals of similar size displayed almost 10 fold difference in the growth rate grown under identical conditions for all the faces. Growth rate dispersion increases with increasing growth rate and supersaturation for all the faces. The variance in the GRD for the (0 10) face is twice the variance of the GRD of the (110) and (100) faces and ten times higher than the (0 11) face at different supersaturations and temperatures. The influence of [beta]-lactose on the morphology of [alpha]-lactose monohydrate crystals has been investigated by crystallising [alpha]-lactose monohydrate from supersaturated DMSO ethanol solutions. The slowness of mutarotation in DMSO allowed preparation of saturated solutions with a fixed, chosen [beta]-lactose content. It was found that [beta]-lactose significantly influences the morphology of [alpha]- lactose monohydrate crystals grown from DMSO solution. At low concentrations of [beta]-lactose, the fastest growing face is the (011) face resulting in long thin prismatic crystals. At higher [beta]-lactose concentrations, the main growth occurs in the b direction and the (020) face becomes the fastest growing face (since the (011) face is blocked by [beta]-lactose), producing pyramid and tomahawk shaped crystals.Molecular modeling was used to calculate morphologies of lactose crystals, thereby defining the surface energies of specific faces, and to calculate the energies of interactions between these faces and [beta]-lactose molecules. It was found that as the replacement energy of [beta]-lactose increased, the likelihood of [beta]-lactose to dock onto faces decreased and therefore the growth rate increased. The attachment energy of a new layer of [alpha]-lactose monohydrate to the faces containing [beta]-lactose was calculated for the (010) and (011) faces. For the (0 10) face, the attachment energy of a new layer was found to be lower than the attachment energy onto a pure lactose surface, meaning slower growth rates when [beta]-lactose was incorporated into the surface. For the (011) face, attachment energy calculations failed to predict the slower growth rates of this face in the presence of [beta]-lactose. AFM investigation of [alpha]-lactose monohydrate crystals produced very useful information about the surface characteristics of the different faces of the [alpha]-lactose monohydrate crystal. The growth of the (010) face of the crystal occurs by the lateral addition of growth layers. Steps are 2 nm high (unit cell height in the b direction) and emanate from double spirals, which usually occurred at the centre of the face. Double spirals rotate clockwise on the (010) face, while the direction of spirals is counterclockwise on the (010) face. A polygonised double spiral, showing anisotropy in the velocity of stepswas observed at the centre of the prism-shaped a-lactose monohydrate crystals grown in the presence of 5 and 10 % [beta]-lactose.The mean spacing of the steps parallel to the (011) face is larger than those parallel to the (100) face, indicating higher growth rates of the (011 )face. The edge free energy of the (011) face is 6.6 times larger than the (100) face in the presence of 5% [beta]-lactose. Increase of [beta]-lactose content from 5% to 10 % decreases the edge free energy of the growth unit on a step parallel to the (011) face by 10 %. Tomahawk-shaped [alpha]-lactose monohydrate crystals produced from aqueous solutions where the [beta]-lactose content of the growth solution is about 60 % have shown clockwise double spirals as the source of unit cell high steps on the (010) face of the crystal. However , the spirals are more circular than polygonised, unlike the prism shaped crystals and the mean step spacing of the (011) face is less than the steps parallel to the (110) face, indicating the growth rate reducing effect of [beta]-lactose on the (011) face. The (100) face of the [alpha]-lactose monohydrate crystal grows by step advancement in relative supersaturations of up to 3.1. Steps are 0.8 nm high and parallel to the c rection. Above this supersaturation, rectangular shaped two-dimensional nuclei, 10 nm high, were observed. The (011) face of the crystal grown at low supersaturations (s= 2.1) displayed a very rough surface with no steps, covered by 4-10nm high and 100-200[micro]m wide formations. Triangular shaped macrosteps were observed when the crystal was grown in solutions with s=3.1. In situ AFM investigation of the (010) face (T = 20[degree]C and s = 1.18) has shown that growth occurs by lateral addition of growth units into steps emanated by double spirals.The growth rate of the (010) face from in situ AFM growth experiments was calculated to be 1.25 gm/min. The growth rate of crystals grown in the in situ optical growth cell under identical conditions was 0.69 pm/min. The difference in growth rates can be attributed to the size difference of seed c stals used. The (010) face of a [alpha]-lactosemonohydrate crystal grown at 22.4 C and s=1.31 displayed triangular-shaped growth fronts parallel to the (011) face. The steps parallel to the (O11) face grow in a triangular shape, and spaces between triangles are filled by growth units until the end of the macrosteps is reached. No such formations were observed on steps parallel to the (110) face. Formation of macrosteps, 4-6 nm high, emanating from another spiral present on the surface was also observed on the (010) face of a crystal grown under these conditions.

dc.publisherCurtin University
dc.subjectcrystal growth
dc.subjectgrowth rate dispersion
dc.titleMechanims of lactose crystallisation
curtin.thesisTypeTraditional thesis
curtin.departmentSchool of Applied Chemistry
curtin.accessStatusOpen access

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