Development of segmented flow crystallisers for in situ X-ray diffraction analysis

The study of crystallisation through in situ analysis methods is key to elucidating the crystallisation processes of polymorphic materials. This thesis presents research on the development of in situ X-ray diffraction (XRD) techniques for the study of segmented flow crystallisation. This work was ca...

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Main Author: Galtry, Elizabeth Sarah
Format: Thesis (University of Nottingham only)
Language:English
Published: 2025
Subjects:
Online Access:https://eprints.nottingham.ac.uk/80261/
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author Galtry, Elizabeth Sarah
author_facet Galtry, Elizabeth Sarah
author_sort Galtry, Elizabeth Sarah
building Nottingham Research Data Repository
collection Online Access
description The study of crystallisation through in situ analysis methods is key to elucidating the crystallisation processes of polymorphic materials. This thesis presents research on the development of in situ X-ray diffraction (XRD) techniques for the study of segmented flow crystallisation. This work was carried out as a joint studentship between University of Nottingham and Diamond Light Source, the UK’s national synchrotron research facility. Chapter 5 describes the commissioning of a temperature-cycling segmented flow crystalliser, the KRAIC-T. Temperature-cycling during crystallisation enabled enhanced control over the crystallisation process of succinic acid. Integration of the KRAIC-T as a sample environment on Beamline I11 at Diamond Light Source involved the use of an upgraded data acquisition technique to improve the signal-to-noise of collected in situ powder X-ray diffraction data (PXRD). The study of the slurrying crystallisation of the polymorphic crystal system, ortho-aminobenzoic acid, was used to verify the improvement of the in situ technique. These data were also used for the development of enhanced data processing techniques. In situ XRD analysis is largely limited to synchrotron facilities due to the high intensity, high energy X-rays required for XRD investigation of complex sample environments. Chapter 4 discusses the development of the KRAIC-Xl, a segmented flow crystalliser for lab-source PXRD analysis at the Flow-Xl facility, University of Leeds. Proof-of-principles studies found the lab-source system was able to achieve time-resolved PXRD studies of glycine (GLY) anti-solvent crystallisation, finding the initial crystallisation of the highly metastable β-GLY and rapid transformation to the more stable α-GLY polymorph. Chapter 3 details the development of Python-based processing methodologies for PXRD data collected from the KRAIC-T and KRAIC-Xl systems. Existing processing techniques are often labour-intensive and time-consuming for processing of PXRD from complex environments; specialist Python modules were used to develop novel processing workflows in Chapter 3 maximise the diffraction signal extracted, whilst minimising data processing time. Chapter 6 discusses the development of the KRAIC-S v2 and v3; upgraded crystalliser designs for serial crystallography during segmented flow at Beamline I19, Diamond Light Source. Beamtime with the KRAIC-S v2 on the cooling crystallisation of paracetamol assessed the system, showing an improved ease-of-use, but highlighted limitations of the serial crystallography technique. Chapter 7 uses the final KRAIC-S v3 design for the study of nonphotochemical laser induced nucleation of potassium chloride, achieving induced nucleation of a single particle per droplet and accompanying in situ XRD.
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spelling nottingham-802612025-07-31T04:40:09Z https://eprints.nottingham.ac.uk/80261/ Development of segmented flow crystallisers for in situ X-ray diffraction analysis Galtry, Elizabeth Sarah The study of crystallisation through in situ analysis methods is key to elucidating the crystallisation processes of polymorphic materials. This thesis presents research on the development of in situ X-ray diffraction (XRD) techniques for the study of segmented flow crystallisation. This work was carried out as a joint studentship between University of Nottingham and Diamond Light Source, the UK’s national synchrotron research facility. Chapter 5 describes the commissioning of a temperature-cycling segmented flow crystalliser, the KRAIC-T. Temperature-cycling during crystallisation enabled enhanced control over the crystallisation process of succinic acid. Integration of the KRAIC-T as a sample environment on Beamline I11 at Diamond Light Source involved the use of an upgraded data acquisition technique to improve the signal-to-noise of collected in situ powder X-ray diffraction data (PXRD). The study of the slurrying crystallisation of the polymorphic crystal system, ortho-aminobenzoic acid, was used to verify the improvement of the in situ technique. These data were also used for the development of enhanced data processing techniques. In situ XRD analysis is largely limited to synchrotron facilities due to the high intensity, high energy X-rays required for XRD investigation of complex sample environments. Chapter 4 discusses the development of the KRAIC-Xl, a segmented flow crystalliser for lab-source PXRD analysis at the Flow-Xl facility, University of Leeds. Proof-of-principles studies found the lab-source system was able to achieve time-resolved PXRD studies of glycine (GLY) anti-solvent crystallisation, finding the initial crystallisation of the highly metastable β-GLY and rapid transformation to the more stable α-GLY polymorph. Chapter 3 details the development of Python-based processing methodologies for PXRD data collected from the KRAIC-T and KRAIC-Xl systems. Existing processing techniques are often labour-intensive and time-consuming for processing of PXRD from complex environments; specialist Python modules were used to develop novel processing workflows in Chapter 3 maximise the diffraction signal extracted, whilst minimising data processing time. Chapter 6 discusses the development of the KRAIC-S v2 and v3; upgraded crystalliser designs for serial crystallography during segmented flow at Beamline I19, Diamond Light Source. Beamtime with the KRAIC-S v2 on the cooling crystallisation of paracetamol assessed the system, showing an improved ease-of-use, but highlighted limitations of the serial crystallography technique. Chapter 7 uses the final KRAIC-S v3 design for the study of nonphotochemical laser induced nucleation of potassium chloride, achieving induced nucleation of a single particle per droplet and accompanying in situ XRD. 2025-07-31 Thesis (University of Nottingham only) NonPeerReviewed application/pdf en cc_by https://eprints.nottingham.ac.uk/80261/1/ElizabethGaltry-10142881-thesis-corrections.pdf Galtry, Elizabeth Sarah (2025) Development of segmented flow crystallisers for in situ X-ray diffraction analysis. PhD thesis, University of Nottingham. In situ X-ray diffraction techniques; Segmented flow crystallisation; Crystallisation; Polymorphic materials
spellingShingle In situ X-ray diffraction techniques; Segmented flow crystallisation; Crystallisation; Polymorphic materials
Galtry, Elizabeth Sarah
Development of segmented flow crystallisers for in situ X-ray diffraction analysis
title Development of segmented flow crystallisers for in situ X-ray diffraction analysis
title_full Development of segmented flow crystallisers for in situ X-ray diffraction analysis
title_fullStr Development of segmented flow crystallisers for in situ X-ray diffraction analysis
title_full_unstemmed Development of segmented flow crystallisers for in situ X-ray diffraction analysis
title_short Development of segmented flow crystallisers for in situ X-ray diffraction analysis
title_sort development of segmented flow crystallisers for in situ x-ray diffraction analysis
topic In situ X-ray diffraction techniques; Segmented flow crystallisation; Crystallisation; Polymorphic materials
url https://eprints.nottingham.ac.uk/80261/