Functionalisation of clay aerogel composites for applications in construction

This thesis was submitted for the award of Doctor of Philosophy and was awarded by Brunel University LondonClay aerogels are relatively a new class of materials with number of merits suitable for many applications in various industrial sectors. With the current mandate to utilise environmentally friendly materials to produce functional materials, clay aerogels provide an attractive potential green solution to overcome thermal issues in construction. However for it to be effectively used as an insulation material, research work is required to address several critical issues and setbacks: the first of these is poor mechanical properties highlighted in the literature as its main weakness; the second is there extremely high hydrophilic and hygroscopic nature identified as the main research gap, which not only can cause a significant increase in thermal conductivity but also can disintegrate the aerogels. This thesis investigates and develops novel methodologies to overcome the associated setbacks through comprehensive characterisation and better understanding of mechanisms of formulation, architecture, behaviour and corresponding performance of clay aerogel constituents and composites: (I) The anisotropic structure of the aerogel was thoroughly investigated and its influence on properties was established; (II) By adjusting and tuning the mixing temperatures, the compressive modulus was enhanced by more than 7 folds; (III) Ultrasonic technologies were used to prepare organoclay- polyvinyl alcohol aerogel composites with 40% less moisture absorption in addition to lower thermal conductivity; (IV) Implementing organosilanes and isocyanates to prepare clay-PVA aerogels resulted in an effective method to reduce the moisture absorption by more than 40% with a 6 fold increase in compressive modulus; (VI) soluble water repellent was incorporated to prepare hydrophobic aerogel composites with contact angles of 140°; and (VII) Organosilanes and isocyanates are combined with a water repellent to generate highly functional clay aerogel composites. Overall this thesis paves the way for the industrialisation of functional clay-aerogel insulation materials for construction and other sectors

Comparison of breast sequential and simultaneous integrated boost using the biologically effective dose volume histogram (BEDVH)

Purpose: A method is presented to radiobiologically compare sequential (SEQ) and simultaneously integrated boost (SIB) breast radiotherapy. Methods: The method is based on identically prescribed biologically effective dose (iso-BED) which was achieved by different prescribed doses due to different fractionation schemes. It is performed by converting the calculated three-dimensional dose distribution to the corresponding BED distribution taking into consideration the different number of fractions for generic α/β ratios. A cumulative BED volume histogram (BEDVH) is then derived from the BED distribution and is compared for the two delivery schemes. Ten breast cancer patients (4 right-sided and 6 left-sided) were investigated. Two tangential intensity modulated whole breast beams with two other oblique (with different gantry angles) beams for the boost volume were used. The boost and the breast target volumes with either α/β = 10 or 3 Gy, and ipsi-lateral and contra-lateral lungs, heart, and contra-lateral breast as organs at risk (OARs) with α/β = 3 Gy were compared. Results: Based on the BEDVH comparisons, the use of SIB reduced the biological breast mean dose by about 3%, the ipsi-lateral lung and heart by about 10%, and contra-lateral breast and lung by about 7%. Conclusion: BED based comparisons should always be used in comparing plans that have different fraction sizes. SIB schemes are dosimetrically more advantageous than SEQ in breast target volume and OARs for equal prescribed BEDs for breast and boost

A prototype low-carbon segmented concrete shell building floor system

Concrete shell structures offer a mechanically efficient solution as a building floor system to reduce the environmental impact of our buildings. Although the curved geometry of shells can be an obstacle to their fabrication and implementation, digital fabrication and affordable robotics provide a means for the automation of their construction in a sustainable manner at an industrial scale. The applicability of such structures is demonstrated in this paper with the realisation of a large-scale concrete shell floor system, completed by columns, tie rods, and a levelled floor. The shell was prefabricated off-site in segments that can be transported and assembled on-site, and which can be disassembled to enable a circular economy of construction. This paper presents the conceptual and structural design; the automation of fabrication, thanks to an actuated, reconfigurable, reusable mould and a robotic concrete spraying process; the strategy and sequence of assembly and disassembly on-site using standard scaffold elements; and the sustainability assessment using life-cycle analysis. This prototype offers a reduction of about 50% of cradle-to-gate embodied carbon benchmarked against regular flat slabs before further improvement and optimisation

Dose-escalated salvage radiotherapy after radical prostatectomy in high risk prostate cancer patients without hormone therapy: outcome, prognostic factors and late toxicity

Purpose: Evaluation of dose escalated salvage radiotherapy (SRT) in patients after radical prostatectomy (RP) who had never received antihormonal therapy. To investigate prognostic factors of the outcome of SRT and to analyze which patient subsets benefit most from dose escalation. Materials and methods: Between 2002 and 2008, 76 patients were treated in three different dose-groups: an earlier cohort treated with 66 Gy irrespective of pre-RT-characteristics and two later cohorts treated with 70 Gy or 75 Gy depending on pre-RT-characteristics. Biochemical-relapse-free-survival (bRFS), clinical-relapse-free-survival (cRFS) and late toxicity were evaluated. Results: Four-year bRFS and cRFS were 62.5% and 85%. Gleason score <8, positive surgical resection margin (PSRM) and low PSA (<= 0.5 ng/ml) before SRT resulted in higher bRFS. Analysis of the whole group showed no clear dose-outcome relationship. Patients with PSRM, however, had improved bRFS when escalating >66 Gy. While >70 Gy did not improve the overall results, 4-year bRFS for patients with manifest local recurrence in the high-dose group was still comparable to those without manifest local recurrences. No grade 4 and minimal grade 3 gastrointestinal and urinary toxicity were observed. Conclusions: Dose-escalated SRT achieves high biochemical control. The data strongly support the application of at least 70 Gy rather than 66 Gy. They do not prove positive effects of doses >70 Gy but do not disprove them as these doses were only applied to an unfavorable patients selection

A fast radiotherapy paradigm for anal cancer with volumetric modulated arc therapy (VMAT)

Background/Purpose: Radiotherapy (RT) volumes for anal cancer are large and of moderate complexity when organs at risk ( OAR) such as testis, small bowel and bladder are at least partially to be shielded. Volumetric intensity modulated arc therapy (VMAT) might provide OAR-shielding comparable to step-and-shoot intensity modulated radiotherapy (IMRT) for this tumor entity with better treatment efficiency. Materials and methods: Based on treatment planning CTs of 8 patients, we compared dose distributions, comformality index (CI), homogeneity index ( HI), number of monitor units (MU) and treatment time (TTT) for plans generated for VMAT, 3D-CRT and step-and-shoot-IMRT (optimized based on Pencil Beam (PB) or Monte Carlo ( MC) dose calculation) for typical anal cancer planning target volumes (PTV) including inguinal lymph nodes as usually treated during the first phase (0-36 Gy) of a shrinking field regimen. Results: With values of 1.33 +/- 0.21/1.26 +/- 0.05/1.3 +/- 0.02 and 1.39 +/- 0.09, the CI's for IMRT (PB-Corvus/PB-Hyperion/MC-Hyperion) and VMAT are better than for 3D-CRT with 2.00 +/- 0.16. The HI's for the prescribed dose (HI36) for 3D-CRT were 1.06 +/- 0.01 and 1.11 +/- 0.02 for VMAT, respectively and 1.15 +/- 0.02/1.10 +/- 0.02/1.11 +/- 0.08 for IMRT (PB-Corvus/PB-Hyperion/MCHyperion). Mean TTT and MU's for 3D-CRT is 220s/225 +/- 11MU and for IMRT (PB-Corvus/PBHyperion/MC-Hyperion) is 575s/1260 +/- 172MU, 570s/477 +/- 84MU and 610s748 +/- 193MU while TTT and MU for two-arc-VMAT is 290s/268 +/- 19MU. Conclusion: VMAT provides treatment plans with high conformity and homogeneity equivalent to step-and-shoot-IMRT for this mono-concave treatment volume. Short treatment delivery time and low primary MU are the most important advantages

INTRAGO: intraoperative radiotherapy in glioblastoma multiforme – a Phase I/II dose escalation study

Background: Glioblastoma multiforme (GBM) is the most frequent primary malignant brain tumor in adults. Despite multimodal therapies, almost all GBM recur within a narrow margin around the initial resected lesion. Thus, novel therapeutic intensification strategies must target both, the population of dispersed tumor cells around the cavity and the postoperative microenvironment. Intraoperative radiotherapy (IORT) is a pragmatic and effective approach to sterilize the margins from persistent tumor cells, abrogate post-injury proliferative stimuli and to bridge the therapeutic gap between surgery and radiochemotherapy. Therefore, we have set up INTRAGO, a phase I/II dose-escalation study to evaluate the safety and tolerability of IORT added to standard therapy in newly diagnosed GBM. In contrast to previous approaches, the study involves the application of isotropic low-energy (kV) x-rays delivered by spherical applicators, providing optimal irradiation properties to the resection cavity. Methods/Design: INTRAGO includes patients aged 50 years or older with a Karnofsky performance status of at least 50% and a histologically confirmed (frozen sections) supratentorial GBM. Safety and tolerability (i.e., the maximum tolerated dose, MTD) will be assessed using a classical 3 + 3 dose-escalation design. Dose-limiting toxicities (DLT) are wound healing deficits or infections requiring surgical intervention, IORT-related cerebral bleeding or ischemia, symptomatic brain necrosis requiring surgical intervention and early termination of external beam radiotherapy (before the envisaged dose of 60 Gy) due to radiotoxicity. Secondary end points are progression-free and overall survival. Trial registration: The study is registered with clinicaltrials.gov, number: NCT02104882 (Registration Date: 03/26/2014)

Critical review on the thermal conductivity modelling of silica aerogel composites

As a new generation of thermal insulation materials, the effective thermal conductivity of aerogel and its composites is extremely low. The nanoporous structure of aerogels demobilises the movement of gas molecules, and the nano-skeleton system restricts solid heat transfer because of the size effect. Numerous research and modelling works have been carried out to understand and predict heat transfers. This review thoroughly discusses the existing theories and models of silica aerogel composites in gas, solid and radiative heat transfers. It investigates the correlation of the pore size distribution and solid skeleton network of the composites with the thermal conductivity. The review then assesses the advances of the development and questions remaining for further development, including 1) some unexplainable performance of existing models and 2) improvements required for gas and solid thermal conductivity models. Bridging the identified research gaps shall lead researchers to understand existing models better, develop a more accurate model based on more realistic microstructure simulation and further innovate the models for other emerging composites

Combined kyphoplasty and intraoperative radiotherapy (Kypho-IORT) versus external beam radiotherapy (EBRT) for painful vertebral metastases - a randomized phase III study

Background: The spine is the most frequent location of bone metastases. Local treatment aims at palliation of pain and, given the increased likelihood of long-term cancer survival, at local control. Kyphoplasty and intraoperative radiotherapy (Kypho-IORT) provided instantaneous pain relief in 70% of patients at the first day after the intervention and resulted in local control rates of > 93% at 1 year in a recently conducted phase I/II trial. To assess its clinical value, we designed a phase III trial which tests Kypho-IORT against the most widespread standard-of-care, external beam radiotherapy (EBRT), in patients with painful vertebral metastases. Methods: This phase III study includes patients ≥50 years of age with up to 4 vertebral metastases and a pain score of at least 3/10 points on the visual/numeric analogy scale (VAS). Patients randomized into the experimental arm (A) will undergo Kypho-IORT (Kyphoplasty plus IORT with 8 Gy prescribed to 13 mm depth). Patients randomized into the control arm (B) will receive EBRT with either 30 Gy in 10 fractions or 8 Gy as a single dose. The primary end point is pain reduction defined as at least − 3 points on the VAS compared to baseline at day 1. Assuming that 40% of patients in the Kypho-IORT arm and 5% of patients in the control arm will achieve this reduction and 20% will drop out, a total of 54 patients will have to be included to reach a power of 0.817 with a two-sided alpha of 0.05. Secondary endpoints are evaluation of the percentage of patients with a pain reduction of at least 3 points at 2 and 6 weeks, local tumor control, frequency of re-intervention, secondary fractures/sintering, complication rates, skin toxicity/wound healing, progression-free survival (PFS), overall survival (OS) and quality of life. Discussion: This trial will generate level 1 evidence on the clinical value of a one-stop procedure which may provide instantaneous pain relief, long-term control and shortened intervals to further adjuvant (systemic) therapies in patients with spinal metastases. Trial registration Registered with ClinicalTrials.gov, number: NCT02773966. Registration date: 05/16/2016