Supramolecular functional assemblies with photo or chemical addressability

Supramolecular self-assembly represents a key technology for the spontaneous construction of nanoarchitectures and for the fabrication of materials with enhanced physical and chemical properties. In addition, a significant asset of supramolecular self-assemblies rests on their reversible formation, thanks to the kinetic lability of their non-covalent interactions. This dynamic nature can be exploited for the development of “self-healing” and “smart” materials towards the tuning of their functional properties upon various external factors. One particular intriguing objective in the field is to reach a high level of control over the shape and size of the supramolecular architectures, in order to produce well-defined functional nanostructures by rational design. In this direction, many investigations have been pursued toward the construction of self-assembled objects from numerous low-molecular weight scaffolds, for instance by exploiting multiple directional hydrogen-bonding interactions. In particular, nucleobases have been used as supramolecular synthons as a result of their efficiency to code for non-covalent interaction motifs. Among nucleobases, guanine represents the most versatile one, because of its different H-bond donor and acceptor sites which display self-complementary patterns of interactions. Interestingly, and depending on the environmental conditions, guanosine derivatives can form various types of structures. Most of the supramolecular architectures reported in this Thesis from guanosine derivatives require the presence of a cation which stabilizes, via dipole-ion interactions, the macrocyclic G-quartet that can, in turn, stack in columnar G-quadruplex arrangements. In addition, in absence of cations, guanosine can polymerize via hydrogen bonding to give a variety of supramolecular networks including linear ribbons. This complex supramolecular behavior confers to the guanine-guanine interactions their upper interest among all the homonucleobases studied. They have been subjected to intense investigations in various areas ranging from structural biology and medicinal chemistry – guanine-rich sequences are abundant in telomeric ends of chromosomes and promoter regions of DNA, and are capable of forming G-quartet based structures– to material science and nanotechnology. This Thesis, organized into five Chapters, describes mainly some recent advances in the form and function provided by self-assembly of guanine based systems. More generally, Chapter 4 will focus on the construction of supramolecular self-assemblies whose self-assembling process and self-assembled architectures can be controlled by light as external stimulus. Chapter 1 will describe some of the many recent studies of G-quartets in the general area of nanoscience. Natural G- quadruplexes can be useful motifs to build new structures and biomaterials such as self-assembled nanomachines, biosensors, therapeutic aptamer and catalysts. In Chapters 2-4 it is pointed out the core concept held in this PhD Thesis, i.e. the supramolecular organization of lipophilic guanosine derivatives with photo or chemical addressability. Chapter 2 will mainly focus on the use of cation-templated guanosine derivatives as a potential scaffold for designing functional materials with tailored physical properties, showing a new way to control the bottom-up realization of well-defined nanoarchitectures. In section 2.6.7, the self-assembly properties of compound 28a may be considered an example of open-shell moieties ordered by a supramolecular guanosine architecture showing a new (magnetic) property. Chapter 3 will report on ribbon-like structures, supramolecular architectures formed by guanosine derivatives that may be of interest for the fabrication of molecular nanowires within the framework of future molecular electronic applications. In section 3.4 we investigate the supramolecular polymerizations of derivatives dG 1 and G 30 by light scattering technique and TEM experiments. The obtained data reveal the presence of several levels of organization due to the hierarchical self-assembly of the guanosine units in ribbons that in turn aggregate in fibrillar or lamellar soft structures. The elucidation of these structures furnishes an explanation to the physical behaviour of guanosine units which display organogelator properties. Chapter 4 will describe photoresponsive self-assembling systems. Numerous research examples have demonstrated that the use of photochromic molecules in supramolecular self-assemblies is the most reasonable method to noninvasively manipulate their degree of aggregation and supramolecular architectures. In section 4.4 we report on the photocontrolled self-assembly of modified guanosine nucleobase E-42: by the introduction of a photoactive moiety at C8 it is possible to operate a photocontrol over the self-assembly of the molecule, where the existence of G-quartets can be alternately switched on and off. In section 4.5 we focus on the use of cyclodextrins as photoresponsive host-guest assemblies: αCD–azobenzene conjugates 47-48 (section 4.5.3) are synthesized in order to obtain a photoresponsive system exhibiting a fine photocontrollable degree of aggregation and self-assembled architecture. Finally, Chapter 5 contains the experimental protocols used for the research described in Chapters 2-4.

Numerical modelling of non-load bearing light gauge cold-formed steel frame walls under fire conditions

Recently an innovative composite panel system was developed, where a thin insulation layer was used externally between two plasterboards to improve the fire performance of light gauge cold-formed steel frame walls. In this research, finite-element thermal models of both the traditional light gauge cold-formed steel frame wall panels with cavity insulation and the new light gauge cold-formed steel frame composite wall panels were developed to simulate their thermal behaviour under standard and realistic fire conditions. Suitable apparent thermal properties of gypsum plasterboard, insulation materials and steel were proposed and used. The developed models were then validated by comparing their results with available fire test results. This article presents the details of the developed finite-element models of small-scale non-load-bearing light gauge cold-formed steel frame wall panels and the results of the thermal analysis. It has been shown that accurate finite-element models can be used to simulate the thermal behaviour of small-scale light gauge cold-formed steel frame walls with varying configurations of insulations and plasterboards. The numerical results show that the use of cavity insulation was detrimental to the fire rating of light gauge cold-formed steel frame walls, while the use of external insulation offered superior thermal protection to them. The effects of real fire conditions are also presented.

Structural and fire behaviour of a new light gauge steel wall system

Fire design is an essential element of the overall design procedure of structural steel members and systems. Conventionally the fire rating of load-bearing stud wall systems made of light gauge steel frames (LSF) is based on approximate prescriptive methods developed on the basis of limited fire tests. This design is limited to standard wall configurations used by the industry. Increased fire rating is provided simply by adding more plasterboards to the stud walls. This is not an acceptable situation as it not only inhibits innovation and structural and cost efficiencies but also casts doubt over the fire safety of these light gauge steel stud wall systems. Hence a detailed fire research study into the performance and effectiveness of a recently developed innovative composite panel wall system was undertaken at Queensland University of Technology using both full scale fire tests and numerical studies. Experimental results of LSF walls using the new composite panels under axial compression load have shown the improvement in fire performance and fire resistance rating. Numerical analyses are currently being undertaken using the finite element program ABAQUS. Measured temperature profiles of the studs are used in the numerical models and the results are used to calibrate against full scale test results. The validated model will be used in a detailed parametric study with an aim to develop suitable design rules within the current cold-formed steel structures and fire design standards. This paper will present the results of experimental and numerical investigations into the structural and fire behaviour of light gauge steel stud walls protected by the new composite panel. It will demonstrate the improvements provided by the new composite panel system in comparison to traditional wall systems.

Full scale fire tests of a new light gauge steel floor-ceiling system

Cold-formed steel members can be assembled in various combinations to provide cost-efficient and safe light gauge floor systems for buildings. Such Light gauge Steel Framing (LSF) systems are widely accepted in industrial and commercial building construction. An example application is in floor-ceiling systems. Light gauge steel floor-ceiling systems must be designed to serve as fire compartment boundaries and provide adequate fire resistance. Fire-rated floor-ceiling assemblies formed with new materials and construction methodologies have been increasingly used in buildings. However, limited research has been undertaken in the past and hence a thorough understanding of their fire resistance behaviour is not available. Recently a new composite floor-ceiling system has been developed to provide higher fire rating under standard fire conditions. But its increased fire rating could not be determined using the currently available design methods. Therefore a research project was carried out to investigate its structural and fire resistance behaviour under standard fire conditions. In this research project full scale experimental tests of the new LSF floor system based on a composite ceiling unit were undertaken using a gas furnace at the Queensland University of Technology. Both the conventional and the new steel floor-ceiling systems were tested under structural and fire loads. Full scale fire tests provided a good understanding of the fire behaviour of the LSF floor-ceiling systems and confirmed the superior performance of the new composite system. This paper presents the details of this research into the structural and fire behaviour of light gauge steel floor systems protected by the new composite panel, and the results.

Improvements to the fire performance of light gauge steel floor systems

Light gauge steel frame (LSF) structures are increasingly used in commercial and residential buildings because of their non-combustibility, dimensional stability and ease of installation. A common application is in floor-ceiling systems. The LSF floor-ceiling systems must be designed to serve as fire compartment boundaries and provide adequate fire resistance. Fire-rated floor-ceiling assemblies have been increasingly used in buildings. However, limited research has been undertaken in the past and hence a thorough understanding of their fire resistance behaviour is not available. Recently a new composite floor-ceiling system has been developed to provide higher fire rating. But its increased fire rating could not be determined using the currently available design methods. Therefore a research project was conducted to investigate its structural and fire resistance behaviour under standard fire conditions. This paper presents the results of full scale experimental investigations into the structural and fire behaviour of the new LSF floor system protected by the composite ceiling unit. Both the conventional and the new floor systems were tested under structural and fire loads. It demonstrates the improvements provided by the new composite panel system in comparison to conventional floor systems. Numerical studies were also undertaken using the finite element program ABAQUS. Measured temperature profiles of floors were used in the numerical analyses and their results were compared with fire test results. Tests and numerical studies provided a good understanding of the fire behaviour of the LSF floor-ceiling systems and confirmed the superior performance of the new composite system.

Numerical modelling of light gauge cold-formed steel compression members subjected to distortional buckling at elevated temperatures

Fire safety design of building structures has received greater attention in recent times due to continuing loss of properties and lives during fires. However, fire performance of light gauge cold-formed steel structures is not well understood despite its increased usage in buildings. Cold-formed steel compression members are susceptible to various buckling modes such as local and distortional buckling and their ultimate strength behaviour is governed by these buckling modes. Therefore a research project based on experimental and numerical studies was undertaken to investigate the distortional buckling behaviour of light gauge cold-formed steel compression members under simulated fire conditions. Lipped channel sections with and without additional lips were selected with three thicknesses of 0.6, 0.8, and 0.95 mm and both low and high strength steels (G250 and G550 steels). More than 150 compression tests were undertaken first at ambient and elevated temperatures. Finite element models of the tested compression members were then developed by including the degradation of mechanical properties with increasing temperatures. Comparison of finite element analysis and experimental results showed that the developed finite element models were capable of simulating the distortional buckling and strength behaviour at ambient and elevated temperatures up to 800 °C. The validated model was used to determine the effects of mechanical properties, geometric imperfections and residual stresses on the distortional buckling behaviour and strength of cold-formed steel columns. This paper presents the details of the numerical study and the results. It demonstrated the importance of using accurate mechanical properties at elevated temperatures in order to obtain reliable strength characteristics of cold-formed steel columns under fire conditions.

Numerical and experimental studies of cold-formed steel floor systems under standard fire conditions

Light gauge cold-formed steel frame (LSF) structures are increasingly used in industrial, commercial and residential buildings because of their non-combustibility, dimensional stability, and ease of installation. A floor-ceiling system is an example of its applications. LSF floor-ceiling systems must be designed to serve as fire compartment boundaries and provide adequate fire resistance. Fire rated floor-ceiling assemblies formed with new materials and construction methodologies have been increasingly used in buildings. However, limited research has been undertaken in the past and hence a thorough understanding of their fire resistance behaviour is not available. Recently a new composite panel in which an external insulation layer is used between two plasterboards has been developed at QUT to provide a higher fire rating to LSF floors under standard fire conditions. But its increased fire rating could not be determined using the currently available design methods. Research on LSF floor systems under fire conditions is relatively recent and the behaviour of floor joists and other components in the systems is not fully understood. The present design methods thus require the use of expensive fire protection materials to protect them from excessive heat increase during a fire. This leads to uneconomical and conservative designs. Fire rating of these floor systems is provided simply by adding more plasterboard sheets to the steel joists and such an approach is totally inefficient. Hence a detailed fire research study was undertaken into the structural and thermal performance of LSF floor systems including those protected by the new composite panel system using full scale fire tests and extensive numerical studies. Experimental study included both the conventional and the new steel floor-ceiling systems under structural and fire loads using a gas furnace designed to deliver heat in accordance with the standard time- temperature curve in AS 1530.4 (SA, 2005). Fire tests included the behavioural and deflection characteristics of LSF floor joists until failure as well as related time-temperature measurements across the section and along the length of all the specimens. Full scale fire tests have shown that the structural and thermal performance of externally insulated LSF floor system was superior than traditional LSF floors with or without cavity insulation. Therefore this research recommends the use of the new composite panel system for cold-formed LSF floor-ceiling systems. The numerical analyses of LSF floor joists were undertaken using the finite element program ABAQUS based on the measured time-temperature profiles obtained from fire tests under both steady state and transient state conditions. Mechanical properties at elevated temperatures were considered based on the equations proposed by Dolamune Kankanamge and Mahendran (2011). Finite element models were calibrated using the full scale test results and used to further provide a detailed understanding of the structural fire behaviour of the LSF floor-ceiling systems. The models also confirmed the superior performance of the new composite panel system. The validated model was then used in a detailed parametric study. Fire tests and the numerical studies showed that plasterboards provided sufficient lateral restraint to LSF floor joists until their failure. Hence only the section moment capacity of LSF floor joists subjected to local buckling effects was considered in this research. To predict the section moment capacity at elevated temperatures, the effective section modulus of joists at ambient temperature is generally considered adequate. However, this research has shown that it leads to considerable over- estimation of the local buckling capacity of joist subject to non-uniform temperature distributions under fire conditions. Therefore new simplified fire design rules were proposed for LSF floor joist to determine the section moment capacity at elevated temperature based on AS/NZS 4600 (SA, 2005), NAS (AISI, 2007) and Eurocode 3 Part 1.3 (ECS, 2006). The accuracy of the proposed fire design rules was verified with finite element analysis results. A spread sheet based design tool was also developed based on these design rules to predict the failure load ratio versus time, moment capacity versus time and temperature for various LSF floor configurations. Idealised time-temperature profiles of LSF floor joists were developed based on fire test measurements. They were used in the detailed parametric study to fully understand the structural and fire behaviour of LSF floor panels. Simple design rules were also proposed to predict both critical average joist temperatures and failure times (fire rating) of LSF floor systems with various floor configurations and structural parameters under any given load ratio. Findings from this research have led to a comprehensive understanding of the structural and fire behaviour of LSF floor systems including those protected by the new composite panel, and simple design methods. These design rules were proposed within the guidelines of the Australian/New Zealand, American and European cold- formed steel structures standard codes of practice. These may also lead to further improvements to fire resistance through suitable modifications to the current composite panel system.

Experimental studies of non-load bearing steel wall systems under fire conditions

Fire safety of buildings has been recognised as very important by the building industry and the community at large. Traditionally, increased fire rating is provided by simply adding more plasterboards to light gauge steel frame (LSF) walls, which is inefficient. Many research studies have been undertaken to investigate the thermal behaviour of traditional LSF stud wall systems under standard fire conditions. However, no research has been undertaken on the thermal behaviour of LSF stud walls using the recently proposed composite panel. Extensive fire testing of both non-load bearing and load bearing wall panels was conducted in this research based on the standard time-temperature curve in AS1530.4. Three groups of LSF wall specimens were tested with no insulation, cavity insulation and the new composite panel based on an external insulation layer between plasterboards. This paper presents the details of this experimental study into the thermal performance of non-load bearing walls lined with various configurations of plasterboard and insulation. Extensive descriptive and numerical results of the tested non-load bearing wall panels given in this paper provide a thorough understanding of their thermal behaviour, and valuable time-temperature data that can be used to validate numerical models. Test results showed that the innovative composite stud wall systems outperformed the traditional stud wall systems in terms of their thermal performance, giving a much higher fire rating.

Thermal performance of load bearing cold-formed steel walls under fire conditions using numerical studies

Cold–formed Light gauge Steel Frame (LSF) wall systems are increasingly used in low-rise and multi-storey buildings and hence their fire safety has become important in the design of buildings. A composite LSF wall panel system was developed recently, where a thin insulation was sandwiched between two plasterboards to improve the fire performance of LSF walls. Many experimental and numerical studies have been undertaken to investigate the fire performance of non-load bearing LSF wall under standard conditions. However, only limited research has been undertaken to investigate the fire performance of load bearing LSF walls under standard and realistic design fire conditions. Therefore in this research, finite element thermal models of both the conventional load bearing LSF wall panels with cavity insulation and the innovative LSF composite wall panel were developed to simulate their thermal behaviour under standard and realistic design fire conditions. Suitable thermal properties were proposed for plasterboards and insulations based on laboratory tests and available literature. The developed models were then validated by comparing their results with available fire test results of load bearing LSF wall. This paper presents the details of the developed finite element models of load bearing LSF wall panels and the thermal analysis results. It shows that finite element models can be used to simulate the thermal behaviour of load bearing LSF walls with varying configurations of insulations and plasterboards. Failure times of load bearing LSF walls were also predicted based on the results from finite element thermal analyses. Finite element analysis results show that the use of cavity insulation was detrimental to the fire rating of LSF walls while the use of external insulation offered superior thermal protection to them. Effects of realistic design fire conditions are also presented in this paper.

Numerical modelling of load bearing light gauge steel frame wall systems exposed to realistic design fires

Fire safety has become an important part in structural design due to the ever increasing loss of properties and lives during fires. Conventionally the fire rating of load bearing wall systems made of Light gauge Steel Frames (LSF) is determined using fire tests based on the standard time-temperature curve in ISO834 [1]. However, modern commercial and residential buildings make use of thermoplastic materials, which mean considerably high fuel loads. Hence a detailed fire research study into the fire performance of LSF walls was undertaken using realistic design fire curves developed based on Eurocode parametric [2] and Barnett’s BFD [3] curves using both full scale fire tests and numerical studies. It included LSF walls without cavity insulation, and the recently developed externally insulated composite panel system. This paper presents the details of finite element models developed to simulate the full scale fire tests of LSF wall panels under realistic design fires. Finite element models of LSF walls exposed to realistic design fires were developed, and analysed under both transient and steady state fire conditions using the measured stud time-temperature curves. Transient state analyses were performed to simulate fire test conditions while steady state analyses were performed to obtain the load ratio versus time and failure temperature curves of LSF walls. Details of the developed finite element models and the results including the axial deformation and lateral deflection versus time curves, and the stud failure modes and times are presented in this paper. Comparison with fire test results demonstrate the ability of developed finite element models to predict the performance and fire resistance ratings of LSF walls under realistic design fires.

Fire performance of cold-formed steel wall panels and prediction of their fire resistance rating

Recent research at the Queensland University of Technology has investigated the structural and thermal behaviour of load bearing Light gauge Steel Frame (LSF) wall systems made of 1.15 mm G500 steel studs and varying plasterboard and insulation configurations (cavity and external insulation) using full scale fire tests. Suitable finite element models of LSF walls were then developed and validated by comparing with test results. In this study, the validated finite element models of LSF wall panels subject to standard fire conditions were used in a detailed parametric study to investigate the effects of important parameters such as steel grade and thickness, plasterboard screw spacing, plasterboard lateral restraint, insulation materials and load ratio on their performance under standard fire conditions. Suitable equations were proposed to predict the time–temperature profiles of LSF wall studs with eight different plasterboard-insulation configurations, and used in the finite element analyses. Finite element parametric studies produced extensive fire performance data for the LSF wall panels in the form of load ratio versus time and critical hot flange (failure) temperature curves for eight wall configurations. This data demonstrated the superior fire performance of externally insulated LSF wall panels made of different steel grades and thicknesses. It also led to the development of a set of equations to predict the important relationship between the load ratio and the critical hot flange temperature of LSF wall studs. Finally this paper proposes a simplified method to predict the fire resistance rating of LSF walls based on the two proposed set of equations for the load ratio–hot flange temperature and the time–temperature relationships.

Design of light gauge steel roofing systems subject to high wind forces

Light gauge steel roofing systems made of thin profiled roof sheeting and battens are used commonly in residential, industrial and commercial buildings. Their critical design load combination is that due to wind uplift forces that occur during high wind events such as tropical cyclones and thunderstorms. However, premature local failures at their screw connections have been a concern for many decades since cyclone Tracy that devastated Darwin in 1974. Extensive research that followed cyclone Tracy on the pull-through and pull-out failures of roof sheeting to batten connections has significantly improved the safety of roof sheeting. However, this has made the batten to rafter/truss connection the weakest, and recent wind damage investigations have shown the failures of these connections and the resulting loss of entire roof structures. Therefore an experimental research program using both small scale and full scale air-box tests is currently under way to investigate the pull-through failures of thin-walled steel battens under high wind uplift forces. Tests have demonstrated that occurrence of pull-through failures in the bottom flanges of steel batttens and the need to develop simple test and design methods as a function of many critical parameters such as steel batten geometry, thickness and grade, screw fastener sizes and other fastening details. This paper presents the details of local failures that occur in light fauge roofing systems, a review of the current design and test methods for steel battens and associated short comings, and the test results obtained to date on pull-through failures of battens from small scale and full scale tests. Finally, it proposes the use of suitable small scale test methods that can be used by both researchers and manufacturers of such screw-fastened light gauge steel batten systems.

Fire performance and design of load bearing light gauge steel frame wall systems exposed to realistic design fires

This paper presents the fire performance results of light gauge steel frame (LSF) walls lined with single and double plasterboards, and externally insulated with rock fibre insulation as obtained using a finite element analysis based parametric study. A validated numerical model was used to study the influence of various fire curves developed for a range of compartment characteristics. Data from the parametric study was utilized to develop a simplified method to predict the fire resistance ratings of LSF walls exposed to realistic design fire curves. Further, this paper also presents the details of suitable fire design rules based on current cold-formed steel standards and the modifications proposed by previous researchers. Of these the recently developed design rules by Gunalan and Mahendran [1] were investigated to determine their applicability to predict the axial compression strengths and fire resistance ratings (FRR) of LSF walls exposed to realistic design fires. Finally, the stud failure times obtained from fire design rules and finite element studies were compared for LSF walls lined with single and double plasterboards, and externally insulated with rock fibres under realistic design fire curves.

Fire resistance rating of light gauge steel frame walls exposed to realistic design fires : a review and development of time equivalent approach

This paper presents the details of research undertaken on the development of an energy based time equivalent approach for light gauge steel frame (LSF) walls. This research utilized an energy based time equivalent approach to obtain the fire resistance ratings (FRR) of LSF walls exposed to realistic design fires with respect to standard fire exposure [1]. It is based on the equal area concept of fire severity and relates to the amount of energy transferred to the member. The proposed method was used to predict the fire resistance of single and double plasterboard lined and externally insulated LSF walls. The predicted fire resistance ratings were compared with the results from finite element analyses and fire design rules for three different wall configurations. This paper presents the review of the available time equivalent approaches and the development of energy based time equivalent approach for the prediction of fire resistance ratings of LSF walls exposed to realistic design fires.

Fire design rules of light gauge steel frame walls – a review

Cold-formed steel members are widely used in load bearing Light gauge steel frame (LSF) wall systems with plasterboard linings on both sides. However, these thin-walled steel sections heat up quickly and lose their strength under fire conditions despite the protection provided by plasterboards. Hence there is a need for simple fire design rules to predict their load capacities and fire resistance ratings. During fire events, the LSF wall studs are subjected to non-uniform temperature distributions that cause thermal bowing, neutral axis shift and magnification effects and thus resulting in a combined axial compression and bending action on the LSF wall studs. In this research a series of full scale fire tests was conducted first to evaluate the performance of LSF wall systems with eight different wall configurations under standard fire conditions. Finite element models of LSF walls were then developed, analysed under transient and steady state conditions, and validated using full scale fire tests. Using the results from fire tests and finite element analyses, a detailed investigation was undertaken into the prediction of axial compression strength and failure times of LSF wall studs in standard fires using the available fire design rules based on Australian, American and European standards. The results from both fire tests and finite element analyses were used to investigate the ability of these fire design rules to include the complex effects of non-uniform temperature distributions and their accuracy in predicting the axial compression strengths of wall studs and the failure times. Suitable modifications were then proposed to the fire design rules. This paper presents the details of this investigation into the accuracy of using currently available fire design rules of LSF walls and the results.