B16-Test Beamline
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Diamond Proposal Number(s):
[28395]
Open Access
Abstract: Carbon fibre composites are widely used in low specific stiffness and high strength structures such as airframes. Compressive loading of these assemblies can lead to buckling and localised deformation around defects and imperfections that can hinder performance and lead to overengineering via excessive safety factors. Synchrotron X-Ray Diffraction (SXRD) has recently been shown to be capable of performing lattice strain mapping within carbon fibre composites at the microscale, a previously unprecedented resolution. In this study SXRD and radiography was performed on carbon fibre composite columns produced via two different methods (standard lamination and half square) at a range of different load states: unbuckled, one-third of the buckling load and post buckling. The results provide quantitative insights into the impact of these different production methods on lattice strain and fibre orientation, as well as the influence these factors have on reducing buckling load (by up to 22%). As well as being the first use of SXRD on industrially representative full-size carbon fibre samples, these insights provide invaluable detail into the factors which limit performance and the origins of column failure; crucial factors required to optimise structural design, production and loading capability.
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Nov 2023
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I22-Small angle scattering & Diffraction
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Abstract: In situations where the stereoregularity of the polymer chains permits, crystals can form in synthetic or natural polymers. These crystals have an immense impact on the properties of the polymeric material. Typically polymers crystallized from a quiescent melt form spherulites, but where the melt exhibits a level of anisotropy, the crystalline morphology, is quite different to the spherulitic structure, although it may well contain chain-folded lamellar crystals. We consider a number of different systems in which the anisotropy has developed in different ways. Despite these differences, there are strong features in common within the semi-crystalline polymer morphology. We consider the strain-induced crystallization in deformed natural rubber, in sheared melts containing both self-assembling nanoparticles and engineered nanoparticles, and during extrusion as part of fused granular deposition-based 3D printing.
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Oct 2023
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B22-Multimode InfraRed imaging And Microspectroscopy
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Diamond Proposal Number(s):
[27504]
Open Access
Abstract: Triboelectric nanogenerator (TENG), a device that can convert mechanical energy into electricity based on the principle of triboelectrification, has gained tremendous attention since its first discovery in 2012. Although TENG has versatile applications in energy harvesting and self-powered sensing, its commercialization is still limited by the low power output. Recently, metal-organic frameworks (MOFs), with their large surface area and excellent tunability, have been explored to enhance the electrical performance of TENG. Herein, we synthesized nanoparticles of hydrophobic zeolitic imidazolate framework ZIF-71 (RHO topology) and its non-porous counterpart ZIF-72 (LCS topology), which were subsequently incorporated in a polydimethylsiloxane (PDMS) matrix as filler materials. By modifying the topology of ZIF nanofillers, we found the dielectric constant and surface adhesion of composites are both enhanced, thereby generating significantly higher triboelectric output. Moreover, we show the resultant ZIF/PDMS nanocomposite films exhibit enhanced triboelectric properties and long-term stability under cyclic mechanical loading. After integrating the prepared nanocomposite films into TENG devices, we accomplished the peak output voltage and current of 578 V and 19 μA for thin films (3 ×3 cm2, thickness ∼0.33 mm), respectively, by embedding 1 wt % of ZIF-72 nanoparticles into PDMS matrix, with an instantaneous maximum power density of ∼5 W m−2. In this study, the mechanism of improved TENG performance by incorporating MOF nanoparticles has, for the first time, been revealed through nanoscale-resolved mechanical and chemical studies. Furthermore, the practicality of MOF-based TENG was demonstrated by harvesting energy from oscillatory motions, for powering up commercial microelectronics, transmitting electrical signals remotely, and functioning as a self-powered Morse code generator.
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Sep 2023
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Open Access
Abstract: Poly(Ni-btt), an organometallic coordination polymer (OMCP) characterized by the coordination between benzene-1,2,4,5-tetrakis(thiolate) (btt) and Ni2+ ions, has been recognized as a promising p-type thermoelectric material. In this study, we employed a constitutional isomer based on benzene-1,2,3,4-tetrakis(thiolate) (ibtt) to generate the corresponding isomeric polymer, poly(Ni-ibtt). Comparative analysis of poly(Ni-ibtt) and poly(Ni-btt) reveals several common infrared (IR) and Raman features attributed to their similar square-planar nickel-sulfur (Ni-S) coordination. Nevertheless, these two polymer isomers exhibit substantially different backbone geometries. Poly(Ni-btt) possesses a linear backbone, whereas poly(Ni-ibtt) exhibits a more undulating, zigzag-like structure. Consequently, poly(Ni-ibtt) demonstrates slightly higher solubility and an increased bandgap in comparison to poly(Ni-btt). The most noteworthy dissimilarity, however, manifests in their thermoelectric properties. While poly(Ni-btt) exhibits p-type behaviour, poly(Ni-ibtt) demonstrates n-type carrier characteristics. This intriguing divergence prompted further investigation into the influence of OMCP backbone geometry on the electronic structure and, particularly, the thermoelectric properties of these materials.
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Sep 2023
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DL-SAXS-Offline SAXS and Sample Environment Development
I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[28661, 29137, 27721]
Open Access
Abstract: In situ small-angle X-ray scattering (SAXS) is a powerful technique for characterizing block-copolymer nano-object formation during polymerization-induced self-assembly. To work effectively in situ, it requires high intensity X-rays which enable the short acquisition times required for real-time measurements. However, routine access to synchrotron X-ray sources is expensive and highly competitive. Flow reactors provide an opportunity to obtain temporal resolution by operating at a consistent flow rate. Here, we equip a flow-reactor with an X-ray transparent flow-cell at the outlet which facilitates the use of a low-flux laboratory SAXS instrument for in situ monitoring. The formation and morphological evolution of spherical block copolymer nano-objects was characterized during reversible addition fragmentation chain transfer polymerization of diacetone acrylamide in the presence of a series of poly(dimethylacrylamide) (PDMAm) macromolecular chain transfer agents with varying degrees of polymerization. SAXS analysis indicated that during the polymerization, highly solvated, loosely defined aggregates form after approximately 100 s, followed by expulsion of solvent to form well-defined spherical particles with PDAAm cores and PDMAm stabilizer chains, which then grow as the polymerization proceeds. Analysis also indicates that the aggregation number (Nagg) increases during the reaction, likely due to collisions between swollen, growing nanoparticles. In situ SAXS conducted on PISA syntheses using different PDMAm DPs indicated a varying conformation of the chains in the particle cores, from collapsed chains for PDMAm47 to extended chains for PDMAm143. At high conversion, the final Nagg decreased as a function of increasing PDMAm DP, indicating increased steric stabilization afforded by the longer chains which is reflected by a decrease in both core diameter (from SAXS) and hydrodynamic diameter (from DLS) for a constant core DP of 400.
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Aug 2023
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I12-JEEP: Joint Engineering, Environmental and Processing
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Diamond Proposal Number(s):
[28460]
Open Access
Abstract: This study focuses on the use of methacrylic acid polymers synthesised via the Reversible Addition Fragmentation chain Transfer (RAFT) polymerisation method for the production of amorphous solid dispersions (ASDs) by ball milling, to kinetically solubilize a poorly water-soluble model drug. The solid-state characteristics and the physical stability of the formulations were investigated using X-ray diffraction, differential scanning calorimetry, and infrared spectroscopy. This was followed by dissolution studies in different media. It was discovered that the acidic polymers of methacrylic acid were capable of interacting with the weakly basic drug lidocaine and its hydrochloride salt form to produce ASDs when a polymer to drug ratio of 70:30 w/w was used. The ASDs remained amorphous following storage under accelerated aging conditions (40 °C and 75% relative humidity) over 8 months. Fast dissolution and increased lidocaine solubility in different media were obtained from the ASDs owing to the reduced microenvironment pH and enhanced solubilization of the drug caused by the presence of the acidic polymer in the formulation. Production of ASDs using well-defined RAFT-synthesised acidic polymers is a promising formulation strategy to enhance the pharmaceutical properties of basic poorly water-soluble drugs.
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Aug 2023
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[28022]
Abstract: Guanine (G) hydrogels are very attractive materials made by the supramolecular organization of G-derivatives in water. In this paper, hydrogels composed by guanosine 5’-monophosphate (GMP) and guanosine (Gua), that make long, flexible and knotted G-quadruplexes, were investigated by Small- and Wide-angle X-ray Scattering (SAXS and WAXS) to comprehend the origin of the unique orientational properties. The SAXS intensity, analysed at a fixed scattering vector modulus Q as a function of the polar angle, allowed us to derive the Maier-Saupe orientation parameter m. The strong dependence of m on hydrogel composition and temperature demonstrated that the preferred orientation is controlled by the quadruplex surface charge and flexibility. Indeed, a possible correlation between the orientation parameter m and the quadruplex-to-quadruplex lateral interactions was explored. Results confirmed that the balance between attractive and repulsive interactions plays a main role in the orientational anisotropy: quadruplex clusters lose their orientational property when attractive interactions decrease. The key role of the number of negative charges-per-unit-length of the G-quadruplex filaments was confirmed by Atomic Force Microscopy (AFM) observations. Indeed, directionality histograms showed that in the presence of large amount of Gua, G-quadruplexes follow other preferential orientations than those related to the strong interactions with the K+ pattern on the mica surface. The fact that lateral quadruplex-to-quadruplex interactions, even in the presence of external (opposing) forces, can tune the hydrogel alignment in a given preferred direction opens novel possibilities for scaffold/3D printing applications.
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Aug 2023
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I14-Hard X-ray Nanoprobe
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Open Access
Abstract: Over recent decades, there has been a dramatic increase in the manufacture of engineered nanomaterials, which has inevitably led to their environmental release. Zinc oxide (ZnO) is among the more abundant nanomaterial manufactured due to its advantageous properties, used for piezoelectric, semiconducting, and antibacterial purposes. Plastic waste is ubiquitous and may break down or delaminate into smaller microplastics, leaving open the question of whether these small polymers may alter the fate of ZnO through adsorption within aquatic media (tap-water and seawater). Here, scanning electron microscopy analysis confirms the effective Zn nano/microstructures adsorption onto polystyrene surfaces after only 24-h incubation in the aquatic media. After pre-aging the nanomaterials for 7-days in different environmental media, nanoprobe X-ray absorption near-edge spectroscopy analysis reveals significant ZnO transformation toward Zn-sulfide and Zn-phosphate. The interaction between a commercial ZnO-based sunscreen with polystyrene and a cleanser consumer containing microbeads with ZnO nanomaterials is also studied, revealing the adsorption of transformed Zn-species in the microplastics surfaces, highlighting the environmental relevancy of this work. Understanding the structural and functional impacts of the microplastics/ZnO complexes, and how they evolve, will provide insights into their chemical nature, stability, transformations, and fate, which is key to predicting their bioreactivity in the environment.
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Jul 2023
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I22-Small angle scattering & Diffraction
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Open Access
Abstract: Polymorphism of semicrystalline polymers has significant influence on their physical properties, with each form having its advantages and disadvantages. However, real-life polymer processing often results in different coexisting crystal polymorphs, and it remains a challenge to determine their shape, spatial distribution, and volume fraction. Here, i-polypropylene (i-PP) sheets containing both α- and β-forms were prepared either by adding β-nucleating agent or by fiber pulling-induced crystallization. By adding a compatible dye that is partially rejected from the growing crystalline aggregates (spherulites and cylindrites), we visualize the shape of these objects in 3D using two-photon fluorescence confocal microscopy. To distinguish between crystal forms, we take advantage of the difference in dye-retaining ability of the α- and β-aggregates. Even in 2D, fluorescence microscopy (FM) distinguishes the two crystal forms better than polarized microscopy. In 3D imaging, the volume fraction and spatial distribution of α- and β-forms in different morphological types could be determined quantitatively. Morphologies described as α-teeth, β-fans, and α-teardrops were visualized for the first time in 3D. Furthermore, internal and surface microcracks were seen to be associated predominantly with the β-form and around the fiber. Spatial distribution of α- and β-forms was also determined by scanning with a synchrotron X-ray beam. Good agreement was obtained with 3D microscopy, but XRD could not match the detail obtainable by the tomography. The work demonstrates the ability of the 3D imaging method to distinguish different crystal forms and their specific morphologies.
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Jul 2023
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I22-Small angle scattering & Diffraction
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Diamond Proposal Number(s):
[30206]
Open Access
Abstract: Dynamic covalent chemistry has been exploited to prepare numerous examples of adaptable polymeric materials that exhibit unique properties. Herein, the chemical adsorption of aldehyde-functional diblock copolymer spherical nanoparticles onto amine-functionalized surface-grafted polymer brushes via dynamic Schiff base chemistry is demonstrated. Initially, a series of cis-diol-functional sterically-stabilized spheres of 30–250 nm diameter were prepared via reversible addition–fragmentation chain transfer (RAFT) aqueous dispersion polymerization. The pendent cis-diol groups within the steric stabilizer chains of these precursor nanoparticles were then oxidized using sodium periodate to produce the corresponding aldehyde-functional spheres. Similarly, hydrophilic cis-diol-functionalized methacrylic brushes grafted from a planar silicon surface using activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) were selectively oxidized to generate the corresponding aldehyde-functional brushes. Ellipsometry and X-ray photoelectron spectroscopy were used to confirm brush oxidation, while scanning electron microscopy studies demonstrated that the nanoparticles did not adsorb onto a cis-diol-functional precursor brush. Subsequently, the aldehyde-functional brushes were treated with excess small-molecule diamine, and the resulting imine linkages were converted into secondary amine bonds via reductive amination. The resulting primary amine-functionalized brushes formed multiple dynamic imine bonds with the aldehyde-functional diblock copolymer spheres, leading to a mean surface coverage of approximately 0.33 on the upper brush layer surface, regardless of the nanoparticle size. Friction force microscopy studies of the resulting nanoparticle-decorated brushes enabled calculation of friction coefficients, which were compared to that measured for the bare aldehyde-functional brush. Friction coefficients were reasonably consistent across all surfaces except when particle size was comparable to the size of the probe tip. In this case, differences were ascribed to an increase in contact area between the tip and the brush-nanoparticle layer. This new model system enhances our understanding of nanoparticle adsorption onto hydrophilic brush layers.
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Jul 2023
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