Cure monitoring of CFRP composites by dynamic mechanical analyser

The cure characteristics of carbon/MTM44-1 epoxy composite prepreg and neat MTM44-1 epoxy resin are monitored using a dynamic mechanical analyser (DMA). This study also assesses whether the simple containment device recommended by the DMA manufacturer for powder and gel is suitable for prepregs. The device is a disposable 0.1-mm thick stainless steel pocket. The cure behaviour of the packaged materials is compared with that of the unpackaged prepreg. All the samples are cured following the manufacturer's 180°C-isothermal schedule with heating rates of 2 °C/min and 5 °C/min. The tests highlight that: (i) the cure of composite prepregs and resin can be monitored using a DMA; (ii) the stainless steel pocket does not influence the cure of the prepreg and resin; and (iii) the softening and melting of the uncured resin, the resin low viscosity state and the subsequent gelation-vitrification-solidification of the resin are detected with this method

Nitrated cross-linked b-cyclodextrin binders exhibiting low glass transition tempratures

Polymeric binders such as β‐cyclodextrins (βCDs) are used to bind with other constituents of energetic formulations and to prevent accidental ignition. One of the advantages of βCDs is the ability to tune their properties by chemical modification. Here, we synthesised nitrated cross‐linked βCDs (βNCXCDs) to produce new binders for energetic formulations. The cross‐linking of βCD with non‐toxic triethylene glycol diglycidyl ether (TEGDGE, X=T) and poly(ethylene glycol) diglycidyl ethers (PEGDGE, X=P) yielded soft, water soluble oligomeric compounds (βCXCDs) which can improve the processability of energetic formulations and contribute to their desensitisation. When the PEGDGE cross‐linker was used, lower glass transition temperatures were achieved, which extended the operative range of the βCPCD binder to −20 °C. The analogous nitrated systems (βNCXCDs) were therefore synthesised using a 1 : 1 (v/v) ratio of 98 % sulfuric acid/100 % nitric acid or 100 % fuming nitric acid, increasing their solubility in acetone and tetrahydrofuran. The nitrated derivatives were characterised by decomposition temperatures (200 °C) and energies (up to 1750 J g−1) comparable to nitrocellulose. Moreover, the glass transition of the inert βCXCDs at low temperatures (<0 °C) was conserved in the corresponding nitrated βNCXCDs, ensuring the desensitisation of energetic compositions even at low temperatures. This is the first time that nitrated derivatives of βCD with glass transition temperatures below 0 °C have been reported, suggesting such derivatives could make suitable replacements for nitrocellulose and other binders in energetic formulations

Thermomechanical characterisation of cross-linked β-cyclodextrin polyether binders

Cyclodextrins are promising building blocks for the synthesis of industrial binders. A new binder was prepared by cross-linking β-cyclodextrin with variable amounts of polyethylene glycol diglycidyl ether (40–60% w/w) to produce a soft polyether network that was soluble in water and alcohol, and the thermomechanical properties of the binder were determined. Increasing the amount of cross-linker reduced the glass transition temperature of the binder, as determined by differential scanning calorimetry and dynamic mechanical analysis. Cooling experiments revealed sudden stress relief below the glass transition temperature, reflecting the de-bonding of the polymer from the metallic supports. This was prevented by contact with polytetrafluoroethylene tape. Optical microscopy confirmed the stress relief in the form of cracking, and revealed self-healing by reptation, promoted by a higher cross-linker content and temperature. The information gained on the influence of the support medium on the thermomechanical properties of the cross-linked β-cyclodextrins can be used by industry for optimising manufacture and storage methods for new binders

CRIM-TRACK: Sensor system for detection of criminal chemical substances

Detection of illegal compounds requires a reliable, selective and sensitive detection device. The successful device features automated target acquisition, identification and signal processing. It is portable, fast, user friendly, sensitive, specific, and cost efficient. LEAs are in need of such technology. CRIM-TRACK is developing a sensing device based on these requirements. We engage highly skilled specialists from research institutions, industry, SMEs and LEAs and rely on a team of end users to benefit maximally from our prototypes. Currently we can detect minute quantities of drugs, explosives and precursors thereof in laboratory settings. Using colorimetric technology we have developed prototypes that employ disposable sensing chips. Ease of operation and intuitive sensor response are highly prioritized features that we implement as we gather data to feed into machine learning. With machine learning our ability to detect threat compounds amidst harmless substances improves. Different end users prefer their equipment optimized for their specific field. In an explosives-detecting scenario, the end user may prefer false positives over false negatives, while the opposite may be true in a drug-detecting scenario. Such decisions will be programmed to match user preference. Sensor output can be as detailed as the sensor allows. The user can be informed of the statistics behind the detection, identities of all detected substances, and quantities thereof. The response can also be simplified to “yes” vs. “no”. The technology under development in CRIM-TRACK will provide custom officers, police and other authorities with an effective tool to control trafficking of illegal drugs and drug precursors

Validation of data from an artificial sniffer dog by common analytical techniques

CRIM-TRACK, an artificial sniffer dog, employs a colourimetric sensor system to monitor the colour change of chromic dyes when in contact with the vapours of illicit molecules (analytes) for detection and identification of substances. Within, the interaction of illicit chemicals and chromic dyes have been studied in solution using Proton Nuclear Magnetic Resonance ( 1 H NMR) spectroscopy and Ultraviolet-Visible (UV-Vis) spectrophotometry, to validate data generated from detection experiments using CRIM-TRACK sniffer. 1 H-NMR revealed the colour change mechanism induced by benzyl methyl ketone (BMK), a precursor chemical of methamphetamines, was hydrogen bonding between the BMK and specific dye molecules. It also revealed that hexamine (HEX), an explosives precursor, induced a colour change by formation of ion pairs with the specific dye molecules. The colour changes detected by CRIM-TRACK were confirmed by UV-Vis where a shift in absorption wavelength and/or a change in absorbance occurred

Cross-linking of hydroxyl-terminated polyols with triethyleneglycol diglycidyl ether: an alternative to toxic isocyanates

Isocyanates are highly reactive and toxic substances with severe health effects. Certain diisocyanates are restricted under REACH – The European Regulation on Registration, Evaluation, Authorisation and Restriction of Chemicals. Triethyleneglycol diglycidyl ether (TEGDGE) was used as an alternative to toxic isocyanates for the cross-linking of hydroxyl-terminated pre-polymers at 70oC. The effect of three curing accelerators was determined while following the reaction kinetics by 1H-NMR spectroscopy and differential scanning calorimetry (DSC). Polybutadiene (Poly BD R45HT-LO) and acrylic ester (HyTemp 4454) successfully cross-linked in 7–10 days to produce thermally stable networks with low glass transition temperatures, as observed by DSC. Pre-aging the polybutadiene resin promoted cross-linking with TEGDGE. Four energetic compositions were then prepared using cyclotrimethylenetrinitramine (RDX) and pentaerythritoltetranitrate (PETN) as fillers, and polybutadiene (Poly BD R45HT-LO) and acrylic ester (HyTemp 4454) as binders. Both binders successfully cross-linked with TEGDGE in the presence of RDX and PETN, but only PETN was found to be chemically compatible with the cross-linked polymers. These results show that TEGDGE is suitable as a replacement for toxic isocyanates for the cross-linking of hydroxyl-terminated polyols

Understanding and controlling the glass transition of HTPB oligomers

In this paper, we use a combination of experiment and simulation to achieve enhanced levels of synthetic control on the microstructure of the much-used binder material hydroxyl terminated polybutadiene (HTPB). Specifically, we determine the appropriate combination of initiator, temperature and solvent required to dial in the relative contents of trans, cis and vinyl monomeric units. When an alkylithium initiator (TBDMSPLi) is used, the vinyl content increases from 18% to >90% as the polymerization solvent is switched from non-polar to polar. Further, in non-polar solvents, the vinyl content increases from 18% to 40% with decreasing polymerization temperature. The glass transition temperature, Tg, is shown to be strongly affected by the microstructure, covering the very wide range of −95 °C to −25 °C. The Tg values of HTPB oligomers with high vinyl content are exceptionally high (−25 °C) and can be associated with their aliphatic backbones with pendant side-groups structures. The experimental indications that intramolecular degrees of freedom have a dominant effect on Tg are confirmed by Molecular Dynamics simulations. These simulations identify crankshaft flips of main-chain sub-sections as the key mechanism and relate this to the vinyl content; the frequency of these rotations increases by an order of magnitude, as the vinyl content is reduced from 90% to 20%. The generic mechanistic understanding gained here into what constitutes a “good binder” material is readily transferrable to the potential identification of future candidate systems with very different chemistries

Classification of colorimetric sensor data using time series

Colorimetric sensors are widely used as pH indicators, medical diagnostic devices and detection devices. The colorimetric sensor captures the color changes of a chromic chemical (dye) or array of chromic chemicals when exposed to a target substance (analyte). Sensing is typically carried out using the difference in dye color before and after exposure. This approach neglects the kinetic response, that is, the temporal evolution of the dye, which potentially contains additional information. We investigate the importance of the kinetic response by collecting a sequence of images over time. We applied end-to-end learning using three different convolution neural networks (CNN) and a recurrent network. We compared the performance to logistic regression, k-nearest-neighbor and random forest, where these methods only use the difference color from start to end as feature vector. We found that the CNNs were able to extract features from the kinetic response profiles that significantly improves the accuracy of the sensor. Thus, we conclude that the kinetic responses indeed improves the accuracy, which paves the way for new and better chemical sensors based on colorimetric responses

Synthesis, structure characterization, Hirshfeld surface analysis, and computational studies of 3-nitro-1,2,4-triazol-5-one (NTO):acridine

To modify the physical features and extend applications of the 3-nitro-1,2,4-triazol-5-one (NTO), we synthesized NTO with acridine (ACR) at a molar ratio of 1:1, a neutralization reaction. Through altering the chemical composition, it was possible to alter physical properties such as thermal stability, free space (voids), packing coefficient, crystal density, difference in pKa of co-formers, morphology, solubility, and impact sensitivity, and detonation parameters . It appears that physical attributes could be entirely altered. Single-crystal and powder X-ray diffraction methods, infrared spectroscopy, mass spectrometry, nuclear magnetic resonance spectroscopy (1H-NMR and 13C-NMR), and thermal analysis were utilized to comprehensively characterize and confirm the formation of the structure of NTO:ACR. The substantial hydrogen bond interactions and planar layered structures observed between the cations and anions generated a complex 3D network, providing insight into the structure–property interrelationship. One intriguing feature discovered is the layered structure present in NTO:ACR, which may be responsible for the low impact sensitivity. According to the experimental results, NTO:ACR showed good thermal stability (Td = 229 °C) and outstanding impact sensitivity (IS = 100 J). Detonation velocity and pressure were calculated using the EXPLO5 software program and found to be 7006 m·s−1 and 20.02 GPa, respectively.This study was funded by the Scientific and Technological Research Council of Türkiye-TUBITAK-BIDEB 2219-International Postdoctoral Research Fellowship Program (Grant number:1059B192100006)

Preformulation studies and bioavailability enhancement of curcumin with a ‘two in one’ PEG-β-cyclodextrin polymer

Drug delivery systems are used to improve the biopharmaceutical properties of curcumin. Our aim was to investigate the effect of a water-soluble ‘two in one’ polymer containing covalently bonded PEG and βCD moieties (βCPCD) on the solubility and bioavailability of curcumin and compare it to a polymeric β-cyclodextrin (βCDP) cross-linked with epichlorohydrin. Phase-solubility and dynamic light scattering (DLS) experiments showed that the solubility of curcumin increased significantly in 10 m/m % βCPCD and βCDP solutions, but βCPCD–curcumin particles had higher hydrodynamic volume. The formation of the βCPCD–curcumin complex in solution and sedimented phase was confirmed by NMR spectroscopy. Biocompatibility and permeability experiments were performed on Caco-2 cells. Polymers did not show cytotoxicity up to 10 m/m % and βCPCD significantly increased the permeability of curcumin. DLS measurements revealed that among the interaction of polymers with mucin, βCPCD formed bigger aggregates compared to βCDP. Curcumin complexes were lyophilized into capsules and structurally characterized by micro-CT spectroscopy. Drug release was tested in a pH 1.2 medium. Lyophilized complexes had a solid porous matrix and both βCPCD and βCDP showed rapid drug release. βCPCD provides an opportunity to create a swellable, mucoadhesive matrix system for oral drug delivery