Crystallisation behaviour of composites of HDPE and MWCNTs: The effect of nanotube dispersion, orientation and polymer deformation

Multi-walled carbon nanotubes (MWCNTs) were readily dispersed and distributed in the high density polyethylene (HDPE) matrix and a very low (<0.3 wt%, 0.17 vol%) rheological percolation threshold obtained. The polymer is seen to coat the MWCNTs, which act as a nucleating agent and induce an oriented nanohybrid shish-kebab (NHSK) crystalline structure, in part an artefact of the injection moulding process. The elastic modulus and yield stress of HDPE increased on addition, but the polymer strain at break increased sharply below percolation before decreasing again above percolation. Addition of MWCNTs, above the percolation threshold, hindered orientation of the polymer chains such that failure occurred before necking during tensile testing, the inclusion of MWCNTs altered the uniaxial deformation behaviour of HDPE. SAXS/WAXS studies on samples post uniaxial drawing revealed that the HDPE and composites of HDPE and MWCNTs developed a highly oriented sheared herringbone lamellar structure. The drawing process also caused surface cavitation and voiding in the composites

The formation of a nanohybrid shish-kebab (NHSK) structure in melt-processed composites of poly (ethylene terephthalate) (PET) and multi-walled carbon nanotubes (MWCNTs)

The combination of synchrotron Small- and Wide-Angle X-ray scattering (SAXS/WAXS), and thermal analysis was used to follow the evolution of crystalline morphology and crystallization kinetics in a series of melt-processed composites of poly(ethylene terephthalate) (PET) and multiwall carbon nanotubes (MWCNT). The as-extruded PET-MWCNT composites underwent both hot and cold isothermal crystallizations where a final oriented nanohybrid shish-kebab (NHSK) crystalline structure was observed. An oriented NHSK structure was seen to persist even after melting and recrystallization of the composites. From the scattering data, we propose a model whereby the oriented MWCNTs act as heterogeneous nucleation surfaces (shish) and the polymer chains wrap around them and the crystallites (kebabs) grow epitaxially outwards during crystallization. However, depending on crystallization temperature, unoriented crystallites also grow in the polymer matrix, resulting in a combination of a NHSK and lamellar morphology. In contrast, the neat PET homopolymer showed the sporadic nucleation of a classic unoriented lamellar structure under the same isothermal crystallization conditions. These results provide a valuable insight into the distinctive modification of the crystalline morphology of melt-processed polymer-MWCNT composites prior to any secondary processing, having a significant impact on the use of MWCNTs as fillers in the processing and modification of the physical and mechanical properties of engineering polymers

Structure evolution in poly(ethylene terephthalate) (PET) - Multi-walled carbon nanotube (MWCNT) composite films during <i>in-situ</i> uniaxial deformation

Combined small- and wide-angle X-ray scattering (SAXS/WAXS), mechanical and thermal techniques have been used to follow the morphology evolution in a series of poly(ethylene terephthalate) (PET) multiwall carbon nanotube (MWCNT) composite films during quasi solid-state uniaxial deformation at low strain rates. Uniaxially deformed PET-MWCNT films displayed improved mechanical properties compared with unfilled PET films. SAXS/WAXS data revealed a well oriented lamellar structure for unfilled PET films. In contrast, the PET-MWCNT composites revealed a nanohybrid shish-kebab (NHSK) morphology, with reduced orientation and crystallinity. Mechanistically, this morphology development is attributed to the MWCNTs acting as shish for the epitaxial growth of PET crystallites. Furthermore, nucleation and crystal growth occurs in the PET matrix, but MWCNTs ultimately inhibit crystallite development and hinder a final lamellar structure developing. The results show unequivocally the role MWCNTs play as nanofillers, in the morphology development, thermal and mechanical properties in composite polymer films

In-situ uniaxial drawing of poly-L-lactic acid (PLLA): Following the crystalline morphology development using time-resolved SAXS/WAXS

Simultaneous synchrotron small- and wide-angle X-ray scattering (SAXS/WAXS) was used to follow the crystalline morphology evolution of poly-L- lactic acid (PLLA) during uniaxial deformation at various draw temperatures (Td). The mechanical behaviour of PLLA, was found to be strongly dependent on Td. 2D SAXS/WAXS data taken during the draw showed that at low Tds cavitation and voiding occurred and the initial crystallites underwent ‘overdrawing’ where they slip and are partially destroyed. SEM confirmed that surface voiding and cavitation had occurred at Td = 60 and 65 °C but was absent at higher Tds. During the draw, no long-range macromolecular lamellar structure was seen in the SAXS, but small crystallites of the disordered α′ crystal form of PLLA were observed in the WAXS at all Tds. The PLLA samples were then step annealed in a second processing stage (post-draw) to develop the oriented crystalline lamellar structure and increase the amount of the stable α crystalline form. SAXS/WAXS data showed that a highly oriented lamellar stack macrostructure developed on annealing, with increased crystallite size and crystallinity at all Tds. Furthermore, step annealing drove the crystalline transition in all samples from the disordered α′ crystal form to the stable α crystal form. Therefore, varying pre- and post-processing parameters can significantly influence the mechanical properties, orientation, crystalline morphology and crystal phase transition of the final PLLA material

Enzymatic hydrolysis of bacterial cellulose in the presence of a non-catalytic cerato-platanin protein

In this work, the effect of an expansin-like cerato-platanin (CP) protein as a pre-treatment for the enzymatic hydrolysis of bacterial cellulose (BC) is investigated. To this scope, cellulases from Trichoderma reesei are used as hydrolyzing agent using different enzyme/BC formulations. Turbidity experiments reveal that for the higher enzyme concentrations (formulations 0.5:1 and 1:1) the enzymatic hydrolysis of BC show similar hydrolysis kinetics and is not dependent of the CP. However, at higher BC concentrations (formulations 0.25:1 and 0.33:1), the hydrolysis of BC is hindered by the non-catalytic protein, as confirmed by the lower content of cellobiose and glucose in the presence of CP. Light scattering experiments show that the addition of CP led to an increase of the BC particle size from (445–630 nm) to (890–1.26 μm) for the formulation 1:1, which is also corroborated by atomic force microscopy and transmission electron microscopy analyses. These results suggest that CP did not positively affect the hydrolysis of BC, in contrast to what was previously observed for plant-derived cellulose. This work for the first time investigates the anomalous behavior of cerato platanin family members with regard to its loosening activity on the structure of bacterial cellulose

Effective and fast-screening route to evaluate dynamic elastomer-filler network reversibility for sustainable rubber composite design

.The introduction of self-healing and reprocessability into conventional vulcanized rubbers has been recognized as a promising strategy to promote elastomer circularity. However, the reversibility and recovery of cross-linking polymer networks have often been assessed by static mechanical testing, which highly limits the understanding of the underlying microscale mechanisms. In this work, we investigated the network recovery of natural rubber (NR)/carbon black (CB) nanocomposites using Fourier transform (FT) rheology coupled with large amplitude oscillation shear (LAOS) technology across linear and nonlinear regimes (0.01–500%). The self-healing process of the rubber composite networks was monitored by using a programmed time–temperature oscillation shear measurement. The role of CB particle size in the filler network recovery was also discussed from the perspective of strain-induced crystallization of NR. Coupling FT-rheology and LAOS analysis, two distinct nonlinear enhancement behaviors beyond the linear viscoelastic regime were detected in the rubber nanocomposites, which were ascribed to the filler network disruption followed by the polymer network deformation. The relationship of the nonlinearity parameter I3/1 as a function of strain amplitude was selected to quantify the nonlinear rheological responses, where the role of the filler and polymer on the network recovery can therefore be differentiated. This work provides an efficient method to evaluate the self-healing and reprocessability of cross-linked rubbers and offers a fast-screen route for formulation development and sustainable rubber composite design

Tuning triboelectric and energy harvesting properties of dielectric elastomers <i>via</i> dynamic ionic crosslinks

The bromination of poly(isobutylene-co-isoprene) rubber introduces a small amount of bromide groups (1–2 mol%) to the elastomer backbone and creates new opportunities for functionalisation, as compared to other saturated and diene elastomers. In this work, three types of nucleophile reagents: namely pyridine, triphenylphosphine and imidazoles bearing four types of side groups of methyl, ethyl, hydroxyl or vinyl group were introduced to brominated poly(isobutylene-co-isoprene) rubber (BIIR) through nucleophile substitution with the bromine via solid-state rubber compounding and curing processes. The resulted ionic aggregates act as physical crosslinks and their size and density directly affected the mechanical reinforcement, self-healing and dynamic mechanical properties of the elastomers. The smaller and polar imidazolyl/bromine pairs led to the highest reinforcement beyond even the sulfur-cured BIIR counterparts. The 1-ethyl imidazole (EIm) modified BIIR showed the highest tensile strength of 17.01 ± 1.89 MPa and elongation at break of 1402 ± 69% with self-healing efficiency of 63.7%, after being treated at 140 °C for 30 min. In addition, the inclusion of the ionic clusters enhanced the relative permittivity of the elastomer, thereby enhancing the energy conversion efficiencies. The nucleophile substitution reaction via conventional solid-state rubber compounding processes provides a facile crosslinking and reinforcement strategy for halogen-containing polymers. In addition, the dynamic ionic crosslinking networks spontaneously benefit electromechanical and self-healing properties of the dielectric elastomers

Effective and Fast-Screening Route to Evaluate Dynamic Elastomer-Filler Network Reversibility for Sustainable Rubber Composite Design

The introduction of self-healing and reprocessability into conventional vulcanized rubbers has been recognized as a promising strategy to promote elastomer circularity. However, the reversibility and recovery of cross-linking polymer networks have often been assessed by static mechanical testing, which highly limits the understanding of the underlying microscale mechanisms. In this work, we investigated the network recovery of natural rubber (NR)/carbon black (CB) nanocomposites using Fourier transform (FT) rheology coupled with large amplitude oscillation shear (LAOS) technology across linear and nonlinear regimes (0.01–500%). The self-healing process of the rubber composite networks was monitored by using a programmed time–temperature oscillation shear measurement. The role of CB particle size in the filler network recovery was also discussed from the perspective of strain-induced crystallization of NR. Coupling FT-rheology and LAOS analysis, two distinct nonlinear enhancement behaviors beyond the linear viscoelastic regime were detected in the rubber nanocomposites, which were ascribed to the filler network disruption followed by the polymer network deformation. The relationship of the nonlinearity parameter I3/1 as a function of strain amplitude was selected to quantify the nonlinear rheological responses, where the role of the filler and polymer on the network recovery can therefore be differentiated. This work provides an efficient method to evaluate the self-healing and reprocessability of cross-linked rubbers and offers a fast-screen route for formulation development and sustainable rubber composite design

Multiorgan MRI findings after hospitalisation with COVID-19 in the UK (C-MORE): a prospective, multicentre, observational cohort study

Introduction: The multiorgan impact of moderate to severe coronavirus infections in the post-acute phase is still poorly understood. We aimed to evaluate the excess burden of multiorgan abnormalities after hospitalisation with COVID-19, evaluate their determinants, and explore associations with patient-related outcome measures. Methods: In a prospective, UK-wide, multicentre MRI follow-up study (C-MORE), adults (aged ≥18 years) discharged from hospital following COVID-19 who were included in Tier 2 of the Post-hospitalisation COVID-19 study (PHOSP-COVID) and contemporary controls with no evidence of previous COVID-19 (SARS-CoV-2 nucleocapsid antibody negative) underwent multiorgan MRI (lungs, heart, brain, liver, and kidneys) with quantitative and qualitative assessment of images and clinical adjudication when relevant. Individuals with end-stage renal failure or contraindications to MRI were excluded. Participants also underwent detailed recording of symptoms, and physiological and biochemical tests. The primary outcome was the excess burden of multiorgan abnormalities (two or more organs) relative to controls, with further adjustments for potential confounders. The C-MORE study is ongoing and is registered with ClinicalTrials.gov, NCT04510025. Findings: Of 2710 participants in Tier 2 of PHOSP-COVID, 531 were recruited across 13 UK-wide C-MORE sites. After exclusions, 259 C-MORE patients (mean age 57 years [SD 12]; 158 [61%] male and 101 [39%] female) who were discharged from hospital with PCR-confirmed or clinically diagnosed COVID-19 between March 1, 2020, and Nov 1, 2021, and 52 non-COVID-19 controls from the community (mean age 49 years [SD 14]; 30 [58%] male and 22 [42%] female) were included in the analysis. Patients were assessed at a median of 5·0 months (IQR 4·2–6·3) after hospital discharge. Compared with non-COVID-19 controls, patients were older, living with more obesity, and had more comorbidities. Multiorgan abnormalities on MRI were more frequent in patients than in controls (157 [61%] of 259 vs 14 [27%] of 52; p&lt;0·0001) and independently associated with COVID-19 status (odds ratio [OR] 2·9 [95% CI 1·5–5·8]; padjusted=0·0023) after adjusting for relevant confounders. Compared with controls, patients were more likely to have MRI evidence of lung abnormalities (p=0·0001; parenchymal abnormalities), brain abnormalities (p&lt;0·0001; more white matter hyperintensities and regional brain volume reduction), and kidney abnormalities (p=0·014; lower medullary T1 and loss of corticomedullary differentiation), whereas cardiac and liver MRI abnormalities were similar between patients and controls. Patients with multiorgan abnormalities were older (difference in mean age 7 years [95% CI 4–10]; mean age of 59·8 years [SD 11·7] with multiorgan abnormalities vs mean age of 52·8 years [11·9] without multiorgan abnormalities; p&lt;0·0001), more likely to have three or more comorbidities (OR 2·47 [1·32–4·82]; padjusted=0·0059), and more likely to have a more severe acute infection (acute CRP &gt;5mg/L, OR 3·55 [1·23–11·88]; padjusted=0·025) than those without multiorgan abnormalities. Presence of lung MRI abnormalities was associated with a two-fold higher risk of chest tightness, and multiorgan MRI abnormalities were associated with severe and very severe persistent physical and mental health impairment (PHOSP-COVID symptom clusters) after hospitalisation. Interpretation: After hospitalisation for COVID-19, people are at risk of multiorgan abnormalities in the medium term. Our findings emphasise the need for proactive multidisciplinary care pathways, with the potential for imaging to guide surveillance frequency and therapeutic stratification

An investigation into the crystalline morphology transitions in poly-L-lactic acid (PLLA) under uniaxial deformation in the quasi-solid-state regime

The mechanical behaviour, crystalline and macromorphology structure development during uniaxial deformation and annealing of poly-L-lactic acid (PLLA), with varying strain rate and draw temperatures (Td) above Tg, have been investigated using small- and wide-angle X-ray scattering (SAXS/WAXS), microscopy, thermal and mechanical techniques. The mechanical behaviour of PLLA, was strongly dependent on Td where embrittlement and eventual failure were observed as Td was increased, during uniaxial drawing of the amorphous polymer. This was mirrored in the bulk surface morphology where crazing, microvoiding and cavitation occurred with increasing Td. SAXS/WAXS data showed that strain-induced crystallization occurs on drawing, but crystallite orientation decreased with increasing Td, due to chain relaxation at temperatures ≥30 oC above Tg. However, no long-range oriented lamellar macromorphology was observed post-draw directly and only developed in the samples that were step annealed at temperatures above Td. Also, the disordered α’ crystal form was observed post-draw at Td between 60 – 80 oC, whereas Td ≥ 90 oC, resulted in the ordered α crystal form directly. However, on annealing at temperatures of ≥110 oC, the α’- α crystal transition ensued and in all samples, an oriented lamellar macromorphology developed. Therefore, Td and post-draw annealing, have a significant influence on the mechanical properties, crystallinity and crystalline phase transformation in PLLA, which in-turn, affects the polymers medical and industrial applications