Interaction of cationic starch derivatives and cellulose fibres in the wet end and its correlation to paper strength with a statistical evaluation

The adsorption onto a softwood pulp of cationic modified starches with a degree of substitution (DS) ranging from 0.015 to 0.130 and native potato starch was investigated using a method based on size exclusion chromatography‐multi angle laser light scattering (SEC‐MALLS). This technique provides information about the amount and molecular composition of the adsorbed starch product such as the AP–AM‐ratio, the average MW and molar mass distribution. Factors influencing adsorption, like the electrolyte content in the suspension and the initial starch polysaccharide concentration, were investigated. Furthermore, hand sheets were made and the resulting mechanical paper strength was tested. Results were analysed statistically using analysis of variance. Representative results were discussed in detail. In general, low‐substituted cationic starch (DS 0.030) exhibited a higher degree of adsorption and resulted in high paper strength when there was a low electrolyte content in the starch–pulp‐suspension. However, high amounts of electrolytes impeded electrostatic interaction of the charged groups of the starch polysaccharides and cellulose fibre due to partial screening and therefore strongly limited adsorption. This resulted in lowered mechanical paper strength. The water quality of the suspensions had little impact on the polyelectrolyte adsorption of the highly substituted cationic starch (DS 0.100). However, paper strength was markedly higher in the case of starch adsorption where there was a high ionic content and when both starch polysaccharides–AP and AM– were adsorbed. The initial starch concentration determined starch adsorption both quantitatively and qualitatively and subsequently paper strength as well. The relation between adsorption behaviour and paper strength was discussed, particularly in the case of 6% initial starch concentration. In deionised water (DW), the low‐substituted starch (DS 0.03) adsorbed onto the pulp to a greater extent with an AP–AM‐ratio similar to that of the initial starch. Moreover, this achieved the best strength properties in contrast to 36 dGH, where less starch adsorbed and that being almost exclusively AP. In water with 36 dGH, the highly substituted starch (DS 0.100) with both the AP and AM was absorbed and this resulted in higher paper strength. In contrast, AM was almost exclusively adsorbed in DW. Increasing the initial starch concentration increased the amount adsorbed while subsequently changing the AP–AM‐ratio towards increased AM adsorption and decreased AP adsorption in the case of DS 0.100 in DW. Exclusive adsorption of AM markedly lowered the development of the paper strength.     

Phase variation and mechanical properties of waste calcium carbonate to substitute quartz in composite slab production

Owing to the fast-emerging nature and rapid advancements in the construction industry, huge volumes of marble dust (MD) are generated as reject during slab cutting in marble processing, causing significant environmental hazards. Nowadays, quartz composite slabs have increasingly been preferred in building works due to their excellent hygienic property and mechanical strength. Composite slab is produced using micronized quartz as filler, the grinding of which is an energy-intensive process. Substitution of micronized quartz with MD at different percentages was investigated in natural form and after roasting. Natural MD offered appreciable physical properties closer to those of a quartz composite slab. Physical properties slightly retrograded by quartz supplementation in the raw form. Roasting the filler led to the formation of rounded Ca–silicate. Wollastonite was the first phase formed after sintering at the lowest MD percentage and shortest roasting times. Larnite became dominating phase first by increasing MD percentage and roasting time, and then calcio-olivine formed. Physical characterization test results demonstrated that hardnesses of new phase and particle shape were the key parameters that improved slabs’ mechanical properties of. Hard rounded larnite particles improved mechanical behavior of slabs having the synergic effect of quartz, whereas wollastonite did not show a significant effect.     

V-notched rail shear test applied to geopolymer composites

This work presents a systematic study of the shear properties of a potassium-based geopolymer reinforced with distinct types of fibers. Chopped basalt reinforcements in lengths from 3 mm up to 50 mm and 13 μm in diameter were compared with thicker 20-mm length, basalt mini bars, sand-coated basalt mini rods, and steel fibers. The samples were tested under a V-notched rail shear tests (ASTM D7078), coupled with optical measurements, namely, digital image correlation, allowing a novel study of their crack patterns and failure modes under shear loading. In general, the use of chopped fibers resulted in shear strengths of up to 9 MPa and shear moduli of 4.3 GPa, with no significant variation with fiber length increments, neither in shear stress nor strain at peak load (0.1%). Mini bars and steel fiber reinforcements resulted in slightly lower shear stresses of 7.1 and 8.4 MPa, respectively. They exhibited greater strain values at peak loads, up to 2.1% which were attributed to fiber-matrix enhanced adhesions, thereby allowing gradual debonding and increased ductility. This effect was also recorded for mini rods, but at much lower strength levels, which did not contribute to their multiple cracking capacities. The alignment of the mini rods in 45° directions resulted in a 50% increase in shear stress, showing the feasibility of tailoring the manufacturing process to attend to distinct demands.     

Isolating the effects of thixotropy in geopolymer pastes

The rheological properties of potassium-based geopolymers were investigated through a series of experiments intended to isolate the influence of shear rate, recovery time, and shear ramping on thixotropy for a greater understanding of geopolymer thixotropic properties within the context of the geopolymer setting reaction. It is shown that for thixotropic disruption to occur a critical shear rate of 100 s⁻¹ must be reached or surpassed, full thixotropic restructuring occurs at around 90–100 min of total undisturbed rest time, and that reaching a state of full thixotropic disturbance heavily depends on subjected processing parameters. In addition, a consistent crossover between the storage and loss modulus within 1–3 min of oscillation during cyclical oscillatory measurements greatly indicates the repeatability and reversibility of thixotropy in geopolymers and the potential for tailorable viscosity. Overall, it is found that geopolymer pastes exhibit strong evidence of thixotropy, which is favorable for additive manufacturing, and that allotted rest time before shear and shear rate greatly influence the overall rheological properties.     

Rheological assessment of metakaolin-based geopolymer composites through squeeze flow

Geopolymer (GP) composites show great potential as a replacement for ordinary Portland cement (OPC) in construction material, extrusion-based, and additive manufacturing. The rheological properties of highly viscous and reinforced systems have not yet been well studied, due to limitations in the current state of the art rheometers and viscometers, such as size and torque limits. In this study, the basic rheological properties of highly reinforced, geopolymer composites with potential for 3D printing are innovatively investigated with “squeeze flow” and “flow table” tests commonly used in civil engineering. Squeeze-flow rates of 0.1, 1.0, and 3.0 mm/s were assessed with varying sand weight percentages or basalt fiber lengths and compared to a conventional OPC mixture to differentiate the flow properties and deformation resistance of both materials. It is shown that the deformation resistance as a result of jamming increases with increasing solid reinforcement percentages, but that the overall effect of fiber size is somewhat inconclusive. In addition, the effect of squeeze-flow rate exhibits an increase in load required to initiate flow at lower squeezing rates, but, upon reaching a certain ratio of solids to liquid in the matrix, the results become variable.     

The influence of alkaline treatment on the mechanical performance of geopolymer composites reinforced with Brazilian malva and curaua fibers

Lignocellulosic fibers obtained from the curaua (Ananas erectifolius) and malva (Malva sylvestris) plants in Brazil can be used as suitable reinforcements for geopolymers (GPs) owing to their high strength, ready regional availability, and low cost. In this work, the tensile and flexural strengths of untreated and NaOH alkali-treated curaua and malva fiber-reinforced GP composites were measured according to ASTM standards. Curaua reinforced GP composites had an average tensile strength of 25.7 (±) 7.1 MPa and flexural strength of 18.9 (±) 4.72 MPa. Malva GP composites withstood 19.18 (±) 9.0 MPa in tension and 31.5 (±) 7.6 MPa in flexure. Additionally, pullout tests were performed to investigate the debonding mechanisms for both fibers, with and without alkaline treatment, finding increases in chemical bonding for the treated samples due to roughness enhancements through fiber surface modifications with alkali treatment. Thermogravimetric analysis and X-ray diffraction were used to characterize the physical fiber modifications after alkali treatment, evidencing lignin and hemicellulose removals. Scanning electron microscopy and energy-dispersive X-ray spectroscopy were used to further examine the fiber–matrix interaction, with proofs of interfacial tailoring.     

Improving In Vitro Detection of Sensitization to Lipid Transfer Proteins: A New Molecular Multiplex IgE Assay

Scope

LTP-syndrome is characterized by sensitization (IgE) to multiple non-specific lipid transfer proteins (nsLTPs) with a variable clinical outcome. The treatment is primarily based on offending food avoidance. However, the determination of Pru p 3-specific IgE is currently the main diagnostic tool to assess sensitization to nsLTPs. Herein, the study evaluates improvement of LTP-syndrome diagnosis and clinical management using a new IgE multiplex-immunoblot assay with a high diversity of food nsLTPs.

Methods and results

An EUROLINE-LTP strip with 28 recombinant nsLTPs from 18 allergenic sources is designed. In total the study investigates 38 patients with LTP-syndrome and compares results from the nsLTPs (LTP-strip) with the respective food extracts of Prick-by-prick (PbP) testing. The agreement exceeds 70% for most nsLTPs, e.g., Pru p 3 (100%), Mal d 3 (97%), Pru av 3 (89%), Pha v 3 isoforms (87%/84%), Ara h 9 (82%), Cor a 8 (82%), and Jug r 3 (82%). The functionality and allergenic relevance of nine recombinant nsLTPs are proven by Basophil activation testing (BAT).

Conclusions

The new IgE multiplex-immunoblot nsLTP assay shows a good diagnostic performance allowing culprit food assessment. Negative results from LTP-strip may indicate potentially tolerable foods, improving diet intervention and patients’ quality of life.     

Fabrication and mechanical properties of metakaolin-based geopolymer composites reinforced with auxetic fabrics

This work presents a novel experimental study on the use of auxetic fabrics as the main reinforcement in geopolymer composites, aiming at higher energy dissipation in impact demanding applications. For this, a potassium-based geopolymer was reinforced with an auxetic fabric consisting of basalt fiber fillings positioned between helical auxetic yarns (HAY) made of a thermoplastic polyester core, and a stiffer liquid-crystal polymer wrap, which dispersed the load demands into several single elements having different capabilities. The composites were investigated under quasi-static flexural and tensile loadings, in both longitudinal and transverse directions. The latter showed increased mechanical strengths, up to 26 MPa in tension, and 12.8 MPa in flexural strength. Each fiber portion was tested in tension separately, reaching flexible (core) and stiffer (wrap and basalt) responses, whereas HAYs displayed combined performances due to a suitable auxeticity effect, that is, a negative Poisson's ratio. The pullout investigation justified the cracking and delamination of the composites, due to its cyclic lateral area modification, which created a load demand much higher than what the brittle geopolymer can sustain in this type of solicitation. Thermogravimetric analyses helped to predict the use of such configurations under thermal exposure, pointing out that the geopolymer material could be a suitable thermal barrier to prevent sudden degradation of the fabric under these conditions.