ABSTRACT
Nanocelluloses are emerging as natural materials with favourable properties for coating industry and can be applied by state-of-the-art spraying technology. While additional functionalities are commonly introduced through chemical modification, the surface microstructuring of nanocellulose coatings with high throughput methods remains unexplored. Here, a femtosecond laser is used for texturing spray-coated coatings made of cellulose nanofibrils (CNF) or cellulose nanocrystals (CNC). For coating thickness of 1.5 to 8 µm, processing limits were determined with maximum ablation energy linearly increasing with coating thickness and minimum ablation energy decreasing or increasing depending on the apparent coating density. Within applicable processing window of pulse rate and power setting, the operational ranges were determined for creating one-dimensional and two-dimensional surface patterns, requiring a higher laser energy for CNC compared to CNF coatings and yielding thinnest possible resolved patterns of 17 µm as determined by the laser spot diameter. The laser ablation under low energy corresponds to an increase in surface roughness and intensifies surface hydrophilicity, while the line patterns are able to pin water droplets with rising water contact angles up to 90°. Present feasibility study opens future possibilities for managing surface properties of nanocellulose coatings in applications where tuning of surface hydrophilicity is required.
ABSTRACT
While adding different micro- and nanocellulose types into epoxy coating formulations with waterborne phenalkamine crosslinker, effects on processing conditions and coating performance were systematically investigated. The variations in viscosity, thermal and thermomechanical properties, mechanical behavior, abrasive wear, water contact angles, and coating morphologies were evaluated. The selected additives include microcrystalline cellulose (MCC) at 1 to 10 wt.% and cellulose nanocrystals (CNC), cellulose nanofibers (CNF), cellulose microfibers (CMF), and hydrophobically modified cellulose microfibers (mCMF) at 0.1 to 1.5 wt.%. The viscosity profiles are determined by the inherent additive characteristics with strong shear thinning effects for epoxy/CNF, while the epoxy/mCMF provides lower viscosity and better matrix compatibility owing to the lubrication of encapsulated wax. The crosslinking of epoxy/CNF is favored and postponed for epoxy/(CNC, CMF, mCMF), as the stronger interactions between epoxy and CNF are confirmed by an increase in the glass transition temperature and reduction in the dampening factor. The mechanical properties indicate the highest hardness and impact strength for epoxy/CNF resulting in the lowest abrasion wear rates, but ductility enhances and wear rates mostly reduce for epoxy/mCMF together with hydrophobic protection. In addition, the mechanical reinforcement owing to the specific organization of a nanocellulose network at percolation threshold concentrations of 0.75 wt.% is confirmed by microscopic analysis: the latter results in a 2.6 °C (CNF) or 1.6 °C (CNC) increase in the glass transition temperature, 50% (CNF) or 20% (CNC) increase in the E modulus, 37% (CNF) or 32% (CNC) increase in hardness, and 58% (CNF) or 33% (CNC) lower abrasive wear compared to neat epoxy, while higher concentrations up to 1.5 wt.% mCMF can be added. This research significantly demonstrates that nanocellulose is directly compatible with a waterborne phenalkamine crosslinker and actively contributes to the crosslinking of waterborne epoxy coatings, changing the intrinsic glass transition temperatures and hardness properties, to which mechanical coating performance directly relates.
ABSTRACT
The properties of epoxy can be adapted depending on the selection of bio-based diluents and crosslinkers to balance the appropriate viscosity for processing and the resulting mechanical properties for coating applications. This work presents a comprehensive study on the structure-property relationships for epoxy coatings with various diluents of mono-, di-, and bio-based trifunctional glycidyl ethers or bio-based epoxidized soybean oil added in appropriate concentration ranges, in combination with a traditional fossil-based amine or bio-based phenalkamine crosslinker. The viscosity of epoxy resins was already reduced for diluents with simple linear molecular configurations at low concentrations, while higher concentrations of more complex multifunctional diluents were needed for a similar viscosity reduction. The curing kinetics were evaluated through the fitting of data from differential scanning calorimetry to an Arrhenius equation, yielding the lowest activation energies for difunctional diluents in parallel with a balance between viscosity and reactivity. While the variations in curing kinetics with a change in diluent were minor, the phenalkamine crosslinkers resulted in a stronger decrease in activation energy. For cured epoxy resins, the glass transition temperature was determined as an intrinsic parameter that was further related to the mechanical coating performance. Considerable effects of the diluents on coating properties were investigated, mostly showing a reduction in abrasive wear for trifunctional diluents in parallel with the variations in hardness and ductility. The high hydrophobicity for coatings with diluents remained after wear and provided good protection. In conclusion, the coating performance could be related to the intrinsic mechanical properties independently of the fossil- or bio-based origin of diluents and crosslinkers, while additional lubricating properties are presented for vegetable oil diluents.
ABSTRACT
The phenalkamines (PK) derived from cardanol oil can be used as a bio-based crosslinker for epoxy coatings as an alternative for traditional fossil amines (FA). First, the reaction kinetics of an epoxy resin with four PK and FA crosslinkers are compared by differential scanning calorimetry, illustrating a fast reaction rate and higher conversion of PK at room temperature in parallel with a moderate exothermal reaction. Second, the performance of coatings with various concentrations of PK and PK/FA ratios indicates good mixing compatibility between crosslinkers resulting in higher hardness, scratch resistance, hydrophobicity, and abrasive wear resistance of coatings with PK. The superior performance is confirmed over a broad range of resin/crosslinker ratios, facilitating the processing with viscosity profiles depending on the PK type. Although fossil- and bio-based crosslinkers have different chemical structures, the unique linear relationships between intrinsic mechanical properties (i.e., ductility and impact resistance) and coating performance indicate that the degree of crosslinking is a primary parameter controlling coating performance, where PK simultaneously provides high hardness and ductility. In conclusion, the optimization of the processing range for bio-based PK as a crosslinker for epoxy coatings delivers suitable processing conditions and superior mechanical performance compared to traditional amine crosslinkers.
Subject(s)
Amines , Epoxy Resins , Epoxy Resins/chemistry , Benchmarking , Fossils , Tensile StrengthABSTRACT
Materials that confer antimicrobial activity, be that by innate property, leaching of biocides or design features (e.g., non-adhesive materials) continue to gain popularity to combat the increasing and varied threats from microorganisms, e.g., replacing inert surfaces in hospitals with copper. To understand how efficacious these materials are at controlling microorganisms, data is usually collected via a standardised test method. However, standardised test methods vary, and often the characteristics and methodological choices can make it difficult to infer that any perceived antimicrobial activity demonstrated in the laboratory can be confidently assumed to an end-use setting. This review provides a critical analysis of standardised methodology used in academia and industry, and demonstrates how many key methodological choices (e.g., temperature, humidity/moisture, airflow, surface topography) may impact efficacy assessment, highlighting the need to carefully consider intended antimicrobial end-use of any product.