A One-Step Approach for a Durable and Highly Hydrophobic Coating for Flax Fabrics for Self-Cleaning Application.

Highly hydrophobic flax fabrics with durable properties were prepared using the "dip-coating" method for self-cleaning application. Flax fabrics were coated with a polysiloxane coating via a hydrosilylation reaction with a Karstedt catalyst at room temperature. The coated fabrics displayed highly and durable hydrophobic properties (contact angle and sliding angle of about 145° and 23°, respectively) with good self-cleaning ability for certain pollutants and excellent durability. Moreover, the influence of the coating process on the mechanical properties of fabrics was investigated. A decrease in E modulus and an increase in tensile stress at maximum force and elongation at maximum force has been observed. Furthermore, this influence of the coating process can be easily controlled by adjusting the proportion of curing agent in the treatment solution.

Flame Retardancy of Short Flax Fibers Modified by Radiation-Induced Grafting of Phosphonated Monomers: Comparison between Pre- and Simultaneous Irradiation Grafting.

Short flax fibers have been modified by radiation-induced grafting using methacrylate monomers containing phosphorus to give them a flame-retardant character. Two methodologies, namely pre-irradiation and simultaneous irradiation grafting, were examined. Certain parameters, notably the dose and the irradiation source (e-Beam and γ rays), were evaluated. The grafting efficiency, in terms of phosphorus content (mass percentage), was measured by X-ray fluorescence spectrometry (XRF). Using simultaneous irradiation, 2.39 wt% phosphorus could be obtained from 10 kGy, compared to 100 kGy in pre-irradiation. Furthermore, for similar phosphorus levels, the location of the grafted polymer chains was different for the two methodologies. The effect of phosphorus content on thermal properties and fire behavior was evaluated on a microscopic scale using a pyrolytic flow combustion calorimeter (PCFC) and on a laboratory scale using a cone calorimeter. It was then pointed out that flammability was linked to the phosphorus content and likely its location, which is associated with the radiation-induced grafting methodology, showing that the grafting conditions influence the final fire properties. Simultaneous irradiation, thus, proved to be more interesting in terms of efficiency and final properties.

Flame Retardant-Functionalized Cotton Cellulose Using Phosphonate-Based Ionic Liquids.

Cellulose from cotton fibers was functionalized through a dissolution-regeneration process with phosphonate-based ionic liquids (ILs): 1,3-dimethylimidazolium methylphosphonate [DIMIM][(MeO)(H)PO2] and 1-ethyl-3-methylimidazolium methylphoshonate [EMIM][(MeO)(H)PO2]. The chemical modification of cellulose occurred through a transesterification reaction between the methyl phosphonate function of ILs and the primary alcohol functions of cellulose. The resulting cellulose structure and the amount of grafted phosphorus were then investigated by X-ray diffraction, ICP-AES, and ¹³C and ³¹P NMR spectroscopy. Depending on the IL type and initial cotton / IL ratio in the solution, regenerated cellulose contained up to 4.5% of phosphorus. The rheological behavior of cotton cellulose/ILs solutions and the microscale fire performances of modified cellulose were studied in order to ultimately prepare flame retardant cellulosic materials. Significant improvement in the flame retardancy of regenerated cellulose was obtained with a reduction of THR values down to about 5-6 kJ/g and an increase of char up to about 35 wt%.

One-Step Multifunctionalization of Flax Fabrics for Simultaneous Flame-Retardant and Hydro-Oleophobic Properties Using Radiation-Induced Graft Polymerization.

This study concerns the one-step radiografting of flax fabrics with phosphonated and fluorinated polymer chains using (meth)acrylic monomers: dimethyl(methacryloxy)methyl phosphonate (MAPC1), 2-(perfluorobutyl)ethyl methacrylate (M4), 1H,1H,2H,2H-perfluorooctyl acrylate (AC6) and 1H,1H,2H,2H-perfluorodecyl methacrylate (M8). The multifunctionalization of flax fabrics using a pre-irradiation procedure at 20 and 100 kGy allows simultaneously providing them with flame retardancy and hydro- and oleophobicity properties. The successful grafting of flax fibers is first confirmed by FTIR spectroscopy. The morphology of the treated fabrics, the regioselectivity of grafting and the distribution of the fluorine and phosphorus elements are assessed by scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (SEM-EDX). The flame retardancy is evaluated using pyrolysis combustion flow calorimetry (PCFC) and cone calorimetry. The hydro- and oleophobicity and water repellency of the treated fabrics is established by contact angle and sliding angle measurements, respectively. The grafting treatment of flax irradiated at 100 KGy, using M8 and MAPC1 monomers (50:50) for 24 h, allows achieving fluorine and phosphorus contents of 8.04 wt% and 0.77 wt%, respectively. The modified fabrics display excellent hydro-oleophobic and flame-retardant properties with water and diiodomethane contact angles of 151° and 131°, respectively, and a large decrease in peak of heat release rate (pHRR) compared to pristine flax (from 230 W/g to 53 W/g). Relevant results are also obtained for M4 and AC6 monomers in combination with MAPC1. For the flame retardancy feature, the presence of fluorinated groups does not disturb the effect of phosphorus.

h-BN Modification Using Several Hydroxylation and Grafting Methods and Their Incorporation into a PMMA/PA6 Polymer Blend.

Hexagonal boron nitride (h-BN) has recently gained much attention due to its high thermal conductivity and low electrical conductivity. In this study, we proposed to evaluate the impact of the modification of h-BN for use in a polymethylmethacrylate/polyamide 6 (PMMA/PA6) polymer blend. Different methods to modify h-BN particles and improve their affinity with polymers were proposed. The modification was performed in two steps: (1) a hydroxylation step for which three different routes were used: calcination, acidic treatment, and ball milling using gallic acid; (2) a grafting step for which four different silane agents were used, carrying different molecular or macromolecular groups: the octadecyl group (Si-C18), propyl amine group (Si-NH2), polystyrene chain (Si-PS), and PMMA chain (Si-PMMA). The modified h-BN samples after hydroxylation and functionalization were characterized by FTIR and TGA. Py-GC/MS was also used to prove the successful graft with Si-C18 groups. Sedimentation tests and multiple light scattering were performed to assess the surface modification of h-BN. Granulometry and SEM observations were performed to evaluate the particle size distribution after hydroxylation. After the addition of Si-PMMA modified h-BN into a PMMA/PA6 co-continuous blend, the morphology of the polymer blend nanocomposites was characterized using SEM. The calculation of the wetting parameter based on the surface tension measurement using the liquid drop model showed that h-BN dispersed in the PA6 phase. Grafting PMMA chains onto hydroxylated h-BN particles combined with an adequate sequence mixing led to a successful localization of the grafted h-BN particles at the interface of the PMMA/PA6 blend.

Fire behavior of innovative alginate foams.

A new biosourced composite foam (AF, associating foamed alginate matrix and orange peel filler) is successfully tested for fire-retardant properties. This material having similar thermal insulating properties and density than fire-retardant polyurethane foam (FR-PUF, a commercial product) shows promising enhanced properties for flame retardancy, as assessed by different methods such as thermogravimetric analysis (TGA), pyrolysis combustion flow calorimetry (PCFC) and a newly designed apparatus called RAPACES for investigating large-scale samples. All these methods confirm the promising properties of this alternative material in terms of fire protection (pHRR, THR, EHC, time-to-ignition, flame duration or production of residue), especially for heat flux not exceeding 50 kW m-2. At higher heat flux (i.e., 75 kW m-2), flame retardant properties tend to decrease but maintain at a higher level than FR-PUF. The investigation of the effect of AF thickness shows that the critical thickness (CT) is close to 1.5-1.7 cm: heat diffusion and material combustion are limited to the CT layer that protects the underlying layers from combustion. A multiplicity of factors can explain this behavior, such as: (a) negligible heat conduction, (b) low heat of combustion, (c) charring formation, and (d) water release. Water being released from underlying layers, dilutes the gases emitted during the combustion of superficial layers and promotes the flame extinction.

Exploring the Contribution of Two Phosphorus-Based Groups to Polymer Flammability via Pyrolysis-Combustion Flow Calorimetry.

From a set of around 100 phosphorus-containing polymers tested in pyrolysis-combustion flow calorimetry, the contributions to flammability of two phosphorus-containing pendant groups (called 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and PO3) were calculated using an advanced method previously proposed and validated. The flammability properties include total heat release (THR) and heat release capacity (HRC) measured in standard conditions, i.e., anaerobic pyrolysis and complete combustion. The calculated contributions are in good agreement with the main modes of action of both phosphorus groups, i.e., flame inhibition for DOPO and char promotion for PO3. Moreover, the results provide first conclusions about the cooperative interaction between phosphorus and nitrogen, as well as the influence of the architecture of tested co-polymers.