High-performance thermally insulating materials from renewable resources are needed to improve the energy efficiency of buildings. Traditional fossil-fuel-derived insulation materials such as ...expanded polystyrene and polyurethane have thermal conductivities that are too high for retrofitting or for building new, surface-efficient passive houses. Tailored materials such as aerogels and vacuum insulating panels are fragile and susceptible to perforation. Here, we show that freeze-casting suspensions of cellulose nanofibres, graphene oxide and sepiolite nanorods produces super-insulating, fire-retardant and strong anisotropic foams that perform better than traditional polymer-based insulating materials. The foams are ultralight, show excellent combustion resistance and exhibit a thermal conductivity of 15 mW m(-1) K(-1), which is about half that of expanded polystyrene. At 30 °C and 85% relative humidity, the foams retained more than half of their initial strength. Our results show that nanoscale engineering is a promising strategy for producing foams with excellent properties using cellulose and other renewable nanosized fibrous materials.
Cellulose from wood fibers can be modified for use in flame-retardant composites as an alternative to halogen-based compounds. For this purpose, sulfite dissolving pulp fibers have been chemically ...modified by phosphorylation, and the resulting material has been used to prepare cellulose nanofibrils (CNF) that have a width of approximately 3 nm. The phosphorylation was achieved using (NH4)2HPO4 in the presence of urea, and the degree of substitution by phosphorus was determined by X-ray photoelectron spectroscopy, conductometric titration, and nuclear magnetic resonance spectroscopy. The presence of phosphate groups in the structure of CNF has been found to noticeably improve the flame retardancy of this material. The nanopaper sheets prepared from phosphorylated CNF showed self-extinguishing properties after consecutive applications of a methane flame for 3 s and did not ignite under a heat flux of 35 kW/m2, as shown by flammability and cone calorimetry measurements, respectively.
Pure cellulosic foams suffer from low thermal stability and high flammability, limiting their fields of application. Here, light-weight and flame-resistant nanostructured foams are produced by ...combining cellulose nanofibrils prepared from phosphorylated pulp fibers (P-CNF) with microfibrous sepiolite clay using the freeze-casting technique. The resultant nanocomposite foams show excellent flame-retardant properties such as self-extinguishing behavior and extremely low heat release rates in addition to high flame penetration resistance attributed mainly to the intrinsic charring ability of the phosphorylated fibrils and the capability of sepiolite to form heat-protective intumescent-like barrier on the surface of the material. Investigation of the chemical structure of the charred residue by FTIR and solid state NMR spectroscopy reveals the extensive graphitization of the carbohydrate as a result of dephosphorylation of the modified cellulose and further dehydration due to acidic catalytic effects. Originating from the nanoscale dimensions of sepiolite particles, their high specific surface area and stiffness as well as its close interaction with the phosphorylated fibrils, the incorporation of clay nanorods also significantly improves the mechanical strength and stiffness of the nanocomposite foams. The novel foams prepared in this study are expected to have great potential for application in sustainable building construction.
Flexible polyurethane foam (PUF) is widely used in bedding, transportation, and furniture, despite being highly flammable. In an effort to decrease the flammability of the polymer, an environmentally ...friendly flame retardant coating was deposited on polyurethane foam (PUF) via layer-by-layer assembly. Treated foam was subjected to three different fire scenarios, 10 s torch test, cone calorimetry, and a 900 s burn-through test, to evaluate the thermal shielding behavior of an eight bilayer chitosan/vermiculite clay nanocoating. In each fire scenario, the nanocoating acts as a thermal shield from the flames by successfully protecting the backside of the PUF, whereas the side directly exposed to the flame results in a hollowed nanocoating that maintains the complex three-dimensional porous structure of the foam. Cone calorimetry reveals that the coating reduces the peak heat release rate and total smoke release by 53 and 63%, respectively, whereas a temperature gradient greater than 200 °C is observed across a 2.5 cm thick coated foam sample during the rigorous burn-through fire test. The thermal shielding behavior of this polymer/clay nanocoating makes this system very attractive in improving the fire safety of polyurethane foam used for insulating applications.
Ultrathin nanocomposite films were prepared by combining cellulose nanofibrils (CNFs) prepared from phosphorylated pulp fibers (P-CNF) with montmorillonite (MMT), sepiolite (Sep) clay, or sodium ...hexametaphosphate (SHMP). The flame-retardant and heat-protective capability of the prepared films as casings for a polyethylene (PE) film was investigated. Heating the coated PE in air revealed that the polymer film was thoroughly preserved up to at least 300 °C. The P-CNF/MMT coatings were also able to completely prevent the ignition of the PE film during cone calorimetry, but neither the P-CNF/Sep nor the P-CNF/SHMP coating could entirely prevent PE ignition. This was explained by the results from combined thermogravimetry Fourier transform infrared spectroscopy, which showed that the P-CNF/MMT film was able to delay the release of PE decomposition volatiles and shift its thermal degradation to a higher temperature. The superior flame-retardant performance of the P-CNF/MMT films is mainly attributed to the unique compositional and structural features of the film, where P-CNF is responsible for increasing the char formation, whereas the MMT platelets create excellent barrier and thermal shielding properties by forming inorganic lamellae within the P-CNF matrix. These films showed a tensile strength of 304 MPa and a Young’s modulus of 15 GPa with 10 wt % clay so that this composite film was mechanically stronger than the previously prepared CNF/clay nanopapers containing the same amount of clay.
In this work polyurethane (PU) and phenolic foam (PF) panels were mechanically grinded and incorporated within an expanded polyurethane matrix utilized for thermal insulation, in order to reduce the ...use of virgin material and to promote a circular re-utilization of recycled materials. As observed by scanning electron microscopy, the formulations containing both recyclates showed a rather homogeneous cell structure, however their presence led to a strong reduction of the closed porosity. This reflected in a slight increase in the thermal conductivity, reaching maximum values of 0.030 W/m∙K in foams with 7.5%wt of PF particles. The introduction of the recyclates slightly improved the thermal stability of the PU foams and led to a general decrease in flexural and compression properties. Cone calorimetry tests demonstrated that the inclusion of PF particles reduced the peak heat release rate up to 28 % compared to neat PU foam, enhancing the fire safety of the insulating panels.
•Mechanical recycling of PU and PF foams for the development of more eco-sustainable expanded polyurethane insulating panels.•Foams with homogeneous cell structure and notable thermal insulation capability.•Reduced combustion rates are observed for the foams containing recycled material.
Foam-like clay-nanocellulose hybrids are of great interest as load-bearing structural foams with excellent fire retardancy, due to unique effects from clay on thermal cellulose degradation. For the ...first time, the fire retardancy of clay-nanocellulose foams are studied in detail, in particular the effect of a third polymer phase, poly(vinyl alcohol). The composition with optimum mechanical properties and fire retardancy is identified and analyzed. Foams are prepared by freeze-drying and the compositions are varied systematically. Thermogravimetric analysis is performed on foam degradation. Mechanical properties from compression tests and fire retardancy data from cone calorimetry are reported, together with cellular structures from SEM and relative density estimates for the foams. Self-extinguishing foams are obtained with superior flame retardancy to commercial polymer foams. Addition of poly(vinyl alcohol) is beneficial for mechanical properties of clay-nanocellulose foams, but impedes the fire retardancy by reducing clay-cellulose synergies and cellulose charring during degradation.
The highly flammable character of cellulose-rich fibers from wood limits their use in some advanced materials. To suppress the flammability and introduce flame-retardant properties to individual pulp ...fibers, we deposited nanometer thin films consisting of cationic chitosan (CH) and anionic poly(vinylphosphonic acid) (PVPA) on fibers using the layer-by-layer (LbL) technique. The buildup of the multilayer film was investigated in the presence and absence of salt (NaCl) using model cellulose surfaces and a quartz crystal microbalance technique. Fibers were then treated with the same strategy, and the treated fibers were used to prepare paper sheets. A horizontal flame test (HFT) and cone calorimetry were conducted to evaluate the combustion behavior of paper sheets as a function of the number of bilayers deposited on fibers. In HFT, paper made of fibers coated with 20 CH/PVPA bilayers (BL), self-extinguished the flame, while uncoated fibers were completely consumed. Scanning electron microscopy of charred paper after HFT revealed that a thin shell of the charred polymeric multilayer remained after the cellulose fibers had been completely oxidized. Cone calorimetry demonstrated that the phosphorus-containing thin films (20 BL is ∼25 nm) reduced the peak heat release rate by 49%. This study identifies a unique and highly effective way to impart flame-retardant characteristic to pulp fibers and the papers made from these fibers.
Multilayered coatings deposited using the layer-by-layer (LbL) assembly technique have attracted great interest in recent years as a sustainable and efficient solution for conferring flame retardant ...properties to fabrics. The unique structure and interaction established upon the coating assembly are the key factors for successful flame retardant properties. In this study we aimed at the deposition of multilayered coatings comprising chitosan and montmorillonite with a LbL-like structure and interactions by the simple processing of compacted chitosan/montmorillonite complexes obtained by the direct mixing of an oppositely charged solution/suspension. Upon drying, the prepared complex yielded a continuous coating characterized by a brick-and-mortar multi-layered structure, in which oriented clay nanoplatelets were held together by a continuous chitosan matrix. When deposited on acrylic fabrics these coatings were able to suppress the melt-dripping phenomenon, and at 10 and 20% add-ons achieved self-extinguishing behavior within a few seconds after ignition. Cone calorimetry testing revealed an increase in time to ignition (up to +46%) and considerable reductions of the rates at which heat is released (up to −62 and −49% for peak of heat release rate and total heat release, respectively). A reduction in the total smoke release (up to −49%) was also observed.
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