Rigid Polyurethane Foam Composites Research Articles

Bio-based rigid polyurethane foam prepared from apricot stone shell-based polyol for thermal insulation application – Part 2: Morphological, mechanical, and thermal properties

The procedure for the liquefaction of apricot stone shells was reported in Part 1. Part 2 of this work determines the morphological, mechanical, and thermal properties of the bio-based rigid polyurethane foam composites (RPUFc). In this study, the thermal conductivity, compressive strength, compressive modulus, thermogravimetric analysis, flammability tests (horizontal burning and limited oxygen index (LOI)) in the flame retardants), and scanning electron microscope (SEM) (cell diameter in the SEM) tests of the RPUFc were performed and compared with control samples. The results showed the thermal conductivity (0.0342 to 0.0362 mW/mK), compressive strength (10.5 to 14.9 kPa), compressive modulus (179.9 to 180.3 kPa), decomposition and residue in the thermogravimetric analysis (230 to 491 °C, 15.31 to 21.61%), UL-94 and LOI in the flame retardants (539.5 to 591.1 mm/min, 17.8 to 18.5%), and cell diameter in the SEM (50.6 to 347.5 μm) of RPUFc attained from liquefied biomass. The results were similar to those of foams obtained from industrial RPUFs, and demonstrated that bio-based RPUFc obtained from liquefied apricot stone shells could be used as a reinforcement filler in the preparation of RPUFs, specifically in construction and insulation materials. Moreover, liquefied apricot stone shell products have potential to be fabricated into rigid polyurethane foam composites.

Biobased rigid polyurethane foam prepared from apricot stone shell-based polyol for thermal insulation application, Part 1: Synthesis, chemical, and physical properties

Polyurethane foam is one of the most versatile construction insulation materials because of its low density, high mechanical properties, and low thermal conductivity. This study examined biobased rigid polyurethane foam composites from apricot stone shells, which are lignocellulosic residues. The apricot stone shells were liquefied with a PEG-400 (polyethylene glycol-400) and glycerin mixture in the presence of sulfuric acid catalyst at 140 to 160 °C for 120 min. Rigid polyurethane-type foam composites from the reaction were successfully prepared with different chemical components. Biobased polyurethane-type foam composites were successfully produced from the liquefied apricot stone shells. The FTIR spectra of liquefaction products confirmed successful liquefaction of products and that they are sources of hydroxyl groups. The liquefaction yield (81.6 to 96.7%), hydroxyl number (133.5 to 204.8 mg KOH per g), the highest elemental analysis amount (C, H, N, S, O) (62.08, 6.32, 6.12, 0.13, and 25.35%), and density (0.0280 to 0.0482 g per cm3) of the rigid polyurethane foam composites were comparable to foams made from commercial RPUF composites.

The influence of carbon-encapsulated transition metal oxide microparticles on reducing toxic gases release and smoke suppression of rigid polyurethane foam composites

The rapid development and massive consumption of rigid polyurethane foams (RPUF) has drawn attention to their fire safety related problems, such as the heat release and notable generation of smoke and toxic gases in fire. Three novel types of carbon-encapsulated transition metal oxide microparticles, Cu@C, Fe2O3@C and Cu2O@Fe2O3@C, were prepared via a simple hydrothermal method in this research. Potential smoke and toxicity suppression by the as-prepared carbon-encapsulated hybrids in flame-retardant RPUF composites with ammonium polyphosphate (APP) and dimethylmethylphosphonate (DMMP) were investigated. Compared with pure RPUFs, the peak heat release rate (pHRR) value of RPUF/A5-D5/5.0Fe2O3@C decreased by 40.5%, indicating the obvious improved flame retardancy. Besides, the related mechanisms of smoke suppression and toxic based on the catalytic effect of transition metal oxide was also proposed on the basis of experiment results.

Synergistic effects of expandable graphite and ammonium pentaborate octahydrate on the flame‐retardant, thermal insulation, and mechanical properties of rigid polyurethane foam

AbstractThe use of flame retardants (FRs) to improve the flame retardancy but also having good insulation and mechanical properties of rigid polyurethane foam (RPUF) has become significant due to the increasing demand in both the industry and academia. In the present study, a series of RPUF composites containing expandable graphite (EG), ammonium pentaborate (APB) octahydrate, and their binary blends were prepared with one‐shot and free‐rise methods. The effects of FRs on the FR and physical‐mechanical properties of RPUFs were investigated. The results show that both EG and APB could improve the flame retardancy of RPUFs and reduced the smoke production. The FR effect of EG was better than APB and more importantly, synergistic effect was found between EG and APB. The best results were obtained by the foam in the composition of 15E and 5A. The cone calorimeter test results showed that the peak heat release rate (pHRR) and total smoke release (THR) of 15E/5A foam were lower than the foams of 20E and 20A. The pHRR and THR values of 15E/5A foam decreased about 57.5% and 42.8% compared to the neat RPUF, respectively. Total smoke production (m2) also reduced about 77.0% by 20E and 83.6% by 15E/5A foams. Thermogravimetric analysis indicates that the char residue of 15E/5A foam increased to 39.5%, which provided better flame retardancy. The foam composites have high compressive strength (105‐150 kPa) and low thermal conductivity values (19.9‐21.3 mW/mK). While the thermal conductivity of 15E/5A foam increased by 0.5%, its compressive strength increased by 6.1%.

Investigation on flammability of rigid polyurethane foam‐mineral fillers composite

SummaryThis study investigates the incorporation of castor oil–based rigid polyurethane foam with mineral fillers feldspar or kaolinite clay in order to enhance the mechanical, thermal, and flame retardant properties. Influence of mineral fillers on the mechanical strength was characterized by compressive strength and flexural strength measurement. Thermogravimetric analysis (TGA) was performed to diagnose the changes in thermal properties, while cone calorimeter test was performed to ascertain the flame retardancy of the mineral filler–incorporated rigid polyurethane foam composites. Results showed that the foams incorporated with mineral filler demonstrated up to 182% increase in compressive strength and 351% increase in flexural strength. Thermal stability of these composite foams was also found to be enhanced on the incorporation of kaolinite clay filler with an increase in 5% weight loss temperature (T5%) from 192°C to 260°C. Furthermore, peak heat release rate (PHRR), total heat release (THR), smoke production rate (SPR), and total smoke release (TSR) were also found to decreased on the incorporation of mineral filler in the rigid polyurethane foam. So mineral fillers are ascertained as a potential filler to enhance the mechanical, thermal, and flame retardant behaviors of bio‐based rigid polyurethane foam composites.

Mechanical, acoustic, and thermal performances of shear thickening fluid–filled rigid polyurethane foam composites: Effects of content of shear thickening fluid and particle size of silica

ABSTRACTShear thickening fluid (STF) features a rheological property, and rigid polyurethane (PU) foams feature low thermal conductivity and excellent acoustic insulation. In this study, an STF/PU rigid foam composite sandwich structure was designed using different contents (0, 0.5, 1, or 1.5 wt %) of STF that contained 14 nm, 40 nm, or 75 nm silicon dioxide (SiO2). The effects of STF content and silica size on the cell structure, mechanical performance, acoustic absorption, and thermal performance of the STF/PU foam were explored. The test results show that STF/PU foam exhibited three characteristic acoustic absorption peaks, and the maximum acoustic absorption coefficient reached 0.841. STF addition increased compression, bending strength, and maximum acoustic coefficient, as well as initial mass loss temperature. STF‐filled PU foam composites containing 14 nm and 40 nm SiO2 had a mild rise in thermal insulation. The rigid STF/PU foam composites with a cell structure had the maximum thermal conductivity of 0.22 W m−1 K−1 and sound absorption coefficient of 0.841, which confirm that they are a good candidate for sound‐absorbing energy conservation materials. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47359.

Effects of hydrotalcite on rigid polyurethane foam composites containing a fire retarding agent: compressive stress, combustion resistance, sound absorption, and electromagnetic shielding effectiveness.

Polyether polyol, isocyanate, and a flame retardant (10 wt%), hydrotalcite (0, 1, 3, 5, 7, and 9 wt%) are used to form a rigid PU foam, while a nylon nonwoven fabric (400 g m−2) and a polyester aluminum foil are combined to serve as the panel. The rigid PU foam and the panel are then combined to form the rigid foam composites. The cell structure, compressive stress, combustion resistance, thermal stability, sound absorption, and electromagnetic shielding effectiveness of the rigid foam composites are evaluated, examining the effects of using hydrotalcite. When the hydrotalcite is 5 wt%, the rigid foam composites have an optimal density of 0.168 g cm−3, an average cell size of 0.2858 mm, a maximum compressive stress of 479.95 kpa, an optimal LOI of 29, an optimal EMSE of 45 dB, and the maximum thermal stability and sound absorption.

Effects of preparation conditions on properties of rigid polyurethane foam composites based on liquefied bagasse and jute fibre

Rigid polyurethane foams based on liquefied bagasse and reinforced with jute fibre were prepared. The effects of preparation conditions were investigated using a paper cup with a small horizontal section area as a mould. They were reflected in the foam height, which acted as a sensitive indicator. Density gradient existed in the foam rise direction and decreased from the bottom to top. Although the amount of blowing agent water was fixed, the foam height increased with stirring time after the addition of diphenyl methane diisocyanate, the isocyanate index and the catalyst content. This was partly due to the released heat that also contributed to the foam expansion. The relative intensity of the C─N stretching band at 1510 cm−1 and the N─H out-of-plane bending band at 1527 cm−1 in the FTIR spectrum reflected isocyanate reactions, which had a close relationship with the crosslink density. The normalized compressive strength was essentially attributed to the combined effects of the crosslink density and the thickness of cell walls and struts. Jute fibre enhanced the compressive strength only slightly due to poor interfacial adhesion between some fibres and the matrix.

Rigid polyurethane foam composites with vegetable filler for application in the cosmetics industry

This study was designed towards the development of rigid polyurethane foam (RPURF) composites for application in the cosmetics industry using ground hazelnut shell waste as filler. Additionally, the influence of the filler content on the structure of the composites, as well as on their physico-mechanical, thermal, and biological properties was investigated. The particle size distribution and chemical structure of the natural filler, was examined. The synthesized foams were analyzed using a variety of techniques such as infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and scanning electron microscopy (SEM). Furthermore, the apparent density, water absorption, dimensional stability, compressive strength, and resistance to aging of the materials were determined. Due to the proposed application, the toxicity analysis of the synthesized materials was essential. The conducted research resulted in the development of the composition and preparation procedure for the synthesis of rigid polyurethane foam biocomposites incorporating a high content of ground hazelnut shell as filler.

Phosphorus and Nitrogen-Containing Polyols: Synergistic Effect on the Thermal Property and Flame Retardancy of Rigid Polyurethane Foam Composites

In this work, the investigation mainly focused on the synergistic effect of phosphorus-containing polyol (BHPP) and nitrogen-containing polyol (MADP) in improving the flame retardancy of EG/rigid polyurethane foam (RPUF). BHPP and MADP were synthesized through dehydrochlorination and Mannich reaction, respectively. The influence of the weight ratio of BHPP and MADP was studied by thermogravimetric analysis and limiting oxygen index (LOI) tests. The results demonstrated that the optimal weight percentage of BHPP and MADP in flame-retarding RPUF was 1/1. In addition, the incorporation of expandable graphite (EG) into the RPUF/BHPP/MADP system could greatly improve the flame-retardant properties of RPUF composites. When the content of EG was 15 wt %, LOI value of RPUF composites reached 33.5%. Furthermore, the value of the peak of the heat release rate was reduced by 52.4% compared to that of pristine RPUF. Based on the analysis and discussion, a condensed flame-retardant mechanism was primarily proposed.

Development and applicational evaluation of the rigid polyurethane foam composites with egg shell waste

This study was designed towards the development of a series of rigid polyurethane foam (RPUF) composites with egg shells (ES) used as natural filler. Another goal was the determination of the filler content influence on the structure of the materials as well as on their physico-mechanical and biological properties. The synthetic procedure for the production of RPUF composites with high content of the natural filler was successfully established and the properties of obtained materials were tested using a variety of analytical procedures. Infrared spectroscopy was applied in order to analyse the chemical constitution of the materials as well as the degree of phase separation and changes related to the aging process. Scanning electron microscopy was used to determine the changes in cell structure of the materials and thermal degradation processes were investigated using thermogravimetric analysis. Powder x-ray diffraction experiments were performed in order to verify the presence of crystalline phase in the samples. Additionally the apparent density, dimensional stability, water absorption, friability and compressive strength were determined for synthesised materials. The biological properties of the obtained RPUFs were examined using the toxicity test employing human monocyte cell line as well as by bacteria adhesion tests. The selection of the optimal product was based on the optimisation of the renewable substrate content and the application properties in order to develop an environmentally-friendly material with the most valuable characteristics.

The study of mechanical behavior and flame retardancy of castor oil phosphate-based rigid polyurethane foam composites containing expanded graphite and triethyl phosphate

Abstract The goal of this work was the synthesis of novel flame-retarded polyurethane rigid foam with a high percentage of castor oil phosphate flame-retarded polyol (COFPL) derived from renewable castor oil. Rigid flame-retarded polyurethane foams (PUFs) filled with expandable graphite (EG) and diethyl phosphate (TEP) were fabricated by cast molding. Castor oil phosphate flame-retarded polyol was derived by glycerolysis castor oil (GCO), H2O2, diethyl phosphate and catalyst via a three-step synthesis. Mechanical property, morphological characterization, limiting oxygen index (LOI) and thermostability analysis of PUFs were assessed by universal tester, scanning electron microscopy (SEM), oxygen index testing apparatus, cone calorimeter and thermogravimetric analysis (TGA). It has been shown that although the content of P element is only about 3%, the fire retardant incorporated in the castor oil molecule chain increased thermal stability and LOI value of polyurethane foam can reach to 24.3% without any other flame retardant. An increase in flame retardant was accompanied by an increase in EG, TEP and the cooperation of the two. Polyurethane foams synthesized from castor oil phosphate flame-retarded polyol showed higher flame retardancy than that synthesized from GCO. The EG, in addition to the castor oil phosphate, provided excellent flame retardancy. This castor oil phosphate flame-retarded polyol with diethyl phosphate as plasticizer avoided foam destroy by EG, thus improving the mechanical properties. The flame retardancy determined with two different flame-retarded systems COFPL/EG and EG/COFPL/TEP flame-retarded systems revealed increased flame retardancy in polyurethane foams, indicating EG/COFPL or EG/COFPL/TEP systems have a synergistic effect as a common flame retardant in castor oil-based PUFs. This EG/COFPL PUF exhibited a large reduction of peak of heat release rate (PHRR) compared to EG/GCO PUF. The SEM results showed that the incorporation of COFPL and EG allowed the formation of a cohesive and dense char layer, which inhibited the transfer of heat and combustible gas and thus increased the thermal stability of PUF. The enhancement in flame retardancy will expand the application range of COFPL-based polyurethane foam materials.

Core-shell structure design of pulverized expandable graphite particles and their application in flame-retardant rigid polyurethane foams

Pulverized expandable graphite (pEG) and melamine − formaldehyde (MF) resin core − shell structure particles (pEG@MF) as specific flame retardants for rigid polyurethane foam (RPUF) were synthesized by encapsulating pEG particles with a layer of MF resin via in situ polycondensation. The initial feed weight ratio of pEG and MF prepolymer was found to be the key factor affecting the shell forming process, and the shell growth can be regarded as a combination of ‘raspberry-like’ and conventional ‘core–shell’ formation mechanisms. With the encapsulation of a well formed MF shell, the expandability of pEG particles was significantly enhanced from 42 mL g–1 to 76 mL g–1 and thus the pEG@MF particles showed good flame-retardant performance in RPUF. The RPUF/pEG@MF composites passed the V-0 rate and the limiting oxygen index was remarkably increased from 21 to 28 vol% by adding only 10 wt% pEG@MF particles; both the expandability and available expandable graphite content played an important role in controlling the flame-retardant performance of pEG@MF particles. With a loading of fine sized pEG@MF particles, desirable mechanical and thermal insulation properties of RPUF/pEG@MF composites were achieved by preserving the complete cell structure of RPUF and screening the high thermal conductivity of the pEG particles with the thermally inert MF resin shell. The exciting application of the novel pEG@MF particles indicates that the core–shell structure design of expandable graphite can serve as promising solution for fabricating halogen-free flame-retardant RPUF composites with high performance. © 2013 Society of Chemical Industry

Enhanced mechanical and thermal properties of rigid polyurethane foam composites containing graphene nanosheets and carbon nanotubes

AbstractThe comparative study of rigid polyurethane foam (RPUF) nanocomposites based on graphene nanosheets (GNSs) and carbon nanotubes (CNTs) has been reported. A GNS content of 0.3 wt% in polyol turns to be optimal for its foamability with the isocyanate component, as verified by rheology measurements. Scanning electron microscopy and transmission electron microscopy observations reveal a homogeneous dispersion of GNSs and CNTs in the RPUF nanocomposites. Only 0.3 wt% loading of GNSs and CNTs led to 36% and 25% improvement respectively in the compressive modulus of the RPUF nanocomposites. Meanwhile, 16 °C and 14 °C improvements in the glass transition temperature confirm the important role of both the nanofillers in the heat resistance of RPUF nanocomposites. These results additionally indicate that GNSs work more effectively than CNTs in mechanical property and heat resistance enhancement of the RPUF nanocomposites. The superiority of GNSs over CNTs can be attributed to their wrinkled surface structure, unique two‐dimensional geometrical morphology and higher specific surface area, which results in stronger interaction and restriction of segmental motion at the interface between the GNSs and the RPUF matrix. In addition, changes in the thermal conductivity of the nanocomposites are negligible, indicating that incorporation of GNSs and CNTs will not hinder the application of RPUF nanocomposites as thermal insulators. On the contrary, the enhancement in mechanical properties and heat resistance will undoubtedly expand the application range of polyurethane foam materials. Copyright © 2012 Society of Chemical Industry

Expandable graphite‐methyl methacrylate‐acrylic acid copolymer composite particles as a flame retardant of rigid polyurethane foam

AbstractAn emulsion polymerization method was employed to prepare pulverized expandable graphite (pEG)‐poly(methyl methacrylate‐acrylic acid) copolymer [(PMA)] composite particles, and then the pEG‐P(MA) particles were used for a flame retardant of the rigid polyurethane foam (RPUF). Fourier transform infrared (FTIR) spectroscopy data demonstrated the existence of P(MA) in the pEG‐P(MA) particles, and the result of the thermogravimetric analysis (TGA) indicated that the content of P(MA) was 24.3 wt %. Morphological observation showed that the pEG particles were encapsulated by a layer of polymer coating to form typical core–shell composite particles. Due to the possible reaction between COOH of pEG‐P(MA) and R‐CNO of isocyanate, the compatibility between the composite particles and the RPUF matrix was highly enhanced. In contrast to the pEG, the limiting oxygen index (LOI), the horizontal and vertical burning tests showed the pEG‐P(MA) composite particles could improve the flame retardancy effectively. The improved flame retardancy of the RPUF matrix was attributed to the increased expansion volume ratio of pEG‐P(MA) particles as exposed to fire. The dynamical mechanical analysis (DMA) showed that the incorporation of the core–shell particles could improve the storage modulus and tan δ of the RPUF composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Effect of surface modification of montmorillonite on the properties of rigid polyurethane foam composites

This study investigated the influence of various organically modified montmorillonites (organoclays) on the structure and properties of rigid polyurethane foam (RPUF) nanocomposites. The organoclays were modified with cetyltrimethyl ammonium bromide (CTAB), methyl tallow bis(2-hydroxyethyl) quaternary ammonium chloride (MT2ETOH) and tris(hydroxymethyl)aminomethane (THMA) and denoted as CMMT, Cloisite 30B and OMMT, respectively. MT2ETOH and THMA contain hydroxyl groups, while THMA does not have long aliphatic tail in its molecule. X-ray diffraction and transmission electron microscopy show that OMMT and Cloisite 30B can be partially exfoliated in the RPUF nanocomposites because their intercalating agents MT2ETOH and THMA can react with isocyanate. However, CMMT modified with nonreactive CTAB is mainly intercalated in the RPUF matrices. At a relatively low filler content, the RPUF/CMMT composite foam has a higher specific compressive strength (the ratio of compressive strength against the apparent density of the foams), while at relatively high filler contents, RPUF/Cloisite 30B and RPUF/OMMT composites have higher specific compressive strengths, higher modulus and more uniform pore size than the RPUF/CMMT composite.

Effects of expandable graphite and ammonium polyphosphate on the flame‐retardant and mechanical properties of rigid polyurethane foams

AbstractIn this work, the effect of expandable graphite (EG) and ammonium polyphosphate (APP) on the flame retardancy and mechanical properties of the rigid polyurethane foam (RPUF) was studied. The results indicated that both EG and APP could effectively improve the flame retardancy of RPUF, while the retardancy of EG was better than APP. When the flame‐retardant loading was 15 wt %, the limited oxygen index (LOI) values of APP‐ and EG‐filled RPUF were 24.5 and 32 vol %, respectively. According to the LOI test, the optimal ratio of APP to EG in RPUF composites was 1 : 1 by weight, at which the LOI value of 15 wt % (APP + EG)/RPUF was 30.5 vol %. Thermal degradation test of RPUF composites by thermogravimetric analysis indicated that the addition of APP and EG to RPUF could lead to an increase in the amount of high‐temperature residue. Under the same conditions, the residue amount of EG/RPUF was less than that of APP/RPUF at the same temperature. Compression test and dynamic thermal mechanical analysis indicated that both the compressive strength and modulus decreased at a certain extent with the EG‐ or APP‐filled into RPUF, respectively, but with the mixture of EG and APP added into RPUF, the mechanical properties of these materials increased. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Flame retardancy of different‐sized expandable graphite particles for high‐density rigid polyurethane foams

AbstractThe effects of expandable graphite (EG) of different particle sizes, on the fire‐retardant properties of high‐density rigid polyurethane foam (RPUF) (0.45 g cm−3) were studied. Samples of EG with different particle sizes were obtained by pulverization in an ultra‐high‐speed mixer for 4 and 13 min, respectively. It was shown that as received (EG0) and 4 min pulverized EG (EG4) efficiently improved the fire‐retardant properties of RPUF composites, while 13 min pulverized EG (EG13) did not. The char of the burned composites filled with EG0 and EG4 covered the whole surface of the samples and formed a complete physical barrier. This barrier material prevented combustible gases from feeding the flame and also isolated oxygen efficiently from the burning material. EG13 did not produce enough char to cover the whole surface of the burning sample, resulting in poor fire‐retardant property of the RPUF composites. Thermal degradation tests of the foams by thermogravimetric analysis indicated that EG showed negligible effects on the thermal stability of the RPUFs. Copyright © 2006 Society of Chemical Industry

Expandable Graphite For Halogen-Free Flame-Retardant of High-Density Rigid Polyurethane Foams

ABSTRACT We obtained the high-density rigid polyurethane foam (RPUF) filled with expandable graphite (EG) by airtight cast molding, and its fire performance was evaluated. The results show that the LOI values increase linearly with EG content, especially the LOI value of the 20 wt% EG-filled RPUF composites increases rapidly to 39.5% from 22.5% of pure RPUF. When the pure RPUF was burned, no clear transition process between burning spots and virgin material is observed. But when the EG/RPUF composite was burned, EG produced high-volume expanded graphite and covered the surfaces of the materials, which can prevent combustible gases from feeding the flame, and it also separates oxygen from the burning material efficiently. The thermal degradation of foam was investigated using thermogravimetric analysis (TGA). The result shows that the thermo-oxidative degradation of pure RPUF takes place in the range of 220–350°C and 450–650°C, respectively. The thermal stability of RPUF composites increased slightly when it contained 20 wt% EG. The mechanical and electrical properties of EG/RPUF were also discussed. Generally, addition of EG resulted in a slight decrease in the mechanical properties and no influence on the electrical conductivity.