Rigid polyurethane foams reinforced with disilanolisobutyl POSS: Synthesis and properties

This work reports the synthesis of rigid polyurethane (PU) foams modified by disilanolisobutyl polyhedral oligomeric silsesquioxane (DSIPOSS). This open‐cage nanostructure silsesquioxane has 2 hydroxyl groups and therefore can be chemically built directly in the PU backbone to form hybrid polyurethane‐POSS foam. Synthesis procedure using polymeric 4,4′‐diphenylmethane diisocyanate, polyetherol, and DSIPOSS has been elaborated, and the influence of POSS on the cell structure, closed cell content, apparent density, thermal conductivity, and compression strength of the rigid polyurethane composites has been evaluated. The hybrid composite foams containing 1.5 and 2.0 wt% DSIPOSS showed a reduced number of cells and an increased average area of foam cells in comparison with the unmodified PU, while the addition of 0.5wt% of DSIPOSS causes an increase in the number of cells of the foam as compared with the reference and thus a reduction in the average area of cells. X‐ray microtomography provided data on the porous structure of polyurethane hybrid materials, including reduction of the pore surface area. Scanning electron microscopy and energy‐dispersive X‐ray spectroscopy analysis revealed a good homogenization of DSIPOSS in polyurethane matrix. Thermogravimetric analysis results have shown that incorporation of POSS nanoparticles into PU foam does not significantly change the degradation process. The compressive strength of PUF‐POSS hybrids in the direction parallel and perpendicular to the direction of foam rise is greater than the strength of the reference foam already for the lowest DSIPOSS content.     

Carbon nanofiber reinforced syntactic foams: Degradation mechanism for long term moisture exposure and residual compressive properties

Hollow particle filled polymer matrix composites, called syntactic foams, are challenging for studies related to environmental exposure and degradation mechanisms due to the possible role of matrix, particle–matrix interface, and particle material and wall thickness. In the current study, syntactic foams reinforced with 1 wt.% vapor grown carbon nanofibers (CNFs) are subjected to water immersion and characterized for residual compressive properties under quasi-static and high strain rates. The testing is conducted on four different types of syntactic foams, fabricated with glass hollow particles of two different densities: 220 and 460 kg/m³ in 30 and 50 vol.% quantities. After a period of 6 months, a maximum of 7% weight gain is observed in the worst performing syntactic foam. The exposed specimens are tested for residual compressive properties and the results are compared with the properties of dry specimens. The quasi-static compressive strength of CNF reinforced syntactic foams is found to decrease and the modulus remained unaffected due to the moisture exposure. The high strain rate compressive strength was 1.3–2.2 times higher for wet and dry specimens compared to the quasi-static strength of the same type of syntactic foams.     

Sound absorption and compressive property of PU foam‐filled composite sandwiches: Effects of needle‐punched fabric structure,porous structure,and fabric‐foam interface

The flexible polyurethane (PU) foam‐filled composite sandwiches are constructed using three types of needle‐punched fabrics (upper layer), PU foam (core layer), and nylon (bottom layer). Different contents of deionized water were used to adjust the pore size and bulk density of PU foam by free‐foaming. Effects of needle‐punched fabric components, cell structure, and fabric‐foam interface on sound absorption and compressive property of the composite sandwiches were investigated. Fabric‐foam interface contributes to improve high‐frequency sound absorption efficiency. When containing 0.5 wt% water in the core and nylon‐glass grid needle‐punched composite fabric (NPUN‐G) in the upper face, the composite sandwiches exhibited optimal sound absorption of 0.78 at low frequency of 450 Hz, and optimal compressive strength of 14.4 kPa. Combination of needle‐punched composite fabric improved the sound absorption coefficient and compressive strength, as high as 223% and 121%, respectively, compared with pure PU foam. This study provided an important basis for the preparation of high‐strength composite sandwiches with low‐frequency sound absorption.     

Mechanical properties,thermal stability,sound absorption,and flame retardancy of rigid PU foam composites containing a fire‐retarding agent: Effect of magnesium hydroxide and aluminum hydroxide

Isocyanate, polyether polyol, a flame retardant (10 wt%), and aluminum hydroxide/magnesium hydroxide (0, 5, 10, 15, and 20 wt%) are used to form the rigid polyurethane (PU) foam, while nylon nonwoven fabrics and a polyester aluminum foil are combined to serve as the panel. The rigid PU foam and panel are combined to form the rigid foam composites. The cell structure, compressive stress, combustion resistance, thermal stability, sound absorption, and electromagnetic interference shielding effectiveness (EMI SE) of the rigid foam composites are evaluated, examining the effects of using aluminum hydroxide and magnesium hydroxide. Compared with magnesium hydroxide, aluminum hydroxide exhibits superior performance to the rigid foam composites. When aluminum hydroxide is 20 wt%, the rigid foam composite has an optimal density of 0.153 g/cm³, an average cell size of 0.2466 mm, a maximum compressive stress of 546.44 Kpa, an optimal limiting oxygen index (LOI) of 29.5%, an optimal EMI SE of 40 dB, and excellent thermal stability and sound absorption.     

Lanthanum phenylphosphonate–based multilayered coating for reducing flammability and smoke production of flexible polyurethane foam

In the present work, lanthanum phenylphosphonate (LaPP)–based multilayered film was fabricated on the surface of flexible polyurethane (PU) foam by layer‐by‐layer self‐assembled method. The successful deposition of the coating was confirmed by scanning electron microscopy (SEM) and energy‐dispersive X‐ray (EDX). Subsequently, the thermal decomposition and burning behavior of untreated and treated PU foams were investigated by thermogravimetric analysis (TGA) and cone calorimeter, respectively. The TGA results indicated that T_max2 of treated PU foams were increased by approximately 15°C to 20°C as compared with untreated PU foam. The peak heat release rate (PHRR) and total heat release (THR) of PU‐6 (with 19.5 wt% weight gain) were 188 kW/m² and 20.3 MJ/m², with reductions of 70% and 15% as compared with those of untreated PU foam, respectively. Meanwhile, the smoke production of treated PU foam was suppressed after the construction of LaPP‐based coating.     

The effect of post-consumer PET particles on the performance of flexible polyurethane foams

In this work, the use of post-consumer PET (polyethylene terephthalate), PET_pc, as reinforcement filler in flexible polyurethane foams was studied, with the aim of finding alternatives for the recycling of polymer packaging. Density, number of cells per linear centimeter, tensile resistance, strain at break and tear resistance of standard foams were compared to those of foams with PET_pc in the formulation, using 1.5 parts per hundred of polyol of PET_pc (granulometric range 0–297 μm). The produced foams were sectioned into top, mid-top, mid-bottom and bottom layers. Tensile resistance, strain at break and tear resistance of the reinforced foam surpassed those of the standard foam for all layers. The number of cells was constant but density increased towards the base of the block. In addition, the filled foams yielded better wear, compression set and compression resistance than the standard foam, whereas no significant variation in morphology (cell shape) was found.     

Synthesis and morphology of rigid polyurethane foams with POSS as pendant groups or chemical crosslinks

This work reports on the preparation of polyurethane foams (PUFs) chemically modified by functionalized 1,2‐propanediolisobutyl polyhedral oligosilsesquioxane (PHI‐POSS) as pendant groups and octa(3‐hydroxy‐3‐methylbutyldimethylsiloxy) POSS (OCTA‐POSS) as chemical crosslinks. The resulting foams, which contain 0 to 15 wt% POSS (versus polyol), were characterized in terms of their structure, morphology, density, thermal conductivity, compressive strength, and water absorption. Fourier transform infrared‐attenuated total reflectance revealed good reaction rate between POSS and PUF. PHI‐POSS suppresses the formation of the hydrogen bonds in the soft phase. The composite foams with OCTA‐POSS showed a reduced number of cells and increased average area of foam cells in comparison with the PUF, while the addition of PHI‐POSS causes an increase in the number of cells of the foam as compared with the reference, and thus a reduction in the average area of cells. Scanning electron microscopy–energy‐dispersive X‐ray spectroscopy analysis revealed that POSS moieties form lamellae‐shaped crystals of different sizes, distributed homogeneously in the bulk (PHI‐POSS) or close to the self surfaces (OCTA‐POSS). The compressive strength of PUF/POSS hybrids in the direction parallel and perpendicular to the direction of foam rise is greater than the strength of the reference foam. PHI‐POSS improves monotonically the compressive strength in the studied loading range. About 5 wt% OCTA‐POSS also provides reinforcement, but further loading reverses the phenomenon. PUF/POSS hybrids absorb less water than the pristine foam because of an increase of foam density. Copyright © 2015 John Wiley & Sons, Ltd.     

Effect of walnut shells and silanized walnut shells on the mechanical and thermal properties of rigid polyurethane foams

In the study walnut shells (WS) and silanized walnut shells (S_WS) were used as cellulosic fillers for novel polyurethane (PU) composite foams. The impact of 1, 2 and 5 wt% of WS and S_WS on the foaming parameters, mechanical and thermo-mechanical properties of obtained materials were evaluated. The results have shown that compared to untreated WS filler, the application of S_WS leads to PU foams with more regular structure and improved physico-mechanical behavior of PU materials. For example, compared to controlled WS_0 foam, PU foams enhanced with 1 wt% of the S_WS exhibited better mechanical properties, such as higher compressive strength (~15% of improvement), better impact strength (~6% of improvement), and improved tensile strength (~9% of improvement). The addition of S_WS improved the thermomechanical stability of PU foams. This work provides a better understanding of a relationship between the surface modification of the walnut shell filler and the mechanical, insulating and thermal properties of the PU composites. Due to these positive and beneficial effects, it can be stated that the use of WS and S_WS as natural fillers in PU composite foams can promote a new application path in converting agricultural waste into useful resources for creating a new class of green materials.     

Nutmeg filler as a natural compound for the production of polyurethane composite foams with antibacterial and anti-aging properties

Polyurethane (PU) composite foams were successfully reinforced with different concentrations (1 wt%, 2 wt%, 5 wt%) of nutmeg filler. The effect of nutmeg filler concentration on mechanical, thermal, antimicrobial and anti-aging properties of PU composite foams was investigated. PU foams were examined by rheological behavior, processing parameters, cellular structure (Scanning Electron Microscopy analysis), mechanical properties (compression test, impact test, three-point bending test, impact strength), thermal properties (Thermogravimetric Analysis), viscoelastic behavior (Dynamic Mechanical Analysis) as well as selected application properties (thermal conductivity, flammability, apparent density, dimensional stability, surface hydrophobicity, water absorption, color characteristic). In order to Disc Diffusion Method, all PU composites were tested against selected bacteria (Escherichia coli and Staphylococcus aureus). Based on the results, it can be concluded that the addition of 1 wt% of nutmeg filler leads to PU composite foams with improved compression strength (e.g. improvement by ~19%), higher flexural strength (e.g. increase of ~11%), improved impact strength (e.g. increase of ~32%) and comparable thermal conductivity (0.023–0.034 W m⁻¹ K⁻¹). Moreover, the incorporation of nutmeg filler has a positive effect on the fire resistance of PU materials. For example, the results from the cone calorimeter test showed that the incorporation of 5 wt% of nutmeg filler significantly reduced the peak of heat release rate (pHRR) by ca. 60% compared with that of unmodified PU foam. It has been also proved that nutmeg filler may act as a natural anti-aging compound of PU foams. The incorporation of nutmeg filler in each amount successfully improved the stabilization of PU composite foams. Based on the antibacterial results, it has been shown that the addition of nutmeg filler significantly improved the antibacterial properties of PU composite foams against both Gram-positive and Gram-negative bacteria.     

Hydrophobic,superabsorbing materials from reduced graphene oxide/MoS2 polyurethane foam as a promising sorbent for oil and organic solvents

This study illustrates the preparation of robust superhydrophobic and superoleophilic reduced graphene oxide (rGO) and MoS₂ nanoparticles incorporated polyurethane (PU) foam by in-situ polymerization via the one-shot method. Spectroscopic analyses confirmed the successful formation of nanoparticles and also the development of the hybrid PU material. The sponges were evaluated based on hydrophobicity and oil absorbance capacities and the modified foam exhibits the water contact angle of 151°. The pore size of the foam analyzed using an optical microscope and the effect on the density and porosity were also analyzed. The oil absorption capacity of the foam was studied using standard sorption testing. The oil and organic solvent selectivity and recyclability of hybrid PU foam were performed to estimate whether the foams could be recycled and reused. The modified system shows very high selectivity (83–94%). The recyclability of the foam was about 35 cycles without much reduction in its own weight and after 55 cycles more than 80% of the oil absorption capacity was conserved. The resulting hybrid PU material is highly efficient, porous, ultralight, hydrophobic and reusable sorbent material and displays great potential for versatile environmental remediation.     

Compressive stress relaxation of metallocene‐based polyolefin foams: Effect of gamma‐ray‐induced crosslinking

Metallocene‐based polyolefin (MPO) foams possess a closed‐cell structure which is in contrast to the open‐celled structure of polyurethane (PU) foams. In this study, we investigate the effects of gamma‐irradiation on the mechanical behavior of MPO foams using PU foam behavior as a basis. Compressive step‐strain experiments reveal a two‐step relaxation process in MPO foams, dominated by polymer chain relaxation at short times and gas diffusion from the closed cells at longer times. On the other hand, the relaxation in PU foams is similar to fully crosslinked polymers with the relaxation modulus reaching an equilibrium value after an initial decay. The closed‐celled structure of MPO foams lends to rapid stress relaxation and low structural recoverability upon application of compressive loads. Exposure to gamma radiation induces crosslinking in MPO foams and improves their resilience and recoverability. Stress relaxation tests reveal that nonradiated MPO foams show complete relaxation and structural loss at high temperatures. In contrast, radiated MPO foams show a significant retardation in relaxation kinetics and structural stability attributed to radiation‐induced crosslinking. Dynamic rheology and solvent‐extraction studies also support the results obtained from stress‐relaxation experiments. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1045–1056, 1999     

Melamine,silica, and ionic liquid as a novel flame retardant for rigid polyurethane foams with enhanced flame retardancy and mechanical properties

Rigid polyurethane (PU) foams were successfully filled with different weight ratios of melamine (1 wt%, 5 wt%, 10 wt%), silica (0.1 wt%) and ionic liquid, 1-Ethyl-3-methylimidazolium chloride, [EMIM]Cl (0.3 wt%). The aim of this study was to improve the flame retardancy of PU foams and to develop the synergistic effect between melamine, silica and ionic liquid on the flame-retardant PU foams. The influence of different loadings of the fillers was examined. The results showed that in comparison with unfilled foam, all modified compositions are characterized by higher density (41–46 kg m⁻³), greater compression strength (134–148 kPa), and comparable thermal conductivity (0.023–0.026 W m⁻¹ K⁻¹). Moreover, the reaction to fire of the PU composites has been investigated by the cone calorimeter test. The results showed that the fire resistance of PU foams containing as little as 1 wt% of melamine is significantly improved. For example, the results from the cone calorimeter test showed that the incorporation of the melamine, silica and ionic liquid significantly reduced the peak of heat release rate (pHRR) by ca. 84% compared with that of unmodified PU foam. SEM results showed that incorporated fillers can form an intumescent char layer during combustion which improves the reaction to fire of the composite foams.     

The deformation and failure response of closed-cell PMDI foams subjected to dynamic impact loading

The present work aims to investigate the bulk deformation and failure response of closed-cell Polymeric Methylene Diphenyl Diisocyanate (PMDI) foams subjected to dynamic impact loading. First, foam specimens of different initial densities are examined and characterized in quasi-static loading conditions, where the deformation behavior of the samples is quantified in terms of the compressive elastic modulus and effective plastic Poisson's ratio. Then, the deformation response of the foam specimens subjected to direct impact loading is examined by taking into account the effects of material compressibility and inertia stresses developed during deformation, using high speed imaging in conjunction with 3D digital image correlation. The stress-strain response and the energy absorption as a function of strain rate and initial density are presented and the bulk failure mechanisms are discussed. It is observed that the initial density of the foam and the applied strain rates have a substantial influence on the strength, bulk failure mechanism and the energy dissipation characteristics of the foam specimens.     

On the role of TiO<Subscript>2</Subscript> nanoparticles on thermal behavior of flexible polyurethane foam sandwich panels

A series of flexible polyurethane foam (FPUF) and monolithic polyurethane (PU) sandwich panels reinforced with different contents of TiO₂ nanoparticles (0, 0.5 and 1 mass%) have been successfully prepared by compression molding process at room temperature. The influence of TiO₂ nanoparticles on the thermal properties of PU matrix has been investigated by thermogravimetric and dynamic mechanical thermal analysis (DMTA). The morphology of porous structure of FPUF sandwich panels has been characterized by scanning electron microscopy. The presence of TiO₂ nanoparticles as reinforcement has improved the thermal properties of the FPUF and PU sandwich panel samples. It has been observed that FPUF and PU sandwich panel reinforced with 1 mass% of TiO₂ nanoparticles possessed the highest enhancement in thermal properties in all accomplished thermal tests. The DMTA results for the FPUF and PU sandwich panel reinforced with 1 mass% of TiO₂ nanoparticles indicated that the storage modulus and loss modulus have increased about 1.22 and 1.25 times, 1.5 and 1.55 times, respectively, compared to pure samples. Furthermore, the glass transition (T _g) obtained from the damping factor (tanδ) curves has increased 2 and 1 °C for FPUF and PU sandwich panels, respectively.     

聚氨酯/环氧树脂互穿网络硬质泡沫塑料反应过程和微观结构

聚氨酯／环氧树脂互穿网络(PU／EPIPN)硬泡中异氰酸根的消耗速度较纯PU硬泡高，是由于环氧树脂的固化荆同时也是异氰酸根反应的催化荆。而PU／EP IPN硬泡中环氧基的反应速度和反应程度均较纯EP网络低，归因于互穿网络对基团扩散的阻碍。在互穿网络硬泡形成过程中，存在环氧开环中所新产生的羟基与异氰酸根的反应、大分子多元醇中羟基与环氧基的反应以及异氰酸根与环氧基形成嗯唑烷酮的反应三种形成网络间的化学键的途径。同时由于PU／EPIPN硬泡高度的交联，使得IPN硬泡中两个网络具有良好的相容性。动态力学性能表明所有IPN样品都只有一个玻璃化温度。透射电镜表明IPN样品无明显的相界面。     

Poly(ether–imide)/polyurethane foams reinforced with graphene nanoplatelet: Microstructure,thermal stability,and flame resistance

Novel poly(ether–imide)/polyurethane (PEI/PU)-based nanocomposite and foamed systems reinforced with graphene nanoplatelet (GNP) were developed. Field emission scanning electron microscopy revealed hexagonal nanocelluar morphology due to fine interaction between PEI/PU and functional GNP. Compression strength and modulus values were raised up to 72.3 MPa and 27.3 GPa, respectively, for PEI/PU/GNP Foam 1, thus revealing a defensive role of GNP layer against damage. T_max of PEI/PU/GNP Foam 0.1–1 was measured as 479–565°C. The UL 94 showed V-0 rating for nanocomposite, while foams attained V-1 rating. Water absorption capacity was improved steadily with time and was at maximum after 96 h for PEI/PU/GNP Foam 1 (12.3%).     

Influence of iron content on thermal stability of magnetic polyurethane foams

Magnetorheological (MR) materials are a group of smart materials which have the controllable magnetic properties with an external magnetic field. Magnetic foams, a specific type of MR solids, were synthesized from flexible polyurethane (PU) foams and carbonyl iron particles. Effects of the carbonyl iron particles on the thermal stability of the magnetic foams have been studied. Thermogravimetric analysis (TGA) was applied to characterize the thermal degradation process of the magnetic foams and then the apparent activation energy of degradation was calculated by using Ozawa's method [Ozawa T. A new method of analyzing thermogravimetric data. Bulletin of the Chemical Society of Japan 1965; 38: 1881-1886.]. The carbonyl iron particles were found to improve the thermal stability of magnetic foams in nitrogen by showing higher 10 wt% loss temperature, slower weight loss rate and higher apparent activation energy than pure PU foams. But the magnetic foams were observed to have slightly worse thermal stability in air than pure PU foams at the earlier degradation stage. At the later degradation stage, the magnetic foams exhibited the higher activation energy than pure PU foams in air.     

毛竹屑与玉米淀粉共液化产物制备聚氨酯泡沫研究

采用单因素试验设计,研究了液化剂组成、液比以及毛竹屑与淀粉的比例对液化产物理化性质、及所制备的聚氨酯泡沫材料的物理力学指标影响.结果显示当以50%乙二醇+50%碳酸亚乙酯混合物作为液化剂、添加相当于液化剂质量3%的浓硫酸为催化剂、在(150±5)℃(油浴)和常压条件下,液化150min,搅拌速度30r/min,取得本试验条件下最好的竹屑液化效果,液化产物中竹屑含量25%,残渣率3.96%,但该液化产物中天然聚合物碎片含量少,所制备的聚氨酯泡沫材料塌陷;竹屑与玉米淀粉共液化有效提高了液化产物中生物质的含量,但占液化剂质量25%竹屑+占液化剂质量125%玉米淀粉共液化产物粘度太高(8.85Pa.s);而20%竹屑+130%玉米淀粉的共液化产物与4,4′-二苯基甲烷二异氰酸酯以及各种助剂按异氰酸酯基/羟基摩尔比为1.1配合时,所制备的聚氨酯泡沫材料表观密度为33.6kg/m3、压缩强度118kPa、弹性模量6.91MPa,在周年生物降解试验中,该生物质基聚氨酯硬质泡沫失重率为12.63%.     

Treatment of low level radioactive liquid wastes using composite ion-exchange resins based on polyurethane foam

Composite ion-exchange resins were prepared by coating copper-ferrocyanide (CFC) and hydrous manganese oxide (HMO) powders on polyurethane (PU) foam. Polyvinyl acetate/Acetone was used as a binder. The foam was loaded with about five times its weight with CFC and HMO powders. The distribution coefficients of CFC-PU foam and HMO-PU foam for cesium and strontium respectively were estimated. Under similar conditions the HMO-PU foam showed higher capacity as well as better kinetics for removal of strontium than CFC-PU foam for Cs. The pilot plant scale studies were conducted using a mixed composite ion-exchange resin bed. About 1000 bed volumes could be passed before attaining a DF of 10 from an initial value of 60–80. The spent resin was digested in alkaline KMnO₄ and the digested liquid was fixed in cement matrix. The matrices were characterized with respect to compressive strength and leach resistance.     

Studying the Suitability of Nineteen Lignins as Partial Polyol Replacement in Rigid Polyurethane/Polyisocyanurate Foam

In this study, nineteen unmodified lignins from various sources (hardwood, softwood, wheat straw, and corn stover) and isolation processes (kraft, soda, organosolv, sulfite, and enzymatic hydrolysis) were used to replace 30 wt.% of petroleum-based polyol in rigid polyurethane/polyisocyanurate (PUR/PIR) foam formulations. Lignin samples were characterized by measuring their ash content, hydroxyl content (Phosphorus Nuclear Magnetic Resonance Spectroscopy), impurities (Inductively Coupled Plasma), and pH. After foam formulation, properties of lignin-based foams were evaluated and compared with a control foam (with no lignin) via cell morphology, closed-cell content, compression strength, apparent density, thermal conductivity, and color analysis. Lignin-based foams passed all measured standard specifications required by ASTM International C1029-15 for type 1 rigid insulation foams, except for three foams. These three foams had poor compressive strengths, significantly larger cell sizes, darker color, lower closed-cell contents, and slower foaming times. The foam made with corn stover enzymatic hydrolysis lignin showed no significant difference from the control foam in terms of compressive strength and outperformed all other lignin-based foams due to its higher aliphatic and p-hydroxyphenyl hydroxyl contents. Lignin-based foams that passed all required performance testing were made with lignins having higher pH, potassium, sodium, calcium, magnesium, and aliphatic/p-hydroxyphenyl hydroxyl group contents than those that failed.