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

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.     

Investigation on flammability of rigid polyurethane foam‐mineral fillers composite

This 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 (T_5%) 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.     

Nanoclay filled soy‐based polyurethane foam

Polyurethane foam was fabricated from polymeric diphenylmethane diisocyanate (pMDI) and soy‐based polyol. Nanoclay Cloisite 30B was incorporated into the foam systems to improve their thermal stabilities and mechanical properties. Neat polyurethane was used as a control. Soy‐based polyurethane foams with 0.5–3 parts per hundred of polyols by weight (php) of nanoclay were prepared. The distribution of nanoclay in the composites was analyzed by X‐ray diffraction (XRD), and the morphology of the composites was analyzed through scanning electron microscopy (SEM). The thermal properties were evaluated through dynamic mechanical thermal analysis (DMTA). Compression and three‐point bending tests were conducted on the composites. The densities of nanoclay soy‐based polyurethane foams were higher than that of the neat soy‐based polyurethane foam. At a loading of 0.5 php nanoclay, the compressive, flexural strength, and modulus of the soy‐based polyurethane foam were increased by 98%, 26%, 22%, and 65%, respectively, as compared to those of the neat soy‐based polyurethane foam. The storage modulus of the soy‐based polyurethane foam was improved by the incorporation of nanoclay. The glass transition temperature of the foam was increased as the nanoclay loading was increased. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Processing and properties of new high-temperature,lightweight composites based on foam polyimide binder

We report a method for making novel, lightweight (ρ = 0.3–1.1 kg/dm³) polymer composites based on high-temperature foam polyimide binder, carbon fibers, and organic fibers. The density and mechanical properties of the foam composite can be varied over a relatively wide range, depending on the volume contents of the fiber and air pores. The resin's high glass transition temperature of 260°C, coupled with the high thermal stability of carbon or polyimide fibers, contributes to its excellent retention of mechanical properties at elevated temperatures. The temperature at the beginning of weight loss is not lower than 570°C and depends on the kind of fiber felt. The combination of excellent thermal and specific mechanical properties of foam composites together with exceptional thermal stability and processability on conventional molding equipment can provide unusual performance for the new design of advanced materials and structures.     

Electrical conductivity and major mechanical and thermal properties of carbon nanotube‐filled polyurethane foams

The carbon nanotubes (CNTs)/rigid polyurethane (PU) foam composites with a low percolation threshold of ～ 1.2 wt % were prepared by constructing effective conductive paths with homogeneous dispersion of the CNTs in both the cell walls and struts of the PU foam. The conductive foam presented excellent electrical stability under various temperature fields, highlighting the potential applications for a long‐term use over a wide temperature range from 20 to 180°C. Compression measurements and dynamical mechanical analysis indicated 31% improvement in compression properties and 50% increase in storage modulus at room temperature in the presence of CNTs (2.0 wt %). Additionally, the incorporation of only 0.5 wt % CNTs induced remarkable thermal stabilization of the matrix, with the degradation temperature increasing from 450 to 499°C at the 50% weight loss. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical and Thermal Performances of Roselle Fiber-Reinforced Thermoplastic Polyurethane Composites

The aim of this paper is to present research findings on the measurements of mechanical, morphological, and thermal properties of Roselle fiber-reinforced thermoplastic polyurethane composites. The Roselle fiber/thermoplastic polyurethane composites were prepared with fibers of different sizes such as 125?µm and lower, 125–300 and 300–425?µm by internal mixer and hot press at 170°C. The results show that mechanical properties (tensile, flexural, and impact properties) of the composites were improved with the increase in fiber sizes. The highest tensile (10.45?MPa), flexural strength (6.93?MPa), and impact strength (20.22 kJ/m²) was obtained from composites with 300–425?µm fiber size of Roselle fiber/thermoplastic polyurethane composites. Morphological properties of dispersion fiber and tensile fracture surfaces were studied using scanning electron microscope. Thermal properties of the composites were studied using thermogravimetric analyses and results showed that the thermal decomposition effect was almost similar for all compositions.     

Effect of zeolite particulate filler on the properties of polyurethane composites

Polymer-Zeolites composites have been prepared, using castor oil based polyurethane (PU) as a host and AlPO₄-5 as particulate filler. The prepared PU/zeolite composites have been characterized for mechanical properties such as tensile strength and tensile modulus. These PU composites exhibited an improved mechanical performance compared to the unfilled PU. Thermo gravimetric analyzer (TGA) curve shows that all the chain-extended PUs are stable up to 250 °C and maximum weight loss occurs at 490 °C. The thermal stability of composites increases with increase in zeolite content. Microcrystalline parameters and micro voids of composites have been measured by using wide-angle X-ray scattering (WAXS) and Positron Annihilation Lifetime (PALS) methods respectively. The microcrystalline parameters and micro-voids from PALS indicate the interaction of the filler with the matrix is stronger beyond 5% of the filler which reflect the mechanical performance as well. Surface morphology of composites has been studied using Scanning Electron Microscopy (SEM). The photomicrograph of SEM indicates a uniform distribution of zeolite filler in the PU matrix.     

The dynamic mechanical behaviour of blends of polyphenylene sulfide with acetylene terminated sulfone

The dynamic mechanical behaviour of blends of poly(phenylene sulfide) (PPS) with the acetylene terminated sulfone bis(4-(4-ethynylphenoxy)phenyl)sulfone (ESF) was investigated by torsional braid analysis (TBA). A uniform dispersed system of ESF/PPS may be obtained by a solution process at 200°C, and can be maintained during the heat treatment up to 400°C. The increase of T_g of the blended system was found to be inappreciable by one-step and short time (e.g. 1 h) heat treatment, whatever the ESF fraction is. By a long term heat treatment or by step-curing, the T_g of the system may be raised from 180 to 220°C, in company with the increase of rigidity at 300°C, compared with pure PPS. The flexural modulus and interlaminar shear strength of continuous unidirectional carbon fibre composites with a blended matrix of ESF/PPS = 10/90 are significantly higher than those of composites with pure PPS matrix.     

Preparation and properties of multi-walled carbon nanotube/carbon/polystyrene composites

Multi-walled carbon nanotube (MWCNT)/C/polystyrene (PS) composite materials were prepared by in situ polymerization of monomer in preformed MWCNT/C foams. MWCNT/C foams were preformed using polyurethane foam as template. The preformed MWCNT/C foams had a more continuous conductive structure than the carbon nanotube networks formed by free assembly in composites. The structure of the MWCNT/C foam network was characterized with scanning electron microscopy. The MWCNT/C/PS composites have an electric conductivity higher than 0.01 S/cm for a filler loading of 1 wt.%. Enhancement of thermal conductivity and mechanical properties by the preformed MWCNT/C foam were also observed.     

Pulverized polyurethane foam particles reinforced rigid polyurethane foam and phenolic foam

Polyurethane consumption has been increasing in recent years, raising concerns about how to deal with the polymer waste. Post‐consumer rigid polyurethane foams or polyurethane foam scraps (PPU) ground into particles were utilized to strengthen mechanical properties of rigid polyurethane foam (PUF) and phenolic foam (PF). Viscosity of prepolymer with PUF was measured and PPU was well dispersed in prepolymer, as observed by optical microscope. Microstructures and morphologies of the reinforced foam were examined with scanning electron microscope (SEM) while cell diameter and density were measured by Scion Image software. Universal testing machine was employed to optimize compressive properties at various weight ratios of PPU. Both PUF and PF with 5 wt % PPU, respectively, exhibited considerable improvement in mechanical properties especially compressive property. The compressive modulus of PUF with 5 wt % PPU was 12.07 MPa, almost 20% higher than pure PUF while compressive strength of PF with 5 wt % PPU reached 0.48 MPa. The thermal stability of the reinforced foam was tested by thermal gravity analysis (TGA) and the result shows no obvious impact with PPU. The decomposition temperatures of PUF with PPU and PF with PPU were 280°C, because PPU has relatively weak thermal stability. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39734.     

The thermal aging of filled polyurethane

Thermal aging and strain endurance experiments on a filled rubber were performed at several temperatures. The rubber was polyurethane (PU) made from hydroxyl-terminated polybutadiene (HTPB) with 4,4′-diphenyl methane disocyanate (MDI). The filler was sodium chloride. The mechanical properties, glass transition temperature, dynamic viscoelasticity, and chemical structures were investigated for filled and unfilled PU under an aging period at 60 and 80°C and 50% relative humidity. We found that at 60°C the chemical structures of the filled and unfilled rubbers had no changes in 30 days during aging. But moisture had some effects on the filled PU and changed its mechanical properties. At 80°C, the chemical structures of the filled and unfilled PU had changed due to the thermal oxidation of polybutadiene in aging. The deterioration was more apparent for the filled rubber than for the unfilled. The prestraining would dewet the filler from the samples and it increased the voids.     

Pultruded fiber-reinforced polyurethane-toughened phenolic resin. II. Mechanical properties,thermal properties,and flame resistance

A novel process has been developed to toughen phenolic resin by polyurethane for fiber-reinforced pultruded composites. The mechanical properties of the composites (tensile strength, flexural strength, and notched Izod impact strength) approach maximum values at 10 wt% of the blocked polyurethane content. The fabricated composites show good mechanical properties and possess low void fraction. Notched Izod impact strength of the composite (with 5 wt% polyurethane content) increases by more than 30% compared to the virgin composite. The thermogravimetric analysis (TGA) showed that the temperature for the 5% weight loss of the phenolic/polyurethane copolymer decreases with the increasing of the polyurethane content; however, the thermal degradation temperature is still higher than 350°C. Differential scanning calorimetric analysis (DSC) showed that the onset point of copolymer is 20°C higher than that of the virgin one. The presence of the blocked polyurethane may hinder the polymerization of phenolic resin. The modified composite shows excellent dimensional stability. The copolymer composite also possesses good fire resistance. © 1996 John Wiley & Sons, Inc.     

The synergistic effects on enhancing thermal conductivity and mechanical strength of hBN/CF/PE composite

In this work, a simple and novel method was applied to prepare polymer composites by taking the advantage of melt flow shear force driving orientation of the fillers. By using this method, hexagonal boron nitride/polyethylene (hBN/PE) and hexagonal boron nitride/carbon fibers/polyethylene (hBN/CF/PE) composites were fabricated to be possessed of high thermal conductivity and mechanical properties. A high thermal conductivity of 3.11 W/mK was realized in the composite containing 35 wt% hBN and 5 wt% CF, which was over 1,200% higher than that of unfilled PE matrix. Under this component, the compressive strength and modulus of hBN/CF/PE composite were determined to be 30.1 and 870.9 MPa, respectively, which were far higher than that of unfilled PE accordingly. The bending performance was also somewhat enhanced. Meanwhile, the bulk resistivity of the composite material reached 2.55 × 10¹¹ Ω·cm, which was basically the same as that of pure PE. The novel composites with high thermal conductivity, excellent mechanical properties, and controllable electrical insulation could be a potential thermal management material for electrical and electronics industries.     

Eugenol‐Derived Bismaleimide High Performance Resins and Composites Using Diisocyanate as Property Modifier

A new kind of high performance bismaleimide resin with good processability and improved toughness is synthesized by chemical modification of 4,4′‐bismaleimidodiphenylmethane (BMI) by eugenol (EG) and different contents of 4,4′‐diphenylmethane diisocyanate (MDI). MDI‐EG‐BMI resins exhibit good thermal stability for its 5% weight loss temperatures around 300 °C and its residue of 41.61% at 900 °C, which are much higher than those of EG‐BMI resin. Then, the carbon fiber‐reinforced MDI‐EG‐BMI composites are fabricated. The mechanical properties of the composites matrixed by MDI‐EG‐BMI resins are better than those by EG‐BMI resin. For carbon/MDI‐EG‐BMI composites, their glass transition temperatures are higher than 300 °C, and their flexural strength, moduli, and toughness are maintained at a range of 217.47–404.36 MPa, 35.12–48.49 GPa, and 1.16–2.63 MJ m^?3 respectively; with the contents increasing of MDI in the resin formulation, the flexural properties first increase then decrease; comprehensively the composite with 30 wt% MDI has the best mechanical and thermal properties.     

The thermal decomposition of polyurethanes and polyisocyanurates

The thermal decomposition of a number of TDI- and MDI-based biscarbamates (model compounds for polyurethane foams) between 200°C and 1000°C showed that the urethane linkage undergoes an O-acyl fission at about 300°C to generate the free isocyanate and alcohol. In the case of the flexible foam analogues, the newly generated TDI reacts further to generate volatile polyureas, termed ‘yellow smoke’. The MDI residues generated in the decomposition of a rigid foams react to yield non-volatile polycarbodiimides. Both the yellow smokes and the polycarbodiimides decompose above 600°C to give a mixture of nitriles (including HCN) as well as a number of olefinic and aromatic compounds. The use of ¹³C labeling indicated that HCN and all the other nitriles generated during the high temperature decompositions originate in the thermal fission of the aromatic ring, the nitrile carbon being the 2-, 4- or 6- carbon of MDI.     

碳纤维/聚氨酯复合材料的制备与性能研究

以聚酯二元醇、异氰酸酯、碳纤维为主要原料,采用预聚体法制备了一系列碳纤维/聚氨酯复合材料,并对该复合材料进行了性能测试和结构表征。研究表明,复合材料的机械性能随着碳纤维长度和含量的增加出现先升高后降低的趋势。当碳纤维长度为3 mm、质量分数为1.0%时,复合材料的机械性能达到最佳值,此时其拉伸强度增加22.7%,撕裂强度增加48.1%,扯断伸长率增加5.9%。热力学分析和动态力学性能研究表明,复合材料的热分解温度提高,质量保留率提高,失重率降低,材料的玻璃化转变温度和软化温度提高,引入碳纤维后材料的耐热性提高。     

Polyurethane/poly[bis(carboxylatophenoxy)phosphazene] blends and their potential as flame‐retardant materials

A functionalized polyphosphazene, poly[bis(carboxylatophenoxy)‐phosphazene], was blended with a structural polyurethane via reactive mixing of the polymer with diisocyante and diol prepolymers. The thermal stabilites of the resultant foams were analyzed by thermogravimetric analysis (TGA). The char yields at both 400°C and 600°C increased relative to the pure polyurethane upon increasing the amount of polyphosphazene from 5 wt% to 20 wt%. At higher incorporations, the char at 400°C remained the same, but the char at 600°C continued to increase. The combustion behavior of these foams was analyzed both qualitatively, by a horizontal flame test, and quantitatively, by oxygen index (OI) measurements. Both of these tests indicated an increase in flame resistance at loadings of 20 wt% and above.     

Injection Molding and Appearance of Cellulose-Reinforced Composites

Composite materials based on an ethylene-acrylic acid (EAA) copolymer and 20 wt% cellulose fibers were compounded by two runs in a twin-screw extruder. The composite material with cellulose fibers (CF) and a reference of unfilled EAA were injection molded into plaques using three different temperature profiles with end zone temperatures of 170°C, 200°C, and 230°C. The injection molded samples were then characterized in terms of their mechanical properties, thermal properties, appearance (color and gloss), and surface topography. The higher processing temperatures resulted in a clear discoloration of the composites, but there was no deterioration in the mechanical performance. The addition of cellulose typically gave a tensile modulus three times higher than that of the unfilled EAA, but the strength and strain at rupture were reduced when fibers were added. The processing temperature had no significant influence on the mechanical properties of the composites. Gloss measurements revealed negligible differences between the samples molded at the different melt temperatures but the surface smoothness was somewhat higher when the melt temperature was increased. In general, addition of the cellulose to the EAA reduced the gloss level and the surface smoothness. POLYM. ENG. SCI., 60:5–12, 2020. © 2019 Society of Plastics Engineers     

Synthesis and properties of networking waterborne polyurethane/silica nanocomposites by addition of poly(ester amine) dendrimer

The second‐generation poly(ester amine) dendrimer was prepared by Michael addition reaction and esterification reaction at first. Then, a series of novel waterborne polyurethane (WPU)‐based composites were prepared by the addition of poly(ester amine) dendrimer into the WPU. The structures and the morphology of the WPU composites were measured with Fourier transform infrared spectrometer, scanning electron microscopy, and X‐ray diffraction. SEM images revealed that the nanosilica was well dispersed in the WPU matrix. The mechanical properties of the WPU composites were improved with the addition of poly (ester amine) dendrimer. The dynamic mechanical thermal analysis results showed that the WPU composites had higher glass transition temperature than that of pure WPU, especially after incorporation of poly(ester amine) dendrimer. This conclusion is in good agreement with the differential scanning calorimetry results. The thermal properties of the pure WPU and its composites were investigated by thermogravimetric analysis. The results showed that the initial decompose temperature began from about 250°C, and had a little increase when introducing poly(ester amine) dendrimer into the WPU matrix. POLYM. COMPOS., 2012. © 2013 Society of Plastics Engineers     

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

The 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