Cushioning performance of flexible polyurethane foams

Impact cushioning and deformation of flexible open-cell polyester polyurethane (PU) foams were studied as a function of specimen geometry, including the incorporation of controlled voids. It was shown that cushioning behavior is dependent on sample geometry, which was in trun due to a complex balance of air compression and air flow, which changes with surface area-to-volume ratio of the impact specimen. Deformation studies show that impact compression proceeded initially by crushing the surface layers with little or no deformation of the center layers. As bulk compression was increased, deformation progressively propagated for the collapsed layers tending to a more uniform strain distribution at high bulk compression strains. Local asymmetric strain patterns were exaggerated using square cushions, because of cornr effects which complicated air flow paths. It was concluded that cushion curve determination of open-cell foams would be more accurately performed using circular samples and deflecting air pressure form the top surface of the cushion to more closely simulate practical conditions. When designing at or near the margin, the number of cushions should be kept to a minimum and open surface area to volume ratios minimized by adopting square rather than strip cushions.     

Morphology of water-blown flexible polyurethane foams

A series of four TDI–polypropylene oxide (PO) water-blown flexible polyurethane foams was produced in which the water content was varied from 2 to 5 pph at a constant isocyanate index of 110. A portion of each foam was thermally compression molded into a plaque. The morphology of both the foams and plaques was investigated using dynamic mechanical spectroscopy (DMS), differential scanning calorimetry (DSC), transmission electron microscopy (TEM), scanning electron microscopy (SEM), swelling, wide angle X-ray scattering (WAXS), and small angle X-ray scattering (SAXS). A high degree of microphase separation occurs in these foams, and its degree is nearly independent of water (hard segment) content. In the foam with the lowest water content the morphology possesses many similarities to that of typical linear segmented urethane elastomers. Small hard segment domains are present with a correlation distance of about 7.0 nm. When the water content is increased a binodal distribution of hard segment material appears. There are the small hard segment domains typical of segmented urethane elastomers as well as larger “hard aggregates” greater than 100 nm in size. The larger domains are thought to be aggregates of rich polyurea that develop by precipitation during the foaming reaction. WAXS patterns of the foams suggest urea and possibly hard segment ordering that may be of a paracrystalline nature but certainly lacking in true 3-dimensional crystallinity.     

Damage evolution in flexible polyurethane foams

Microcrazing in the struts of flexible polyurethane foams was discovered during compressive deformation and observed directly in the scanning electron microscope. Attributed to this phenomena was the decrease in stress at maximum compression and the intensity of acoustic emission during compressive cycling. The higher content of styrene–acrylonitrile (SAN) copolymer in these foams resulted in higher modulus, more severe microcrazing, an increase in acoustic emission activity, and a decrease in the stress at maximum compression as cycling progressed.     

The mechano-sorptive behavior of flexible water-blown polyurethane foams

Samples of flexible water-blown slabstock polyurethane foams were compressed under constant load to study the effects of cycling moisture content on creep behavior and compare this behavior with the creep response where either a constant high or low moisture environment existed at the same temperature. Three sets of foams were tested: (1) 4 pph water content slabstock foam; (2) 5 pph water content slabstock foam; and (3) 2 pph water content molded foam. As the moisture conditions were cycled from low to high humidity while maintaining constant temperature in an environmental chamber, the compressive strain increased in subsequent steps with larger increases observed during the desorption portion of the humidity cycling. All three sets of foams showed similar behavior at a given temperature. At a temperature of 40°C, the strain levels under cyclic moisture conditions surpassed those levels observed at the highest constant relative humidity. During the first absorption step, the creep level increased. During any subsequent absorption step, the creep level either increased very little or none at all. Finally, during any desorption step, the creep level increased. This overall phenomenon of enhanced creep under cyclic moisture levels is attributed to water interacting with the hydrogen bonded structure within the foam. These hydrophillic interactions, principally promoted within the hard segment regions due to high hydrogen bonding, are disrupted causing slippage and increased in strain. As the foam is rapidly dired, regions of free volume are induced by the loss of water thus causing further increases in strain Prior to the reestablishment of well ordered hydrogen bonding. Further support to this proposition was given by the results obtained at a temperature of 90° C where it is well known that hydrogen bonds are much more mobile. Here, the strain levels under cyclic moisture conditions were nearly the same as those under constant high relative humidity. Weakening of the hydrogen bonds by means such as increased temperature resulted in similar strain levels to those under cyclic moisture levels. © 1993 John Wiley & Sons, Inc.     

Segmental orientation behavior of flexible water-blown polyurethane foams

The ambient temperature structure–property orientation behavior in two different polyureaurethane polymers (one cross-linked and one linear) was measured by using infrared dichroism along with mechanical response. Thin films (plaques) thermally compression-molded from TDI-polypropylene (PO) flexible water-blown polyurea-urethane foams and solution-cast TDI–PO polyurea–urethane elastomers were studied. Segmental orientation was measured as a function of elongation and relaxation, as well as of hysteresis behavior. The level of strain was 50–70% for the plaques and up to 240% for the elastomer. The soft segments for both materials exhibited a low state of orientation with elongation. Small changes in orientation with time and upon cyclic straining were also observed for the soft segments. Significant transverse orientation upon stretching was observed in the hard segments of the plaques and up to elongations of 100% for the elastomer. The transverse behavior of the hard segments in the plaques pressed from the foams was attributed to both the smaller hard domains as well as to the polyurea aggregates that have been reported to be present in flexible foams. This transverse behavior also suggested that the smaller hard domains and the polyurea aggregates possess a lamellarlike structure. At low strain levels (up to 50%), only small amounts of orientation hysteresis as well as mechanical hysteresis were observed for the hard segments of the plaques as well as for the elastomer. No significant relaxation in orientation was detected for the hard segments of both materials at a 30% strain level.     

环氧树脂加成多元醇增强聚氨酯软质泡沫塑料

用双酚 A型环氧树脂与乙酸反应,合成了具有刚性骨架的环氧树脂加成多元醇 (EAP),并用 FTIR与 1H－ NMR对其进行了表征。研究结果表明,工业聚醚多元醇中添加 EAP后制备的全水发泡软质聚氨酯（ PU）泡沫塑料的压入硬度显著提高,但回弹性不变。进一步研究了不同水用量对所制备 PU软质泡沫塑料力学性能的影响,并用 FTIR和光学显微镜考察了 PU软质泡沫塑料中脲基的氢键行为和泡孔结构。结果表明,在 PU软质泡沫塑料中引入 EAP刚性链对 PU泡沫塑料的结构及性能有很大影响。     

Substituting soybean oil-based polyol into polyurethane flexible foams

Polyurethane (PU) flexible foams were synthesized by substituting a portion of base polyether polyol with soybean oil-derived polyol (SBOP) as well as well-known substituent: crosslinker polyol and styrene acrylonitrile (SAN) copolymer-filled polyol. Increases in compression modulus were observed in all substituted foams and the most substantial increase was found in the 30% SBOP-substituted sample. Scanning electron microscopy (SEM) was used to examine cellular structure, in particular cell size. Polymer phase morphology, i.e., interdomain spacing and microphase separation, was studied using small-angle X-ray scattering (SAXS) and atomic force microscopy (AFM). Hydrogen bonding was investigated via Fourier transform infrared (FTIR) spectroscopy. Thermal and mechanical behaviors of foams were examined using dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). Compression properties were tested and compared via a 65% indentation force deflection (IFD) test. It was found that substituting SAN-filled polyol slightly reduced foam cell size and had no effect on polymer phase morphology. Crosslinker and SBOP polyols, on the other hand, had appreciable influence on polymer phase morphology. Crosslinker polyol disrupted hydrogen bonding between hard segments and was mixed with hard domains. SBOP polyol reduced hard domain size and soft domain fraction, and showed a broad distribution of interdomain spacings. Compression modulus increases in foams correlated well with shear modulus by DMA and could be associated with the polymer phase morphology changes.     

Nitrogen-containing products from the thermal decomposition of flexible polyurethane foams

The thermal decomposition of a polyester and a polyether flexible foam in a nitrogen atmosphere has been studied by gas chromatography, mass spec-trometry and elemental ultramicroanalysis. It is shown that the decomposition behaviours of the two foams are similar. At low temperatures (200 to 300 °C) there is a rapid and complete loss of the tolylene diisocyanate unit of each foam as a volatile yellow smoke leaving a polyol residue. The smoke has been isolated as a yellow solid (common to both foams) which contains virtually all of the nitrogen of the original foams and, under the conditions of test, is stable at temperatures up to 750 °C. Nitrogen-containing products of low molecular weight (mainly hydrogen cyanide, acetonitrile, acrylonitrile, pyridine and benzonitrile) observed during the high temperature decomposition (over 800 °C) of the foams are shown to be derived from the yellow smokes. At 1000 °C, approximately 70% of the available nitrogen has been recovered as hydrogen cyanide.     

Thermally initiated oxidation and ignition of flexible polyurethane foams

Oxidation and ignition of flexible polyurethane foams have been investigated by observing the effects of internal and external heating. External temperatures of some 190°C are required to induce combustion. Internal temperatures of 250 ?350°C initiate a self-propagating internal reaction which results in foam ignition when the reaction reaches the foam surface. The stability of a polyurethane foam to such heating increases with the age of the foam.     

Solid-state NMR characterization of motion in flexible polyurethane foams

High-resolution solid-state ¹³C-NMR has been used to study the phase separation and molecular motion in two series of polyurethane foams. These two series differ by one possessing the additive of lithium chloride, LiCl. NMR relaxation times can map the motion throughout the polymer molecule and detect changes in that motion arising from either microseparation or phase mixing between the different segments. There are only slight changes in the soft segment T_1p(¹³C) values as well as an increase in the hard segment T_1p(¹H) values with increase in the hard segment content for the foams studied. The T_1p(¹H) and T_1p(¹³C) values do indicate that the phase separation of the hard and soft segments is similar for all foams. A decrease in the T_1p(¹H) and T_1p(¹³C) values with increasing LiCl content indicates that the motion of the soft segments is restricted more by the hard segments. This is explained by more phase mixing in the foams containing the LiCl additive. © 1994 John Wiley & Sons, Inc.     

Polyisobutylene-based urethane foams. II. Synthesis and properties of novel polyisobutylene-based flexible polyurethane foams

Novel polyisobutylene-based flexible polyurethane foams (PIB–PUF) have been prepared manually by the prepolymer method using three-arm star hydroxyl-terminated polyisobutylenes (PIB–triols) and toluene diisocyanate (TDI). Solvent extraction and IR spectroscopy of PIB–PUFs indicated essentially complete crosslinking. Conventional polyether-based polyrethane foams (PE–PUFs) and polybutadiene-based polyurethane foams (PBD–PUFs) have also been prepared by the same method and select physical-mechanical properties of all these urethane foams, such as tensile strength, elongation, resilience, water permeability, hot air stability, and hydrolytic stability, have been examined and compared. Although the density of PIB–PUF is lower than that of PE–PUF, its tensile strength is superior to the latter. Elongation of PIB–PUF is almost the same as those of the other foams. The PIB–PUF exhibits low resilience which indicates good damping properties. Due to the hydrophobicity of the soft segment, PIB–PUF exhibits very low water permeability. The hydrolytic and hot air stability of PIB–PUFs are outstanding. Attempts have been made to determine gas permeabilities; however, due to the open-cell nature of the foams, these studies could not be completed. The new PIB-based urethane foams combine excellent thermal, environmental, barrier, and mechanical properties, unmatched by conventional PUFs.     

Cell distributions in and sound absorption characteristics of flexible polyurethane foams

In this article, the two-dimensional distributions of cells from the cross section of some flexible polyurethane foams were cleared, and the three-dimensional distributions of cells based on Saltykov's theory were estimated further. As a result, it was found that a mean of the two-dimensional distributions of cells was a good linear relation with a mean of the three-dimensional distributions of cells, and it was confirmed that cell structure of the foams which should have been analyzed in the three-dimensional distributions was evaluated by analysis of the two-dimensional distributions fully. It was also found that not only cell number but also cell distribution was necessary in the evaluation of flexible polyurethane foams, and cell diameter was closely related to the sound absorption coefficient in polyester-based flexible polyurethane foams. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 1395–1402, 1997     

Combustion behaviour of polyurethane flexible foams under Cone Calorimetry test conditions

The first part of this study focuses on the effect of cone calorimeter test variables on polyurethane flexible foam properties such as ignitability, heat release rate, effective heat of combustion and mass loss. Three of the main commercial foam types were used, i.e. conventional slabstock foams, high-resilience slabstock foams and all-MDI (methylene diphenyldiisocyanate) moulded foams. A decrease in heat flux (down to 40%) with increasing distance from the conical heater was measured. As a consequence, results were found to depend to a large extent on the thickness and the melting behaviour of the foam samples. To achieve a sufficiently constant and uniform heat flux exposure, sample thickness had to be limited to 25 mm. In addition, repeatability was found to be good under various conditions, with percentage standard deviations for effective heat of combustion, peak rate of heat release and mass loss below 10%. Levels of radiant flux above 25 kW m^?2 were found to be very severe to test flexible polyurethane foams. Under such conditions, foams that show large differences in combustion performance in small-scale flammability tests performed almost identically in the cone calorimeter. In the second part of this study the effects of foam variables, such as foam type, density and melamine content, are defined. These effects were clearly pronounced at radiant flux levels of 15–25 kWm^?2. Density was found to be the key variable in controlling ignition resistance. In addition, high-resilience slabstock foams and all-MDI moulded foams performed better than conventional slabstock foams of the same density. Melamine addition resulted in a delay of ignition for all three foam types and an incomplete combustion, decreased heat release and effective heat of combustion in HR-slabstock and all MDI moulded foams. However, melamine is not effective as a heat sink in conventional slabstock foams. The different performance of the foam types under study can be explained by a different melting behaviour.     

Open-cell flexible polyurethane foams: Comparison of static and dynamic compression properties

Dynamic stress–strain diagrams of polyurethane packaging foams have been obtained from free fall drop tests. The dynamic curves become higher as the deformation rates increase. An equation is proposed to describe the stress–strain dependence for different deformation rates. The model of filament buckling explains the form of the observed stress–strain dependence and phenomena related to repeated loading of the foam.     

Polymer morphology of CO2-blown rigid polyurethane foams: Its fractal nature

Small-angle x-ray scatting (SAXES) and transmission electron microscopy (TEM) have been applied to study polymer morphologies of CO₂,-blown rigid polyurethane foam samples of varying isocyanate index. The results are consistent with an irregular (meso) phase segregated structure with phase boundaries showing fractal symmetry. Phase segregation persists, througtout the index range, althougt the interfacial surfaces tends to smooothen with increasing isocyanate index to evetually results in a significant degree of energetic ‘sharing’ across the4 phase boundary. The latter can satisfactorily be explained by a free volume double layer (PVDL) model. Mechanistically. Fractal symmetry was attributed to the competition between crossliking and phase segregation tendencies in rigid PU foam polymers. The resulting frozen-in morphology represents an early stage of the development towards a more regular spinodal phase segregation, as occurring in polyuethane foam systems of lower crosslink density (e.g. flexible foams). © 1994 John Wiley & Sons, Inc.     

Development of cell morphologies in manufacturing flexible polyurethane urea foams as sound absorption materials

The effect of water content and a type of gelling catalysts [Triethylenediamine (DABCO) and dibutyltin dilaurate (DBTDL)] on chemical and physical structures of the flexible polyurethane foams (the flexible PUFs) is explored by a fourier transform infrared spectroscopy with attenuated total reflectance and a scanning electron microscope techniques. The amount of water usage plays a crucial role in controlling the sizes of cavities and pores of the PUFs. From the two gelling catalysts, the DBTDL reduces the rate of urea formation and NCO (isocyanate functional group) conversion due to the reduced molecular activity from the sterically hindered catalyst structure, comparing with the DABCO catalyst case. Strong gelling effect of the DBTDL can prevent the coalescence of the cavities and thus produce high number of well dispersed pores, but poor cavity and pore morphologies are observed in case of the fast reactions between isocyanate and water with the DABCO catalyst. The size uncertainties of cavity and pores with DBTDL catalyst are relatively smaller than with DABCO catalyst. In the sound absorption characteristics, uniformly distributed cavities and pores show better efficiency than the non-uniform cases.     

Influences of copolymer polyol on structural and viscoelastic properties in molded flexible polyurethane foams

In this study, the viscoelastic and morphological properties of molded foams were investigated to determine the influence of the presence or absence of reinforcing particulate copolymer polyols (CPP). The molded foams were based on toluene diisocyanate (TDI) and glycerol‐initiated ethylene‐oxide endcapped polypropylene oxide and, in most samples, some amount of copolymer polyol. Two series of foams were studied. In Series 1, as CPP is added to the formulation, the amount of TDI fed is kept constant. This results in a constant amount of hard‐segment content as the filler in the system displaces, by weight, the polyether polyol in the foam, and it increases the hard segment to soft segment ratio (HS/SS). In Series 2, the amount of hard‐segment material is proportionally decreased as CPP is added, resulting in a constant HS/SS ratio. Structural investigations of the foams displayed rather similar textures. The cellular structures of a CPP‐containing foam was very similar to a foam lacking the copolymer polyols. Transmission electron microscopy revealed that the CPP particles were well dispersed and that they possessed significant rigidity even at high temperature and under high compression. Although all of the foams were microphase‐separated, they varied slightly in that the copolymer polyol containing foams exhibited higher weight fractions of extractables in both Series 1 and Series 2. This suggests that not all of the CPP material is covalently bonded into the polyol matrix. It was found that temperatures above ambient as well as humidity plasticized the viscoelastic behavior of all the molded foams evaluated. It was also found that the copolymer polyol particles, as added to the molded foams of Series 1, increased load‐bearing capabilities but had a negative effect on the stress relaxation, creep, and compression set properties. In particular, the viscoelastic properties of the CPP‐containing foam were distinctly more time‐dependent than those of the foam lacking these particles. However, the Series 2 foams show that most of these effects are a result of the increased HS/SS ratio and not a result of the CPP particulate. It was shown that adding CPP while maintaining a constant HS/SS ratio improves percent load loss and load bearing under high‐humidity conditions, two important properties in flexible polyurethane foams. Finally, it was shown that at high temperatures (ca. 100°C), an additional relaxation mechanism occurs which cannot be attributed to changes in the HS/SS ratio, but must be a result of the CPP components themselves. This additional mechanism results in higher rates of load relaxation and creep in foams containing CPP at high temperatures for foams of both series. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 766–786, 2000     

Effect of hard segment content and carbon-based nanostructures on the kinetics of flexible polyurethane nanocomposite foams

Reactive flexible polyurethane (PU) foams were synthesized with two contents of hard segments (HS) and filled with multi-walled carbon nanotubes (MWCNTs), functionalized MWCNTs (f-MWCNTs) and functionalized graphene sheets (FGS). The effect of the HS content and the carbon nanofillers on the kinetics of polymerization and the kinetics of phase-separation have been studied by Fourier transform infrared spectroscopy (FT-IR) and synchrotron small-angle X-ray scattering (SAXS). A slow down on the rate of polymerization and on the development of the polymer structure due to the increase of the HS content and the inclusion of the nanoparticles was observed. Therefore, this work demonstrates that there is a relationship between the kinetics of polymerization and the kinetics of phase separation in flexible PU nanocomposite foams. SAXS data was used to generate 3D microstructures of PU nanocomposite foams and the phase-separated morphology was observed by atomic force microscopy (AFM).     

Influence of lithium chloride on the morphology of flexible slabstock polyurethane foams and their plaque counterparts

In continuing efforts to understand urea phase connectivity in flexible polyurethane foams and its implications on physical properties, LiCl is used to alter the phase-separation behavior of slabstock foams. Comparisons are also drawn with plaque counterparts, which are prepared using the same polyol, isocyanate, and chain extender (water). LiCl is shown to alter the solid-state phase separation behavior of the foams and the plaques in a similar manner. This is confirmed using multiple characterization techniques, which provide information at different scale lengths. The foams and plaques with and without LiCl are shown to possess a microphase separated morphology with interdomain spacings of ca. 100 Å. SAXS and TEM reveal that addition of LiCl reduces the urea aggregation behavior, typical in slabstock polyurethane foams, leading to a loss in the urea phase macro connectivity. Hard segment ordering, as studied by WAXS and FTIR, is shown to be of a similar nature in the plaque and foam, which do not incorporate LiCl. Addition of LiCl leads to a loss in the segmental packing behavior, or micro level connectivity of the urea phase, in both the plaques and corresponding foams, as inferred from WAXS and FTIR. The LiCl additive interacts with the polyol soft segments in an insignificant manner as shown from FTIR and DMA. In addition, foams containing LiCl are found to possess more intact cell windows due to the influence of LiCl on reaction kinetics as well as its effect on the precipitation of the urea phase. The experimental observations are supported by quantum mechanical calculations using a density functional theory approach, where molecular interactions between LiCl and model ether, urethane, and urea compounds are investigated. Interaction geometries of most stable complexes and their stability energies are calculated. Stability energies of ether/LiCl, urethane/LiCl, and urea/LiCl were determined to be −189, −617, and −687 kJ/mol, respectively, reinforcing that LiCl interacts predominantly with urea hard segments and in a minimal manner with the polyol soft segments.     

超软质聚氨酯泡沫的制备

概述了超软质聚氯酯泡沫的几种主要制备方法。