The role of microstructure on the mechanical properties of polyurethane foams containing thermoregulating microcapsules

Rigid polyurethane foams with up to 50 wt% of microcapsules from LDPE-EVA containing Rubitherm^®RT27 were synthesized. The influence of microcapsules on the foams density, microstructure and mechanical resistance was studied. Cell size and strut and wall thicknesses were analyzed by SEM. The relationships between densities and foam microstructures with their Young's moduli and collapse stress were found by the Gibson and Ashby formulations and the Kerner equation for mechanical properties of composites. It was found a cell structure change from polyhedral closed-cells to spherical or amorphous open-cells. A good agreement between the experimental and theoretical data was observed but requiring a cell form factor. Thus, Fitting parameters confirmed the high trend of these microcapsules to be incorporated into the foam cell walls and the form factors depicted the abrupt change of cell morphology. Thus, these equations are suitable for predicting the mechanical properties of foams containing fillers of low mechanical resistance.     

The manufacture of microencapsulated phase change materials suitable for the design of thermally enhanced fabrics

Thermal comfort of a fabric is one of the important tasks of the designers that require an engineering approach. In this study, we first aimed to establish a manufacturing technique based on in situ polymerization in order to accomplish the microencapsulation of phase change materials (PCMs) that can ultimately be used in different textile applications, i.e. incorporating such products into the multi-component non-conventional fabrics. This method is suitable for the laboratory-scale work as well as the industrial-scale one, considering some important issues like energy and time savings. Four types of polyurea-formaldehyde microcapsules containing different waxes and a control group of 100% shell material were produced and then examined by DSC, particle size and SEM analyses. Furthermore, we also focused on the contributions of microencapsulated PCMs to the thermal performances of fabrics of certain passive insulation characteristics for the given cold weather and physical activity conditions, based on the model developed for a multi-layer fabric system.     

Polypropylene as a potential matrix for the creation of shape stabilized phase change materials

Phase change materials, based on isotactic polypropylene (PP) blended with soft and hard Fischer−Tropsch paraffin wax respectively, were studied in this paper. DSC, DMA, TGA and SEM were used to determine the structure and properties of the blends. While paraffin waxes in the blend changed state from solid to liquid, the PP matrix kept the material in a compact shape. Strong phase separation was observed in both cases, which was more pronounced in the case of soft paraffin wax. Despite the fact that both grades of paraffin wax are not miscible with PP due to different crystalline structures, it was shown that the hard Fischer−Tropsch paraffin wax is more compatible with PP than the soft one. Both waxes plasticized the PP matrix. TGA showed that PP blended with the hard Fischer−Tropsch wax degrades in just one step, whereas blends containing soft paraffin wax degrade in two distinguishable steps. SEM exposed a completely different morphology for the two paraffin waxes and confirmed the lower compatibility of PP and soft paraffin wax. The soft and hard characters of the waxes were manifested in the viscoelastic properties, where the blends containing soft paraffin wax exhibited a lower elastic modulus than pure polypropylene, whereas the hard Fisher−Tropsch paraffin wax solidified the matrix. However, both kinds of blends were able to sustain the dynamic forces applied by the DMA within five cycle runs implying good shape stability.     

Thermal analysis of phase change emulsion

This paper presents some results obtained by Differential Scanning Calorimetry (DSC) for characterizing the phase transition within an emulsion. The dispersed substances are either hexadecane, octadecane, water or binary solution. A non-equilibrium model taking into account the inter-phase heat transfer between the emulsifying medium and the dispersed droplet is proposed and explains the main experimental features.     

Natural aging of shape stabilized phase change materials based on paraffin wax

Natural aging of shape-stabilized phase change materials containing linear low density polyethylene (LLDPE), paraffin wax and expanded graphite (EG) in Qatari climate has been studied. It was found that expanded graphite significantly improved the performance of prepared SSPCMs in multiple ways. Firstly, EG suppressed leakage of paraffin wax from the compact shape of SSPCMs. The addition of 15 wt% of EG to shape stabilized phase change materials (SSPCMs) containing 50 wt% of wax caused a decreasing in the leakage of wax by 50% over 210 days of natural aging.Secondly, ∖expanded graphite enhanced the photochemical stability of the blends; this was confirmed by FTIR analysis, where carbonyl index decreased with EG content.     

Effects of biopitch on the properties of flexible polyurethane foams

Biopitches are industrial residues obtained by the distillation of the tar recovered during Eucalyptus charcoal production and can be used as a renewable polyol source. Flexible polyurethane foams were prepared with different proportions of biopitch and HTPB (hydroxyl-terminated polybutadiene) and using polymeric MDI (4,4′ diphenyl methane diisocyanate), N,N dimethylcyclohexylamine as a catalyst and water as a blowing agent. Elemental analysis, thermal analysis (TG/DSC), Fourier Transform Infrared Spectroscopy (FTIR), scanning electronic microscopy (SEM), and density results were used aiming to discuss the contribution of biopitch to foams properties. The higher the biopitch content, the higher the thermal stability and the lower the density of the flexible foams (air atmosphere), behaviors similar to those of lignin-based polyurethanes. Biopitch enhanced the oxygen content of the polyurethane foams synthesized, and their reaction with HTPB resulted in stable foams.     

Phase change materials based on low-density polyethylene/paraffin wax blends

Phase change materials, based on low-density polyethylene blended with soft and hard paraffin waxes respectively, were studied in this paper. DSC, DMA, TGA and SEM were employed to determine the structure and properties of the blends. The blends were able to absorb large amounts of heat energy due to melting of paraffin wax, whereas the LDPE matrix kept the material in a compact shape on macroscopic level. The hard paraffin wax was, however, much more miscible with LDPE because of co-crystallization than the soft paraffin wax. LDPE blended with hard paraffin wax degrades in just one step, while blends containing soft paraffin wax degrade in two distinguishable steps. SEM showed completely different morphology for the two paraffin waxes and confirmed the lower miscibility of LDPE and soft paraffin wax. DMA analyses demonstrated the toughening effect of the waxes on the polymer matrix. This technique was also used to follow the thermal expansion as well as the dimensional stability of the samples during thermal cycling. The most visible expansion could be seen in the first cycle, probably due to a totally different thermal history of the sample. With further cycling the dimensions stabilized after two and four cycles for soft and hard paraffin wax, respectively. Controlled force ramp testing on DMA confirmed poor material strength of the blends containing soft wax, especially at temperatures above wax melting.     

Time-dependent structural breakdown of microencapsulated phase change materials suspensions

Microencapsulated phase change materials (MPCM) suspensions are multi-phase heat transfer fluids which exploit the latent heat of phase change materials. The effect of MPCM on the rheological properties of suspensions of microcapsules in glycerol were investigated to explore the suitability of the suspensions as a pumpable heat transfer fluid. Three different rheological models were utilized to characterize the time-dependent structural breakdown of the suspensions, and the second-order structural kinetic model was found to give a better fit to the experimental data than the Weltman and Figoni-Shoemaker models. The MPCM form agglomerates, which are disrupted by shear forces. The breakdown of the agglomerated structures was most pronounced at high shear rates where the microcapsules are subjected to stronger disruptive forces. More agglomerates are present at higher concentrations, which causes a stronger breakdown of the agglomerated structures when the concentration is raised. The time-dependent structural breakdown of MPCM suspensions plays an important role for improving the efficiency of heat transfer liquids based on such materials.GRAPHICAL ABSTRACT     

Synthesis of the polyethylene glycol solid-solid phase change materials with a functionalized graphene oxide for thermal energy storage

Polyethylene glycol (PEG) as a phase change material possesses three obstacles, such as leakage, low thermal conductivity and low thermal stability. A novel solid-solid phase change material (PCM) based on functionalized graphene oxide (GO), Polyethylene glycol (PEG) was prepared, and the three obstacles of PEG as a PCM was solved in one and the same material. Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), Raman and Transmission electron microscope (TEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric analysis (TG) and thermogravimetric analysis/infrared spectrometry (TG-IR) were used to study the properties of supporting material and composite PCM (CPCM). The results indicated that the PEG was grafted on the surface of the supporting material; Compared with pure PEG, the latent heat of CPCM with 9.6 wt% supporting material decreased only 5.3%, however, the thermal conductivity of CPCM increased 111% and the heat peak release rate of CPCM decreased 33.4%.     

Improvement of thermal inertia of styrene–ethylene/butylene–styrene (SEBS) polymers by addition of microencapsulated phase change materials (PCMs)

In this work, microencapsulated phase change materials (PCMs) with a melting temperature of 52 °C have been used to improve thermal inertia phenomena on an elastomeric matrix of styrene–ethylene/butylene–styrene (SEBS) material. The amount of PCMs has varied in the 1–10 wt.% and these materials have been processed by conventional injection molding without PCM degradation. Mechanical characterization of SEBS–PCM compounds has been carried out and the obtained results show good maintenance of both resistant and ductile properties for PCM amounts comprised in the 1–5 wt.% range. Scanning electron microscopy (SEM) analysis has revealed good wetting properties of PCM microcapsules with the SEBS matrix which is a key factor to obtain good mechanical performance. The effect of PCM addition on thermal inertia has been evaluated by active infrared thermography (IRT), showing a remarkable effect on thermal regulation of SEBS in the temperature range close to the melting point of the PCM (52 °C). This thermoregulation effect is more accurate as the PCM content increases. Also, cooling curves have been constructed in order to quantify the thermal inertia effect in a cooling process.     

Kinetics and retention characteristics of some nitrophenols onto polyurethane foams

The kinetics of sorption of the nitrophenols by the unloaded polyurethane foams (PUFs) were found fast, reached equilibrium in few minutes and followed a first-order rate equation with an overall rate constant k in the range (0.16-0.21)±0.01 min⁻¹. The retention of the tested nitrophenols by the unloaded foams is consistent with the “solvent extraction” mechanism. However, the sorption also followed Langmuir, Freundlich and Dubinin-Radushkevich (D-R) isotherms. The mean free sorption energy of the nitrophenols onto the PUF was found equal to 7.5±0.4 kJ/mol, which reflects physical sorption. Thus, a dual-mode involves both absorption related to solvent extraction and an added component for surface adsorption seems a more likely sorption mechanism model. While a dual-mode sorption model explains the observed retention behavior, the data suggest that, solvent extraction plays a much larger role than the added component for surface adsorption. The sorption and recovery percentages of the nitrophenols from fresh, natural and industrial wastewater by the proposed unloaded foam columns were quantitatively achieved. The height equivalent to theoretical plates (HETP), N, the breakthrough capacity and the critical capacity for the unloaded foam columns were found in the range of (0.8-1.1)±0.6 mm, (94-132)±3, 3.2-4.02 and 1.5-2.67 mg/g, respectively. The method was successfully applied for the retention and recovery of the tested nitrophenols spiked to fresh and industrial wastewaters.     

Thermal degradation studies of polyurethane/POSS nanohybrid elastomers

Reported here is the synthesis of a series of polyurethane/POSS nanohybrid elastomers, the characterisation of their thermal stability and degradation behaviour at elevated temperatures using a combination of thermogravimetric Analysis (TGA) and thermal volatilisation analysis (TVA). A series of PU elastomer systems have been formulated incorporating varying levels of 1,2-propanediol-heptaisobutyl-POSS (PHIPOSS) as a chain extender unit, replacing butane diol. The bulk thermal stability of the nanohybrid systems has been characterised using TGA. Results indicate that covalent incorporation of POSS into the PU elastomer network increases the non-oxidative thermal stability of the systems. TVA analysis of the thermal degradation of the POSS/PU hybrid elastomers have demonstrated that the hybrid systems are indeed more thermally stable when compared to the unmodified PU matrix; evolving significantly reduced levels of volatile degradation products and exhibiting a ∼30 °C increase in onset degradation temperature. Furthermore, characterisation of the distribution of degradation products from both unmodified and hybrid systems indicate that the inclusion of POSS in the PU network is directly influencing the degradation pathways of both the soft and hard-block components of the elastomers: The POSS/PU hybrid systems show reduced levels of CO, CO₂, water and increased levels of THF as products of thermal degradation.     

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.     

Preparation and properties of negative ion/polyurethane flexible foam composites

Abstract

In this study, negative ionpowder was modified with a silane coupling agent and then added to the polyurethane flexible foam to prepare NI/PU flexible foam composites by the one-step foaming method. The effects of the amount of negative ion powder on the mechanical properties, thermal properties and release of negative ions were investigated using scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and negative ion detectors. The SEM results showed that modified negative ion powder could be more uniformly distributed around the cell walls of the polyurethane flexible foam. The thermal stability, tensile strength and resilience of the NI/PU flexible foam composite were improved with the increase of the amount of modified negative ion powder. Increasing the amount of modified negative ion powder could also result in an increase in the release of negative ions, and it reached 5500/cm³ or higher at a negative ion content of 3%.     

Thermal degradation characteristics of rigid polyurethane foam and the volatile products analysis with TG-FTIR-MS

Thermal degradation characteristics of rigid polyurethane (PUR) foam in both air and nitrogen gaseous environments were studied using thermogravimetry and differential scanning calorimetry (TG-DSC) hyphenated techniques. And in situ Fourier Transform Infrared (FTIR) was employed to investigate the characteristic functional groups of the decomposition residues at different temperatures. It is found that the thermal degradation of PUR material in air and N₂ present a three-stage and a two-stage process, respectively. And the degradation reaction rate of PUR in air is accelerated significantly due to the presence of oxygen. The thermal degradation mechanism of PUR under non-oxidizing gaseous environment was evaluated using a TGA instrument coupled with Fourier Transform Infrared and mass spectrometer (TG-FTIR-MS). HCFC-141b served as blowing agent is detected at the initial stage. The urethane bond groups of PUR start to break up into isocyanates segments and polyols segments from about 200 °C. With an increase of temperature, the polyols decompose into some kinds of aliphatic ether alcohol. In the temperature range of 350–500 °C, the dominant volatile products are primary amines, secondary amines, vinyl ethers and CO₂.     

The thermal stability of fully charged and discharged LiCoO2 cathode and graphite anode in nitrogen and air atmospheres

Polyethylene glycol (PEG) compounds and mixtures have many properties that make them suitable for thermal applications in buildings, such as having high heat of fusion, phase change repeatability, chemical stability, non-corrosive behavior, and low-cost. In this study, we developed a number of PU rigid foams incorporated with three types of PEGs, as new insulation materials provided with an enhanced thermal capacity, and sought their suitability for various applications such as layer of floor and ceiling coverings in constructions, insulations in controlled temperature transportation packaging, inner coverings of automobile seats, etc. In order to investigate the thermal properties of PEG-containing PU foams, differential scanning calorimeter (DSC) tests were conducted first. Then, a two-layer concrete–PU foam system was designed in the laboratory conditions to examine the insulation performances via using a computer-aided thermal measurement setup which was sensitive to the simulated environmental temperature changes. The PU-PEG composites produced here can be helpful for the design of thermal insulators. PUI, including 44% PEG 600, exhibited fairly efficient thermal regulation under moderate ambient temperature conditions, whereas PUII (49% PEG 1000) is suitable for temperature control in both mild and hot surroundings. PUIII, containing 53% PEG 1500, showed suitable heat storage and thermal stability characteristics. PUIV, containing 38% PEG 600/PEG 1000/PEG 1500, also confirmed good thermal and durability characteristics. The blend of three PEGs is suitable for preventing discontinuous thermal regulation when the external temperature increases or decreases. PU foams containing PEGs can be assumed to be leak-resistant, which is promising for their industrial applications.     

Scalable single-step synthesis of lignin-based liquid polyols with ethylene carbonate for polyurethane foams

A new method for the synthesis of lignin-based liquid polyols was developed. Organosolv lignin was reacted with ethylene carbonate in polyethylene glycol as solvent, leading to a full conversion of the phenolic OH into primary aliphatic OH groups. These aromatic polyols are obtained in a single step, without any purification. Upon modification of the polyethylene glycol molar mass, a wide range of hydroxyl values (I_OH) can be covered. The polyols with up to 30%wt lignin have a viscosity suitable for the direct elaboration of polyurethane (PUR) foams. The method presents significant advantages over oxypropylation, the most common method for producing lignin-based polyols since it is performed at ambient pressure, without any toxic chemicals, does not require purification or post treatment, and allows to produce polyols with tunable properties. Four different aromatic polyols were then synthesized to produce rigid PUR foams, with substitution of up to 100% of a standard polyether polyol. The developed polyols showed very high reactivity, allowing to reduce the catalyst content in the PUR formulation by 75%. Rigid PUR foams prepared with 25% substitution of the standard polyol showed properties in the range of commercial PUR foams, with more than 90% closed cells and thermal conductivity of about 25 mW m^?1/K, perfectly adequate for thermal insulation applications.     

X-ray fluorescence spectrometric determination of germanium after extraction with polyurethane foam

Germanium is extracted onto polyurethane foam as molybdogermanate, and determined by X-ray fluorescence spectrometry in the dried foam. The extraction is effective between pH 0.5 and 3.7 and as little as 7 μg of germanium can be detected in 100 ml of aqueous solution.     

Effect of chemical structure on combustion and thermal behaviour of polyurethane elastomer layered silicate nanocomposites

The effect of polyol molecular weight and functionality on nanodispersion of clay in PU/clay nanocomposites and the investigation of their thermal and combustion properties are reported and discussed. Lamellar elastomer polyurethane nanocomposites were synthesized using polyols with different molecular weight and functionality and according to these parameters they show several degrees of dispersion which affect their thermal and combustion behaviour. A barrier effect of clay layer is shown in TGA experiments by a delay of thermal degradation products release in nanocomposite materials compared to the virgin polymer; this barrier effect also leads to formation of char during combustion which lowers the peak of rate of heat release in cone calorimeter tests and eliminates fire-induced dripping of the nanocomposite sample during UL 94 test. However, in order to achieve non-burning behaviour nanocomposite technology must be combined with conventional flame retardant technology.     

水性聚氨酯相变储能材料的相变机理

以聚乙二醇(PEG)为软段、六亚甲基二异氰酸酯-1,4-丁二醇-二羟甲基丙酸(HDI-BDO-DMPA)为硬段,制备了一系列水性聚氨酯相变储能材料(WPUPCM)。在相变过程中,由于软段PEG由聚合前的固-液相变转化为聚合后的固-固相变,因此,所制备的WPUPCM表现出固-固相变特性。为了研究其固态相变行为的本质和形成机理,揭示该类聚合物的能量贮存和转换机理,应用偏光显微镜、扫描电镜、原子力显微镜、X射线衍射仪分析研究了PEG、WPUPCM在相变过程中的晶体结构变化特征,讨论了WPUPCM固-固相转变的机理。