Cryogenic thermal insulating and mechanical properties of rigid polyurethane foams blown with hydrofluoroolefin: Effect of perfluoroalkane

The effect of perfluoroalkane (PFA) on the morphology, thermal conductivity, mechanical properties and thermal stability of rigid polyurethane (PU) foams was investigated under ambient and cryogenic conditions. The PU foams were blown with hydrofluorolefin. Morphological results showed that the minimum cell size (153 μm) was observed when the PFA content was 1.0 part per hundred polyols by weight (php). This was due to the lower surface tension of the mixed polyol solution when the PFA content was 1.0 php. The thermal conductivity of PU foams measured under ambient (0.0215 W/mK) and cryogenic (0.0179 W/mK at −100°C) conditions reached a minimum when the PFA content was 1.0 php. The low value of thermal conductivity was a result of the small cell size of the foams. The above results suggest that PFA acted as a nucleating agent to enhanced the thermal insulation properties of PU foams. The compressive and shear strengths of the PU foams did not appreciably change with PFA content at either −170°C or 20°C. However, it shows that the mechanical strengths at −170°C and 20°C for the PU foams meet the specification. Coefficient of thermal expansion, and thermal shock tests of the PU foams showed enough thermal stability for the LNG carrier’s operation temperature. Therefore, it is suggested that the PU foams blown by HFO with the PFA addition can be used as a thermal insulation material for a conventional LNG carrier.

Effect of Conditioning on PU Foam Matrix Materials Properties

This article deals with the characterization of the thermal-induced aging of soft polyurethane (PU) foams. There are studied thermal and mechanical properties by means of thermal analysis, tensile, compression and dynamic mechanical vibration testing. It was found in this study, that the increasing relative humidity of the surrounding atmosphere leads to the initiation of the degradation processes. This is reflected in the observed decreased mechanical stiffness. It is attributed to the plasticization of the PU foams wall material. It is in agreement with the observed increase of the permanent deformation accompanied simultaneously with the decrease of Young’s modulus of elasticity. The latter phenomenon is studied by the novel non-destructive forced oscillations vibration-damping testing, which is confirmed by observed lower mechanical stiffness thus indicating the loss of the elasticity induced by samples conditioning. In parallel, observed decreasing of the matrix hardness is confirming the loss of elastic mechanical performance as well. The effect of conditioning leads to the significant loss of the PU foam’s thermal stability.

Computational Study of Catalytic Urethane Formation

Polyurethanes (PUs) are widely used in different applications, and thus various synthetic procedures including one or more catalysts are applied to prepare them. For PU foams, the most important catalysts are nitrogen-containing compounds. Therefore, in this work, the catalytic effect of eight different nitrogen-containing catalysts on urethane formation will be examined. The reactions of phenyl isocyanate (PhNCO) and methanol without and in the presence of catalysts have been studied and discussed using the G3MP2BHandHLYP composite method. The solvent effects have also been considered by applying the SMD implicit solvent model. A general urethane formation mechanism has been proposed without and in the presence of the studied catalysts. The proton affinities (PA) were also examined. The barrier height of the reaction significantly decreased (∆E0 > 100 kJ/mol) in the presence of the studied catalysts, which proves the important effect they have on urethane formation. The achieved results can be applied in catalyst design and development in the near future.

Use of Novel Non-Toxic Bismuth Catalyst for the Preparation of Flexible Polyurethane Foam

Foam products are one of the largest markets for polyurethane (PU) and are heavily used in many sectors. However, current PU formulations use highly toxic and environmentally unfriendly production processes. Meanwhile, the increasing environmental concerns and regulations are intensifying the research into green and non-toxic products. In this study, we synthesized flexible polyurethane foam (PUF) using different weight percentages (0.025%, 0.05% and 0.1%) of a non-toxic bismuth catalyst. The bismuth-catalyzed foams presented a well evolved cellular structure with an open cell morphology. The properties of the bismuth-catalyzed flexible PUF, such as the mechanical, morphological, kinetic and thermal behaviors, were optimized and compared with a conventional tin-catalyzed PUF. The bismuth-catalyst revealed a higher isocyanate conversion efficiency than the stannous octoate catalyst. When comparing samples with similar densities, the bismuth-catalyzed foams present better mechanical behavior than the tin-catalyzed sample with similar thermal stability. The high solubility of bismuth triflate in water, together with its high Lewis acidity, have been shown to benefit the production of PU foams.

Sustainable insulating foams based on recycled polyurethanes from construction and demolition wastes

Background: Polyurethane (PU) foams contained in construction and demolition wastes (CDW) represent a great environmental impact, since they usually end in landfill or incineration processes. The goal of this work is to develop a way to formulate PU foams, maintaining (or ever improving) their performance, by the re-use of those industrial wastes. This procedure will allow minimize both the volume of disposal to be treated by other ways and the amount of pristine raw material needed to produce new PU foams. Methods: In this work, new rigid and soft polyurethane (PU) foams have been formulated with addition of recycled PU foams coming from demolition of buildings. Density, Fourier transform infrared analysis, compression properties and thermal conductivity were measured to characterize the resulting foams. Results: The work showed that addition of filler coming from recycled PU foams should be limited to low percentages, in order to allow good foam evolution from the reactants. Thermal conductivity values of modified rigid foams are worse than those of pristine foam, which is undesirable for thermal insulation purposes; however, in the case of soft foams, this parameter improved to some extent with low levels of recycled PU foam addition. Conclusions: The studied procedure could contribute to reduce the thermal conductivity of pristine soft PU foam, which would be of interest for applications where thermal insulation matters.

The Separation of Oil/Water Mixtures by Modified Melamine and Polyurethane Foams: A Review

Melamine (MA) and polyurethane (PU) foams, including both commercial sponges for daily use as well as newly synthesized foams are known for their high sorption ability of both polar and unipolar liquids. From this reason, commercial sponges are widely used for cleaning as they absorb a large amount of water, oil as well as their mixtures. These sponges do not preferentially absorb any of those components due to their balanced wettability. On the other hand, chemical and physical modifications of outer surfaces or in the bulk of the foams can significantly change their original wettability. These treatments ensure a suitable wettability of foams needed for an efficient water/oil or oil/water separation. MA and PU foams, dependently on the treatment, can be designed for both types of separations. The particular focus of this review is dealt with the separation of oil contaminants dispersed in water of various composition, however, an opposite case, namely a separation of water content from continuous oily phase is also discussed in some extent. In the former case, water is dominant, continuous phase and oil is dispersed within it at various concentrations, dependently on the source of polluted water. For example, waste waters associated with a crude oil, gas, shale gas extraction and oil refineries consist of oily impurities in the range from tens to thousands ppm [mg/L]. The efficient materials for preferential oil sorption should display significantly high hydrophobicity and oleophilicity and vice versa. This review is dealt with the various modifications of MA and PU foams for separating both oil in water and water in oil mixtures by identifying the chemical composition, porosity, morphology, and crosslinking parameters of the materials. Different functionalization strategies and modifications including the surface grafting with various functional species or by adding various nanomaterials in manipulating the surface properties and wettability are thoroughly reviewed. Despite the laboratory tests proved a multiply reuse of the foams, industrial applications are limited due to fouling problems, longer cleaning protocols and mechanical damages during performance cycles. Various strategies were proposed to resolve those bottlenecks, and they are also reviewed in this study.

Comparison of Satisfaction Levels between Conventional and Silicone-Adhesive Polyurethane Foam Materials in Patients with Skin Wounds

Background: Polyurethane (PU) foam dressing materials have been widely used in commercial wound dressing applications. However, the repeated application of adhesive tapes to keep the foam dressings in place can result in minor injuries to the peri-wound skin. Silicone-adhesive PU foam dressing materials have been developed to prevent such injuries. In this study, the satisfaction levels between conventional and silicone-adhesive PU foams were assessed through a survey of patients and physicians.Methods: A survey study of 140 patients with skin wounds was conducted in a single institution between July 2019 and May 2020. The patients were first treated with either conventional PU foam or silicone-adhesive PU foam, after which they were asked to record their levels of pain, adhesiveness, waterproofness, and satisfaction. At the next visit, dressings of the other material were applied to their wounds, and the same assessment process was repeated at the next dressing change.Results: The silicone-adhesive PU foam dressings demonstrably reduced the levels of dressing-related trauma and pain, compared to that of patients treated with conventional PU foam dressings. The silicone-adhesive PU foam dressings were also associated with substantially higher scores of satisfaction and waterproofness. In comparison, the mean adhesiveness score was superior in the group treated with conventional PU foam dressings, compared to that of the group treated with silicone-adhesive PU foam dressings.Conclusion: Silicone-adhesive PU foam contributed to minimizing pain during dressing change and increasing patient’s comfort. As a result, patients preferred dressing with silicone-adhesive PU foam over conventional PU foam.

Nanoparticles Addition in PU Foams: The Dramatic Effect of Trapped-Air on Nucleation

To determine the effect of nanoclays and trapped air on the formation of rigid polyurethane foams, three different production procedures were used. To study the influence of mixing at atmospheric pressure, two approaches were carried out employing either an electric or a magnetic stirrer. The third approach was executed by mixing under vacuum conditions with magnetic stirring. The samples thus obtained were characterized, and the effect of trapped air into the reactive mixtures was evaluated by analyzing the cellular structures. Different levels of trapped air were achieved when employing each manufacturing method. A correlation between the trapped air and the increase in the nucleation density when nanoclays were added was found: the cell nucleation density increased by 1.54 and 1.25 times under atmospheric conditions with electric and magnetic stirring, respectively. Nevertheless, samples fabricated without the presence of air did not show any nucleating effect despite the nanoclay addition (ratio of 1.09). This result suggests that the inclusion of air into the components is key for improving nucleation and that this effect is more pronounced when the polyol viscosity increases due to nanoclay addition. This is the most important feature determining the nucleating effect and, therefore, the corresponding cell size decreases.

Chemically Functionalized Cellulose Nanocrystals as Reactive Filler in Bio-Based Polyurethane Foams

Cellulose Nanocrystals, CNC, opportunely functionalized are proposed as reactive fillers in bio-based flexible polyurethane foams to improve, mainly, their mechanical properties. To overcome the cellulose hydrophilicity, CNC was functionalized on its surface by linking covalently a suitable bio-based polyol to obtain a grafted-CNC. The polyols grafted with CNC will react with the isocyanate in the preparation of the polyurethane foams. An attractive way to introduce functionalities on cellulose surfaces in aqueous media is silane chemistry by using functional trialkoxy silanes, X-Si (OR)3. Here, we report the synthesis of CNC-grafted-biopolyol to be used as a successful reactive filler in bio-based polyurethane foams, PUFs. The alkyl silanes were used as efficient coupling agents for the grafting of CNC and bio-polyols. Four strategies to obtain CNC-grafted-polyol were fine-tuned to use CNC as an active filler in PUFs. The effective grafting of the bio polyol on CNC was evaluated by FTIR analysis, and the amount of grafted polyol by thermogravimetric analysis. Finally, the morphological, thermal and mechanical properties and hydrophobicity of filled PUFs were thoughtfully assessed as well as the structure of the foams and, in particular, of the edges and walls of the cell foams by means of the Gibson–Ashby model. Improved thermal stability and mechanical properties of PU foams containing CNC-functionalized-polyol are observed. The morphology of the PU foams is also influenced by the functionalization of the CNC.

The Influence of Neem Oil and Its Glyceride on the Structure and Characterization of Castor Oil-Based Polyurethane Foam

Neem (Azadirachta indica) oil is a non-edible oil that contains azadirachtin, which can be used as a biopesticide. This study synthesizes bio-based polyurethane (PU) foam from neem and castor (Ricinus communis L.) oil at normal temperature and pressure. Neem oil can be reacted to narrow-distribution polyol by transesterification of oil and glycerol. Neem oil glyceride (NOG) can be used as polyol for bio-based PU foams and can be blended with castor oil homogeneously to reduce the cost of production. The composition of polyol was castor oil and 0 to 20% molar ratios of NOG. Hexamethylene diisocyanate trimer (Desmodur N) was used as isocyanate. The molar ratios of NCO/OH were set as 1.0, 1.5 and 2.0. The average hydroxyl contents of castor oil, neem oil and NOG were 2.7 mmol/g, 0.1 mmol/g and 5.1 mmol/g, respectively. The reaction time of bio-based PU foam could be adjusted between 5 to 10 min, which is acceptable for manufacturing. The densities of PU foams were between 49.7 and 116.2 kg/m3 and decreased with increasing NCO/OH and NOG ratios and decreasing neem oil. The ranges of specific compressive strength of foams were from 0.0056 to 0.0795 kPa·m3/kg. Increasing the NOG and neem oil ratio significantly enhanced the specific compressive strength in the low NCO/OH ratio. The solvent resistance and thermogravimetric (TG) results showed that the foams have high water and thermal stability. NOG can help to increase solvent resistance. Adding neem oil reduces the solvent resistance. The results indicated that increasing NCO/OH and NOG ratios increases the cross-linking density and hard segment content of PU foams. This investigation demonstrated that castor oil-based PU foams are improved by adding NOG to the polyol mixture. PU foam has excellent properties. Neem oil can be used in manufacturing processes to produce high-performance foams via a green synthesis process.