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Cryogenics is the science and technology of very low temperatures, typically below 120 K. The most common applications are liquified natural gas carriers, ground-based tanks, and propellant tanks for space launchers. A crucial aspect of cryogenic technology is effective insulation to minimise boil-off from storage tanks and prevent frost build-up. Rigid closed-cell foams are prominent in various applications, including cryogenic insulation, due to their balance between thermal and mechanical properties. Polyurethane (PU) foam is widely used for internal insulation in cryogenic tanks, providing durability under thermal shocks and operational loads. External insulation, used in liquified natural gas carriers and ground-based tanks, generally demands less compressive strength and can utilise lower-density foams. The evolution of cryogenic insulation materials has seen the incorporation of environmentally friendly blowing agents and bio-based polyols to enhance sustainability. Fourth-generation physical blowing agents, such as HFO-1233zd(E) and HFO-1336mzz(Z), offer low global warming potential and improved thermal conductivity. Additionally, bio-based polyols from renewable resources like different natural oils and recycled polyethylene terephthalate (PET) are being integrated into rigid PU foams, showing promising properties for cryogenic applications. Research continues to optimise these materials for better mechanical performance and environmental impact. [ABSTRACT FROM AUTHOR]

The increasing interest in polyurethane materials has raised the question of the environmental impact of these materials. For this reason, the scientists aim to find an extremely difficult balance between new material technologies and sustainable development. This work attempts to validate the possibility of replacing petrochemical polyols with previously synthesized bio-polyols and their impact on the structure and properties of rigid polyurethane-polyisocyanurate (PUR-PIR). To date, biobased polyols were frequently used in the manufacturing of PU, but application of bio-polyols synthesized via solvothermal liquefaction using different chains of polyethylene glycol has not been comprehensively discussed. In this work, ten sets of rigid polyurethane foams were synthesized. The influence of bio-polyols addition on foam properties was investigated by mechanical testing, thermogravimetric analysis (TGA), and cone calorimetry. The structure was determined by scanning electron microscopy (SEM) and a gas pycnometer. The tests revealed a significant extension of foam growth time, which can be explained by possible steric hindrances and the presence of less reactive secondary hydroxyl groups. Moreover, an increase average size of pores and aspect ratio was noticed. This can be interpreted by the modification of the cell growth process by the introduction of a less reactive bio-polyol with different viscosity. The analysis of foams mechanical properties showed that the normalized compressive strength increased up to 40% due to incorporation of more cross-linked structures. The thermogravimetric analysis demonstrated that the addition of bio-based polyols increased temperature of 2% (T2%) and 5% (T5%) mass degradation. On the other hand, evaluation of flammability of manufactured foams showed increase of total heat release (HRR) and smoke release (TSR) what may be caused by reduction of char layer stability. These findings add substantially to our understanding of the incorporation of bio-polyols into industrial polyurethane systems and suggest the necessity of conducting further research on these materials. [ABSTRACT FROM AUTHOR]

Rigid polyurethane (PUR) foams have been the most effective insulation material used in space launchers since the beginning of cryogenic fuel use, due to their outstanding thermal and mechanical properties. In this study, spray-applied PUR foams using different ratios of amine-based catalysts were produced. Due to climate change, several restrictions have been made regarding the usage of blowing agents used for PUR foam production. Lately, hydrofluoroolefins (HFOs) have been suggested as an alternative for PUR foam production due to their low global warming potential (GWP) and ozone depletion potential (ODP), replacing the hydrofluorocarbons (HFCs) so far used. This change in blowing agents naturally altered the usage of catalysts. Reactive amine-based catalysts are less hazardous because of their low volatility and ability to react successfully with isocyanate or polyols. Spray-applied PUR foams with a potential application for cryogenic insulation were produced and tested for long-term storage, analyzing parameters such as the pH value of polyol composition, foaming kinetics (trise, tcream), etc. Athermal analysis (TG, DSC) was also applied to developed materials, as well as artificial ageing by exposing samples to UV light. It was discovered that PUR foams obtained using reactive amine-based catalysts, such as Polycat 203 and 218, have a higher integral heat capacity, but polyol mixtures containing these catalysts cannot exceed a storage time of more than 4 months. It was also observed from artificial ageing tests of PUR cryogenic insulation by exposure to UV light that the thickness of the degraded layer reached 0.8 mm (after 1000 h), but no significant destruction of cellular structure deeper in the material was observed. [ABSTRACT FROM AUTHOR]

The characteristics of rigid, nanoclay-filled, medium-density NEOpolyol-380 polyurethane foams components can be estimated when two conditions are met: (1) the foam blocks are produced in a sealed mould; and (2) the mass of the reacting mixture is kept constant. It was shown that, with an increase in filler concentration, the total mass of the filled polymeric network stays constant, but the total volume reduces; the higher the ratio of density of the exfoliated nanoclay platelets and polymer, the higher the volume reduction of the polymeric network. Experimental data of polyurethane foam block mass were acquired at concentrations η = 0%, 0.25%, 0.5%, 1%, 2%, 3% and 5% from the mass of a filled reacting mixture. Foam-density dependence in the uniform zone and in the side-sections of the produced blocks on the: (1) mass of the blocks; and (2) the concentration of the filler was analysed. The study demonstrated that the correlation of the specimens' density with the foam block mass is much higher than that of the filler concentration. [ABSTRACT FROM AUTHOR]

Medium-density rigid polyurethane (PU) foams are often produced in sealed molds; therefore, the processes inside the mold and structure of the produced foam blocks need to be understood. The structural and mechanical anisotropy is shown to be the third variable along with (1) concentration of the nanoclay filler and (2) density, to determine the mechanical properties of the filled PU foam composites produced in a sealed mold. The varying anisotropy of the specimens hinders the accurate evaluation of the filling effect. The methodology for the estimation of the anisotropy characteristics of specimens from different locations within the nanoclay filled PU foam blocks is elaborated. A criterion, based on analysis of Poisson's ratios, is formulated for the selection of specimens with similar anisotropy characteristics. The shear and bulk moduli are estimated theoretically, dependent on the filler's concentration, using the experimentally determined constants. [ABSTRACT FROM AUTHOR]

Rigid polyurethane (PUR) foams have outstanding properties, and some of them are successfully used even today as cryogenic insulation. The fourth-generation blowing agent Solstice® LBA and commercial polyols were used for the production of a low-density cryogenic PUR foam composition. A lab-scale pouring method for PUR foam preparation and up-scaling of the processes using an industrial spraying machine are described in this article. For the determination of the foam properties at cryogenic temperature, original methods, devices, and appliances were used. The properties at room and cryogenic temperatures of the developed PUR foams using a low-toxicity, bismuth-based, and low-emission amine catalyst were compared with a reference foam with a conventional tin-based additive amine catalyst. It was found that the values of important cryogenic characteristics such as adhesion strength after cryoshock and the safety coefficient of the PUR foams formed with new reactive-type amine-based catalysts and with the blowing agent Solstice® LBA were higher than those of the foam with conventional catalysts. [ABSTRACT FROM AUTHOR]

In this article, rigid polyurethane foams obtained with the addition of a bio-polyol from rapeseed oil, were modified with the dimethyl propane phosphonate as additive flame retardant and two reactive flame retardants diethyl (hydroxymethyl)phosphonate and diethyl bis-(2-hydroxyethyl)-aminomethylphosphonate. The influence of used flame retardants on the foaming process and characteristic processing times of tested polyurethane systems were determined. The obtained foams were tested in terms of cell structure, physical and mechanical properties, as well as flammability. Modified foams had worse mechanical and thermal insulation properties, caused by lower cellular density and higher anisotropy coefficient in the cross-section parallel to the foam rise direction, compared to unmodified foam. However, the thermal conductivity of all tested foam materials was lower than 25.82 mW/m∙K. The applied modifiers effectively reduced the flammability of rigid polyurethane foams, among others, increasing the oxygen index above 21.4 vol.%, reducing the total heat released by about 41–51% and the rate of heat release by about 2–52%. A correlation between the limiting oxygen index values and both total heat released parameters from the pyrolysis combustion flow calorimetry and cone calorimetry was observed. The correlation was also visible between the value of the heat release capacity (HRC) parameter obtained from the pyrolysis combustion flow calorimetry and the maximum average rate of heat emission (MARHE) from the cone calorimeter test. [ABSTRACT FROM AUTHOR]

This article compares the properties of closed-cell PUR bio-foams produced on a laboratory scale and on an industrial scale. In the formulation used, the polyol premix contained 40 wt.% of a bio-polyol based on rapeseed oil. Selected useful properties of the foams obtained on the two scales and the use of one-step and spraying methods were compared. In the case of the spraying method, the experimental system was compared to a commercial one. Given the possibility of applying the bio-foams in insulation systems for cryogenic and liquefied natural gas (LNG) applications, a compressive strength analysis of the foams was carried out at room temperature as well as at −196 °C. It was found that the foams modified with the bio-polyol were characterized by a higher compressive strength at low temperatures than commercial foams based on a petrochemical polyol. [ABSTRACT FROM AUTHOR]

Practical applications and mathematical modelling of the physical and mechanical properties of medium-density rigid polyurethane foams require knowledge of their structure. It is necessary to determine structural characteristics without destroying the foams and measuring each element. A methodology is described for the use of light microscopy on environmentally sustainable, medium-density rigid polyurethane foams (in the density region of ≈210–230 kg/m3), by the analysis of two types of light microscopy images: (1) Cutting surface images; and (2) Through-cutting surface images. The dimensions of structural elements of polyurethane foams, filled with the nanoclay Cloisite-30B at concentrations of 0.0%, 0.25%, 0.50%, 1.0%, 2.0%, 3.0%, and 5.0% from the mass of the filled reacting mixture, are estimated. Probability density functions of projections of bubbles' diameters and struts' length are determined using images in three mutually perpendicular planes. A mathematical model is developed for the restoration of the actual dimensions of bubbles' diameters using data of cutting circles' diameters. Intercalation and exfoliation of the filler's Cloisite-30B mono-layers is evaluated via the basal spacing by X-ray diffraction at a 5 wt.% concentration of nanoclay. [ABSTRACT FROM AUTHOR]

This paper describes the results of quantifying gaseous chemical compounds in smoke, which were obtained from thermal degradation analyses of rigid polyurethane (PU) and rigid polyisocyanurate (PIR) foam. The analytical method used was evolved gas analysis, which consisted of a combination of two different analytical methods: thermogravimetric/differential thermal analysis-Fourier-transform infrared spectroscopy (TG/DTA-FTIR) and pyrolysis gas chromatography-mass spectrometry (Py-GC/MS). A lack of specific internal standards for measuring the released gases in thermal degradation analyses was solved by introducing a mathematical formula to indirectly determine the absolute mass values for the chemical compounds of interest. The combined method allowed for the quantification of absolute masses of the released gaseous chemical compounds in the smoke without the use of internal standards. This method has the potential to be used in quantifying gaseous chemical compounds in other foam materials as well. • Bio-based PU and PIR foams possess higher thermal stability and leave less residue compared to conventional reference. • CO 2 and H 2 O vapor from experimental formulations are present in lower quantities than from glycerol-based formulations. • The intensity and trends of decomposition product release depend on the formulation. • The developed method does not rely on internal standards for analysis. • The method is applicable for analysing decomposition products in other polymer foams. [ABSTRACT FROM AUTHOR]

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Sawdust, microcellulose and nanocellulose and their silanized forms were used to reinforce rigid polyurethane (PU) foam composites. The concentration of fillers was varied in the range of 0.5–1.5%. For rigid PU foam formulations, three polyols from recycled and renewable materials were used, among other components. Polyols were obtained from rapeseed oil, tall oil fatty acids and recycled polyethylene terephthalate. As rigid PU foam composites in literature have been described as appropriate thermal insulation material, the appliance of obtained composites for cryogenic insulation was investigated by determining the various physical-mechanical properties of composites. The physical-mechanical properties, such as the modulus of elasticity, compressive and tensile strength in both 293 K and 77 K, adhesion measurements with and without cryo-shock, apparent density, thermal conductivity coefficient, and safety coefficient were measured. The results showed that the addition of fillers did not give a significant improvement of characteristics. [ABSTRACT FROM AUTHOR]

In this study, rigid polyurethane (PU) and polyisocyanurate (PIR) foam samples made from renewable material (tall oil fatty acid) based polyols were analyzed by pyrolysis gas chromatography mass spectrometry (Py-GC/MS) to obtain information about the full relative smoke content, with a focus on substance identification by their functional groups and hazardousness. The relative content of gaseous products produced during the thermal degradation was evaluated between the two samples, differenced by their assigned isocyanate (NCO) index value—150 and 300. The main thermal degradation components of the rigid PU-PIR foam were found to originate from the decomposition of isocyanate, primarily forming 4,4′-methylenedianiline, 3,3′-diaminodiphenylmethane, N-methylaniline, aniline, 4-benzylaniline and phenyl isocyanate. Hazard analysis revealed that the most common hazards were the hazards related to health: H315 (36%), H319 (28%), H335 (25%), and H302 (23%). The chemical compound with the highest relative content value—4,4′-methylenedianiline (45.3% for PU and 52.4% for PIR)—was identified to be a suspected carcinogen and mutagen. The focus of the study was identifying and evaluating the relative quantities of the produced gaseous products, examine their hazardousness, and provide information on the released thermal degradation products to form a renewable-source based rigid PU and PIR foam. [ABSTRACT FROM AUTHOR]

Developing polyols derived from natural sources and recycling materials attracts great interest for use in replacing petroleum-based polyols in polyurethane production. In this study, rigid polyurethane (PUR) foams with various isocyanate indices were obtained from polyols based on rapeseed oil and polyethylene terephthalate (RO/PET). The various properties of the prepared PUR foams were investigated, and the effect of the isocyanate index was evaluated. The closed-cell content and water absorption were not impacted by the change of the isocyanate index. The most significant effect of increasing the isocyanate index was on the dimensional stability of the resulting foams. This is due to the increased crosslink density, as evidenced by the increased formation of isocyanurate and increase of the glass transition temperature. Additionally, the influence on compression strength, modulus, and long-term thermal conductivity were evaluated and compared with reference PUR foams from commercially available polyols. Rigid PUR foams from RO/PET polyol were found to be competitive with reference materials and could be used as thermal insulation material. [ABSTRACT FROM AUTHOR]

This study presents the development and analysis of rigid polyurethane-polyisocyanurate (PU-PIR) foam synthesized from high functionality tall oil (TO) based polyols. Three PU-PIR formulations with varied high functionality TO based polyol content (45, 75 and 95 pbw) and a different tier of isocyanate (NCO) indexes (110, 150, 200, 300 and 400) for each formulation were compared to a formulation developed using conventional raw materials, mainly obtained from petrochemicals. Using the Fourier transform infrared spectral analysis (FTIR), the chemical structure of the foams was evaluated with emphasis on the characteristic PU-PIR signal ratio and isocyanurate signal peaks. The thermal properties of the PU-PIR polymer matrix were characterized using the thermogravimetric analysis (TGA) method by comparing the thermal degradation temperatures at 5%, 25% and 50% and residual masses. Technological parameters and thermal degradation results indicate that TO is a suitable renewable resource for polyol in a rigid PU-PIR foam formulation, but the results from FTIR analysis suggest that a small optimization in the foam developing process is necessary due to an increasing amount of unreacted NCO groups in samples with the NCO index above 200. • TO polyol gives the foam a renewable material content up to almost 25% of the mass. • TO polyol ensures an improved thermal degradation stability in rigid PU-PIR foams. • The developed formulation is well-suited for rigid PU and rigid PIR foam both. [ABSTRACT FROM AUTHOR]