Rigid Polyurethane Foams' Development and Optimization from Polyols Based on Depolymerized Suberin and Tall Oil Fatty Acids.

The utilization of polyols derived from renewable sources presents an opportunity to enhance the sustainability of rigid polyurethane (PUR) foams, thereby contributing to the advancement of a circular bioeconomy. This study explores the development of PUR rigid foams exclusively using polyols sourced from second-generation renewable biomass feedstocks, specifically depolymerized birch bark suberin (suberinic acids) and tall oil fatty acids. The polyols achieved a total renewable material content as high as 74%, with a suberinic acid content of 37%. Response surface modeling was employed to determine the optimal bio-polyol, blowing agents, and catalyst content, hence, optimizing the bio-based foam formulations. In addition, response surface modeling was applied to rigid PUR foam formulations based on commercially available petroleum-based polyols for comparison. The results, including apparent density (~40-44 kg/m3), closed cell content (~95%), compression strength (>0.2 MPa, parallel to the foaming direction), and thermal conductivity (~0.019 W/(m·K)), demonstrated that the suberinic acids-based rigid PUR foam exhibited competitive qualities in comparison to petroleum-based polyols. Remarkably, the bio-based rigid PUR foams comprised up to 29% renewable materials. These findings highlight the potential of suberinic acid-tall oil polyols as effective candidates for developing rigid PUR foams, offering promising solutions for sustainable insulation applications.

Effect of bio-polyol molecular weight on the structure and properties of polyurethane-polyisocyanurate (PUR-PIR) foams.

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.

Influence of Long-Term Storage and UV Light Exposure on Characteristics of Polyurethane Foams for Cryogenic Insulation.

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.

Characteristics of Components and Density of Rigid Nanoclay-Filled Medium-Density Polyurethane Foams Produced in a Sealed Mould.

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.

Anisotropy and Mechanical Properties of Nanoclay Filled, Medium-Density Rigid Polyurethane Foams Produced in a Sealed Mold, from Renewable Resources.

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.

Influence of Reactive Amine-Based Catalysts on Cryogenic Properties of Rigid Polyurethane Foams for Space and On-Ground Applications.

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.

Thermal Insulating Rigid Polyurethane Foams with Bio-Polyol from Rapeseed Oil Modified by Phosphorus Additive and Reactive Flame Retardants.

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.

New Thermo-Reflective Coatings for Applications as a Layer of Heat Insulating Materials.

This paper presents new thermo-reflective coatings with different properties. Basic, anti-corrosion and self-extinguishing coatings were analyzed. The coatings were obtained with a thickness varying from 1 to 3 mm. The coatings were subjected to detailed tests assessing their physical-mechanical properties, i.e., tensile strength, abrasion, pull-off test, water absorption, vapor permeability and thermal properties, i.e., the thermal performance of the reflective coatings, thermal transmittance, thermogravimetric analysis, differential scanning calorimetry, as well as thermomechanical analysis and thermal conductivity. In addition, the possibility of using such coatings in a wide range of temperatures and during application to various materials used as a substrate, i.e., concrete, metal and rigid polyurethane foam, was tested. The thermal analysis of coatings revealed that materials are stable to temperatures above 200 °C, there are no thermal transitions in the negative temperature region and shrinking in low temperatures is minimal (less than 0.5%). From the data obtained within the framework of this study, it can be concluded that anticorrosive, basic and self-extinguishing coatings are eligible for thermo-insulation applications in temperatures up to 200 °C.

Scale-Up and Testing of Polyurethane Bio-Foams as Potential Cryogenic Insulation Materials.

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.

Light Microscopy of Medium-Density Rigid Polyurethane Foams Filled with Nanoclay.

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.

The Effect of Manufacture Process on Mechanical Properties and Burning Behavior of Epoxy-Based Hybrid Composites.

The production of hybrid layered composites allows comprehensive modification of their properties and adaptation to the final expectations. Different methods, such as hand lay-up, vacuum bagging, and resin infusion were applied to manufacture the hybrid composites. In turn, fabrics used for manufacturing composites were made of glass (G), aramid (A), carbon (C), basalt (B), and flax (F) fibers. Flexural, puncture impact behavior, and cone calorimetry tests were applied to establish the effect of the manufacturing method and the fabrics layout on the mechanical and fire behavior of epoxy-based laminates. The lowest flammability and smoke emission were noted for composites made by vacuum bagging (approximately 40% lower values of total smoke release compared with composites made by the hand lay-up method). It was demonstrated that multi-layer hybrid composites made by vacuum bagging might enhance the fire safety levels and simultaneously maintain high mechanical properties designed for, e.g., the railway and automotive industries.

Polyurethane Foam Composites Reinforced with Renewable Fillers for Cryogenic Insulation.

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.

Natural Oil-Based Rigid Polyurethane Foam Thermal Insulation Applicable at Cryogenic Temperatures.

This paper presents research into the preparation of rigid polyurethane foams with bio-polyols from rapeseed and tall oil. Rigid polyurethane foams were designed with a cryogenic insulation application for aerospace in mind. The polyurethane systems containing non-renewable diethylene glycol (DEG) were modified by replacing it with rapeseed oil-based low functional polyol (LF), obtained by a two-step reaction of epoxidation and oxirane ring opening with 1-hexanol. It was observed that as the proportion of the LF polyol in the polyurethane system increased, so too did the apparent density of the foam material. An increase in the value of the thermal conductivity coefficient was associated with an increase in the value of apparent density. Mechanical tests showed that the rigid polyurethane foam had higher compressive strength at cryogenic temperatures compared with the values obtained at room temperature. The adhesion test indicated that the foams subjected to cryo-shock obtained similar values of adhesion strength to the materials that were not subjected to this test. The results obtained were higher than 0.1 MPa, which is a favourable value for foam materials in low-temperature applications.

Identification and Evaluation of Hazardous Pyrolysates in Bio-Based Rigid Polyurethane-Polyisocyanurate Foam Smoke.

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.

Polytetrafluoroethylene Films in Rigid Polyurethane Foams' Dielectric Permittivity Measurements with a One-Side Access Capacitive Sensor.

As a non-metallic composite material, widely applied in industry, rigid polyurethane (PUR) foams require knowledge of their dielectric properties. In experimental determination of PUR foams' dielectric properties protection of one-side capacitive sensor's active area from adverse effects caused by the PUR foams' test objects has to be ensured. In the given study, the impact of polytetrafluoroethylene (PTFE) films, thickness 0.20 mm and 0.04 mm, in covering or simulated coating the active area of one-side access capacitive sensor' electrodes on the experimentally determined true dielectric permittivity spectra of rigid PUR foams is estimated. Penetration depth of the low frequency excitation field into PTFE and PUR foams is determined experimentally. Experiments are made in order to evaluate the difference between measurements on single PUR foams' samples and on complex samples "PUR foams + PTFE film" with two calibration modes. A modification factor and a small modification criterion are defined and values of modifications are estimated in numerical calculations. Conclusions about possible practical applications of PTFE films in dielectric permittivity measurements of rigid PUR foams with one-side access capacitive sensor are made.

A Review of Wood Biomass-Based Fatty Acids and Rosin Acids Use in Polymeric Materials.

In recent decades, vegetable oils as a potential replacement for petrochemical materials have been extensively studied. Tall oil (crude tall oil, distilled tall oil, tall oil fatty acids, and rosin acids) is a good source to be turned into polymeric materials. Unlike vegetable oils, tall oil is considered as lignocellulosic plant biomass waste and is considered to be the second-generation raw material, thus it is not competing with the food and feed chain. The main purpose of this review article is to identify in what kind of polymeric materials wood biomass-based fatty acids and rosin acids have been applied and their impact on the properties.

Reinforcement Efficiency of Cellulose Microfibers for the Tensile Stiffness and Strength of Rigid Low-Density Polyurethane Foams.

Rigid low-density closed-cell polyurethane (PU) foams are widely used in both thermal insulation and structural applications. The sustainability of PU foam production can be increased by using bio-based components and fillers that ensure both enhanced mechanical properties and higher renewable material content. Such bio-based foams were produced using polyols derived from rapeseed oil and microcrystalline cellulose (MCC) fibers as filler. The effect of MCC fiber loading of up to 10 wt % on the morphology, tensile stiffness, and strength of foams has been evaluated. For estimation of the mechanical reinforcement efficiency of foams, a model allowing for the partial alignment of filler fibers in foam struts was developed and validated against test results. It is shown that although applying MCC fibers leads to modest gains in the mechanical properties of PU foams compared with cellulose nanocrystal reinforcement, it may provide a higher content of renewable material in the foams.

High Functionality Bio-Polyols from Tall Oil and Rigid Polyurethane Foams Formulated Solely Using Bio-Polyols.

High-quality rigid polyurethane (PU) foam thermal insulation material has been developed solely using bio-polyols synthesized from second-generation bio-based feedstock. High functionality bio-polyols were synthesized from cellulose production side stream-tall oil fatty acids by oxirane ring-opening as well as esterification reactions with different polyfunctional alcohols, such as diethylene glycol, trimethylolpropane, triethanolamine, and diethanolamine. Four different high functionality bio-polyols were combined with bio-polyol obtained from tall oil esterification with triethanolamine to develop rigid PU foam formulations applicable as thermal insulation material. The developed formulations were optimized using response surface modeling to find optimal bio-polyol and physical blowing agent: c-pentane content. The optimized bio-based rigid PU foam formulations delivered comparable thermal insulation properties to the petro-chemical alternative.

Rigid Polyurethane Foams with Various Isocyanate Indices Based on Polyols from Rapeseed Oil and Waste PET.

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.

Synthesis of Nanofibrillated Cellulose by Combined Ammonium Persulphate Treatment with Ultrasound and Mechanical Processing.

Ammonium persulfate has been known as an agent for obtaining nanocellulose in recent years, however most research has focused on producing cellulose nanocrystals. A lack of research about combined ammonium persulfate oxidation and common mechanical treatment in order to obtain cellulose nanofibrils has been identified. The objective of this research was to obtain and investigate carboxylated cellulose nanofibrils produced by ammonium persulfate oxidation combined with ultrasonic and mechanical treatment. Light microscopy, atomic force microscopy (AFM), powder X-Ray diffraction (PXRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and Zeta potential measurements were applied during this research. The carboxylated cellulose suspension of different fractions including nanofibrils, microfibrils and bundles were produced from bleached birch Kraft pulp fibers using chemical pretreatment with ammonium persulfate solution and further defibrillation using consequent mechanical treatment in a high shear laboratory mixer and ultrasonication. The characteristics of the obtained nanofibrils were: diameter 20⁻300 nm, crystallinity index 74.3%, Zeta potential -26.9 ± 1.8 mV, clear FTIR peak at 1740 cm-1 indicating the C=O stretching vibrations, and lower thermostability in comparison to the Kraft pulp was observed. The proposed method can be used to produce cellulose nanofibrils with defined crystallinity.