The use of waste tires is a very critical issue, considering their environmental and economic implications. One of the simplest and the least harmful methods is conversion of tires into ground tire rubber (GTR), which can be introduced into different polymer matrices as a filler. However, these applications often require proper modifications to provide compatibility with the polymer matrix. In this study, we examined the impact of GTR oxidation with hydrogen peroxide and potassium permanganate on the processing and properties of flexible polyurethane/GTR composite foams. Applied treatments caused oxidation and introduction of hydroxyl groups onto the surface of rubber particles, expressed by the broad range of their hydroxyl numbers. It resulted in noticeable differences in the processing of the polyurethane system and affected the structure of flexible composite foams. Treatment with H2O2 resulted in a 31% rise of apparent density, while the catalytic activity of potassium ions enhanced foaming of system decreased density by 25% and increased the open cell content. Better mechanical performance was noted for H2O2 modifications (even by 100% higher normalized compressive strength), because of the voids in cell walls and incompletely developed structure during polymerization, accelerated by KMnO4 treatment. This paper shows that modification of ground tire rubber is a very promising approach, and when properly performed may be applied to engineer the structure and performance of polyurethane composite foams.
Polyurethane (PU) foams are versatile materials with a broad application range. Their performance is driven by the stoichiometry of polymerization reaction, which has been investigated in several works. However, the analysis was often limited only to selected properties and compared samples differing in apparent density, significantly influencing their performance. In the bigger picture, there is still a lack of comprehensive studies dealing with the stoichiometry impact on PU foams’ performance. Herein, flexible PU foams with a similar apparent density but differing in the isocyanate index (IIso) (from 0.80 to 1.20) were prepared. The stoichiometry–structure–performance relationships were investigated considering cellular and chemical structure, as well as the static and dynamic mechanical properties, thermal stability, thermal insulation, and acoustic performance. For IIso of 1.00, the biggest cell diameters of 274 µm were noted, which was 21–25% higher compared to 0.80 and 1.20 values. Increasing IIso reduced open cell content from 83.1 to 22.4%, which, combined with stiffening of structure (rise of modulus from 63 to 2787 kPa) resulting from crosslinking, limited the sound suppression ability around five times. On the other hand, it significantly strengthened the material, increasing tensile and compressive strength 4 and 13 times, respectively. Changes in the foams’ performance were also induced by the glass transition temperature shift from 6.1 to 31.7 °C, resulting from a greater extent of urethane groups’ generation and additional isocyanate reactions. Generally, the presented work provides important insights into preparing flexible PU foams and could be very useful for the future development of these materials.
This article describes how new bio-based polyol during the liquefaction process can be obtained. Selected polyol was tested in the production of polyurethane resins. Moreover, this research describes the process of manufacturing polyurethane materials and the impact of two different types of fibers—synthetic and natural (glass and sisal fibers)—on the properties of composites. The best properties were achieved at a reaction temperature of 150 °C and a time of 6 h. The hydroxyl number of bio-based polyol was 475 mg KOH/g. Composites were obtained by hot pressing for 15 min at 100 °C and under a pressure of 10 MPa. Conducted researches show the improvement of flexural strength, impact strength, hardness, an increase of storage modulus of obtained materials, and an increase of glass transition temperature of hard segments with an increasing amount of fibers. SEM analysis determined better adhesion of sisal fiber to the matrix and presence of cracks, holes, and voids inside the structure of composites.
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.
22 November 2021 in European Journal of Wood and Wood Products
The sustainability of production systems in wood processing, wood industry, and wooden waste disposal is an important issue for European industry and society. Proper development of products based on renewable wood resources gives an opportunity to provide materials with long-term environmental, social, and economic sustainability. This study aims to establish a new way of forestry and agricultural waste materials utilization by synthesis of bio-based polyols and manufacturing of polyurethane wood composites (PU-WC). The first part of this paper describes the liquefaction of wood shavings at a temperature of 150 °C for 6 h in three different solvents—glycerol, poly (ethylene glycol) and their mixture in a 1:1 ratio. The second part deals with the synthesis of polyurethane (PU) resins containing 90% of biopolyol. Eight sets of materials with different NCO:OH ratios were obtained in a one-step method using a hydraulic press. These materials were characterized, and the material with the most promising properties was selected for polyurethane wood composites production. Composites with 40%, 50%, 60%, and 70% of wood shavings were obtained. The addition of filler caused an increase in flexural strength, Young`s modulus, hardness, and impact strength. Scanning electron microscopy (SEM) showed good adhesion between the polymer and the filler. The optimum filler content is between 50 and 60% by weight of the composite. The presented study provides a significant step toward a greener alternative for materials produced mainly from non-renewable resources.
This work aims to investigate the process of obtaining highly filled glass and carbon fiber composites. Composites were manufactured using previously obtained cellulose derived polyol, polymeric methylene diphenyl diisocyanate (pMDI). As a catalyst, dibutyltin dilaurate 95% and Dabco® 33-LV were used. It was found that the addition of carbon and glass fibers into the polymer matrix causes an increase in the mechanical properties such as impact and flexural strength, Young’s modulus, and hardness of the material. Moreover, the dynamic mechanical analysis (DMA) showed a significant increase in the material’s storage modulus and rigidity in a wide range of temperatures. The increase in glass transition of soft segments can be noticed due to the limitation of macromolecules mobility in the material. The thermogravimetric analysis showed a four step decomposition, with maximal degradation rate at TmaxII = 320–330 °C and TmaxIII = 395–405 °C, as well as a significant improvement of thermal stability. Analysis of the material structure using a scanning electron microscope showed the presence of material defects such as voids, fiber pull-outs, and agglomerates of both fibers.