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1.
Polymers (Basel) ; 16(12)2024 Jun 07.
Article in English | MEDLINE | ID: mdl-38931968

ABSTRACT

Polymer biocompositions of poly(3-hydroxybutyrate) (P3HB) and linear polyurethanes (PU) with aromatic rings were produced by melt-blending at different P3HB/PU weight ratios (100/0, 95/5, 90/10, and 85/15). Polyurethanes have been prepared with 4,4'-diphenylmethane diisocyanate and polyethylene glycols with molar masses of 400 g/mol (PU400), 1000g/mol (PU1000), and 1500 g/mol (PU1500). The compatibility and morphology of the obtained polymer blends were determined by infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). The effect of the polyurethane content in the biocompositions on their thermal stability and mechanical properties was investigated and compared with those of the native P3HB. It was shown that increasing the PU content in P3HB-PU compositions to 10 wt.% leads to an improvement in the mentioned properties. The obtained results demonstrated that the thermal stability and mechanical properties of P3HB were improved, particularly in terms of increasing the degradation temperature, reducing hardness, and increasing impact strength. The best thermal and mechanical properties were shown by the P3HB-PU polymer compositions containing 10 wt.% of polyurethane modifiers, especially PU1000, which was also confirmed by the morphology analysis of these biocompositions. The presence of polyurethanes in the resulting polymer biocomposites decreases their glass transition temperatures, i.e., makes the materials more flexible. The resulting polymer biocompositions have suitable mechanical properties and thermal properties within the processing conditions for the predicted application as biodegradable, short-lived products for agriculture.

2.
Polymers (Basel) ; 16(2)2024 Jan 16.
Article in English | MEDLINE | ID: mdl-38257051

ABSTRACT

This study investigated the successful synthesis and characterization of nonisocyanate polyurethanes (NIPUs) based on polylactide. The NIPUs were synthesized by a condensation reaction of oligomers with hard segments (HSs) and synthesized carbamate-modified polylactic acid containing flexible segments (FSs). The oligomers with HSs were prepared from phenolsulfonic acid (PSA) or a mixture of PSA and hydroxynaphthalenesulfonic acid (HNSA), urea and formaldehyde. The mixing of oligomeric compounds with different amounts of formaldehyde was carried out at room temperature. Obtained NIPU samples with different hard segment content were tested for their mechanical and thermal properties. The tensile strength (TS) of all NIPU samples increased with an increasing amount of HSs, attaining the maximum value at an HS:FS ratio of 1:3. Samples prepared from PSA and HNSA showed higher tensile strength (TS) without significant change in elongation at break compared to the samples based only on PSA. Thermogravimetric analysis data indicated an absence of weight loss for all samples below 100 °C, which can be considered a safe temperature for using NIPU materials. Maximum degradation temperatures reached up to 385 °C. Fourier transform infrared spectroscopy results confirmed the existence of expected specific groups as well as the chemical structure of the prepared polyurethanes. DSC analysis showed the existence of two characteristic phase transitions attributed to the melting and crystallization of hard segments in the NIPU samples.

3.
Int J Mol Sci ; 24(24)2023 Dec 12.
Article in English | MEDLINE | ID: mdl-38139234

ABSTRACT

Due to the growing interest in biopolymers, biosynthesizable and biodegradable polymers currently occupy a special place. Unfortunately, the properties of native biopolymers make them not good enough for use as substitutes for conventional polymers. Therefore, attempts are being made to modify their properties. In this work, in order to improve the properties of the poly(3-hydroxybutyrate) (P3HB) biopolymer, linear aliphatic polyurethane (PU) based on 1,4-butanediol (BD) and hexamethylene 1,6-diisocyanate (HDI) was used. The conducted studies on the effect of the amount of PU used (5, 10, 15 and 20 m/m%) showed an improvement in the thermal properties of the prepared polymer blends. As part of the tested mechanical properties of the new polymer blends, we noted the desired increase in the tensile strength, and the impact strength showed a decrease in hardness, in particular at the presence of 5 m/m% PU. Therefore, for further improvement, hybrid nanobiocomposites with 5 m/m% PU and organically modified montmorillonite (MMT) (Cloisite 30®B) were produced. The nanoadditive was used in a typical amount of 1-3 m/m%. It was found that the obtained nanobiocomposites containing the smallest amount of nanofillers, i.e., 1 m/m% Cloisite®30B, exhibited the best mechanical and thermal properties.


Subject(s)
Polymers , Polyurethanes , Bentonite , 3-Hydroxybutyric Acid , Biopolymers
4.
Polymers (Basel) ; 15(6)2023 Mar 10.
Article in English | MEDLINE | ID: mdl-36987179

ABSTRACT

This article presents a review on the recent advances in the field of ternary diglycidyl ether of bisphenol A epoxy nanocomposites containing nanoparticles and other modifiers. Particular attention is paid to their mechanical and thermal properties. The properties of epoxy resins were improved by incorporating various single toughening agents, in solid or liquid states. This latter process often resulted in the improvement in some properties at the expense of others. The use of two appropriate modifiers for the preparation of hybrid composites, possibly will show a synergistic effect on the performance properties of the composites. Due to the huge amount of modifiers that were used, the present paper will focus mainly on largely employed nanoclays with modifiers in a liquid and solid state. The former modifier contributes to an increase in the flexibility of the matrix, while the latter modifier is intended to improve other properties of the polymer depending on its structure. Various studies which were carried out on hybrid epoxy nanocomposites confirmed the occurrence of a synergistic effect within the tested performance properties of the epoxy matrix. Nevertheless, there are still ongoing research works using other nanoparticles and other modifiers aiming at enhancing the mechanical and thermal properties of epoxy resins. Despite numerous studies carried out so far to assess the fracture toughness of epoxy hybrid nanocomposites, some problems still remain unresolved. Many research groups are dealing with many aspects of the subject, namely the choice of modifiers and preparation methods, while taking into account the protection of the environment and the use of components from natural resources.

5.
Nanomaterials (Basel) ; 13(2)2023 Jan 04.
Article in English | MEDLINE | ID: mdl-36677979

ABSTRACT

This paper presents an attempt to improve the properties of poly(3-hydroxybutyrate) (P3HB) using linear aliphatic polyurethane (PU400) and organomodified montmorillonite (MMT)-(Cloisite®30B). The nanostructure of hybrid nanobiocomposites produced by extrusion was analyzed by X-ray diffraction and transmission electron microscopy, and the morphology was analyzed by scanning electron microscopy. In addition, selected mechanical properties and thermal properties were studied by thermogravimetric analysis, TGA, and differential scanning calorimetry, DSC. The interactions of the composite ingredients were indicated by FT IR spectroscopy. The effect of the amount of nanofiller on the properties of prepared hybrid nanobiocomposites was noted. Moreover, the non-equilibrium and equilibrium thermal parameters of nanobiocomposites were established based on their thermal history. Based on equilibrium parameters (i.e., the heat of fusion for the fully crystalline materials and the change in the heat capacity at the glass transition temperature for the fully amorphous nanobiocomposites), the degree of crystallinity and the mobile and rigid amorphous fractions were estimated. The addition of Cloisite®30B and aliphatic polyurethane to the P3HB matrix caused a decrease in the degree of crystallinity in reference to the unfilled P3HB. Simultaneously, an increase in the amorphous phase contents was noted. A rigid amorphous fraction was also denoted. Thermogravimetric analysis of the nanocomposites was also carried out and showed that the thermal stability of all nanocomposites was higher than that of the unfilled P3HB. An additional 1% mass of nanofiller increased the degradation temperature of the nanocomposites by about 30 °C in reference to the unfilled P3HB. Moreover, it was found that obtained hybrid nanobiocomposites containing 10 wt.% of aliphatic polyurethane (PU400) and the smallest amount of nanofiller (1 wt.% of Cloisite®30B) showed the best mechanical properties. We observed a desirable decrease in hardness of 15%, an increase in the relative strain at break of 60% and in the impact strength of 15% of the newly prepared nanobiocomposites with respect to the unfiled P3HB. The produced hybrid nanobiocomposites combined the best features induced by the plasticizing effect of polyurethane and the formation of P3HB-montmorillonite-polyurethane (P3HB-PU-MMT) adducts, which resulted in the improvement of the thermal and mechanical properties.

6.
Acta Bioeng Biomech ; 24(1): 75-89, 2022.
Article in English | MEDLINE | ID: mdl-38314483

ABSTRACT

Poly(3-hydroxybutyrate) (P3HB) is the most important of the polyhydroxyalkanoates. It is biosynthesized, biodegradable, biocompatible, and shows no cytotoxicity and mutagenicity. P3HB is a natural metabolite in the human body and, therefore, it could replace the synthetic, hard-to-degrade polymers used in the production of implants. However, P3HB is a brittle material with limited thermal stability. Therefore, in order to improve its mechanical properties and processing parameters by separating its melting point and degradation temperature, P3HB-based composites can be produced using, for example, linear aliphatic polyurethanes as modifiers. The aim of the study is a modification of P3HB properties with the use of linear aliphatic polyurethanes synthesized in reaction of hexamethylene diisocyanate (HDI) and polypropylene glycols (PPG) by producing their composites. Prepared biocomposites were tested by the scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetry (TGA). Furthermore, selected mechanical properties were evaluated. It has been confirmed that new biocomposites showed an increase in impact strength, relative strain at break, decrease of hardness and higher degradation temperature compared to the unfilled P3HB. The biocomposites also showed a decrease in the glass transition temperature and the degree of crystallinity. Biocomposites obtained with 10 wt. % polyurethane synthesized with polypropylene glycol having 1000 g ⋅ mole-1 and HDI have the best thermal and mechanical properties.

7.
Acta Bioeng Biomech ; 23(2): 91-105, 2021.
Article in English | MEDLINE | ID: mdl-34846041

ABSTRACT

PURPOSE: Poly(3-hydroxybutyrate) (P3HB) is a biopolymer, but storing products from P3HB causes the deterioration of their properties leading to their brittleness. P3HB has also low thermal stability. Its melting point almost equals its degradation temperature. To obtain biodegradable and biocompatible materials characterized by higher thermal stability and better strength parameters than the unfilled P3HB, composites with the addition of polyurethanes were produced. METHODS: The morphology, thermal, and mechanical property parameters of the biocomposites were examined using scanning electron microscopy, thermogravimetric analysis, standard differential scanning calorimetry, and typical strength machines. RESULTS: Aliphatic polyurethanes, obtained by the reaction of 1,6-hexamethylene diisocyanate and polyethylene glycols, were used as modifiers. To check the influence of the glycol molar mass on the properties of the biocomposites, glycols with a molecular weight of 400 and 1000 g/mol were used. New biocomposites based on P3HB were produced with 5, 10, 15, and 20 wt. % content of polyurethane by direct mixing using a twin-screw extruder. The following property parameters of the prepared biocomposites were tested: degradation temperature, glass transition temperature, tensile strength, impact strength, and Brinell hardness. CONCLUSIONS: Improvement of the processing property parameters of P3HB-biocomposites with the addition of aliphatic polyurethanes was achieved by increasing the degradation temperature in relation to the degradation temperature of the unfilled P3HB by over 30 °C. The performance property parameters have also been improved by reducing the brittleness compared to the P3HB, as evidenced by the increase in impact strength and the decrease in hardness with an increase in the amount of polyurethane obtained by the reaction of 1,6-hexamethylene diisocyanate and polyethylene glycol with a molecular weight of 400 g/mol (PU400) as modifier.


Subject(s)
Polyesters , Polyurethanes , 3-Hydroxybutyric Acid , Biopolymers , Hydroxybutyrates
8.
Materials (Basel) ; 14(14)2021 Jul 08.
Article in English | MEDLINE | ID: mdl-34300741

ABSTRACT

The paper presents the results of investigations on the glass fiber reinforced composite for the floor panels with quartz powder additions of different percentages in terms of wear resistance, friction coefficient, hardness, and strength. The wear resistance was assessed using the specific wear work parameter determined by the novel tribotester with friction band. It was found that an increase in quartz powder addition to the tested polymer composite does not enhance its mechanical increasingly properties. From the wear tests it can be concluded that only the composite with four layers of glass fibers and 6 wt.% of the quartz powder exhibited improvement of the wear resistance, but its shear strength was lower than that of the two layer specimens with similar powder proportions. On the other hand, the highest friction coefficient's, which is microhardness HV05, shear strength and impact strength were attained for the composite with two layers of glass fibers and 3 wt.% of the quartz powder. Among four layer samples, very close results were obtained for the samples with 10% of powder and insignificantly lower strength were observed for the samples with no powder added. The results revealed that there is no clear trend for the effect of silica filler percentage on the composite performance, which indicates the need for individual purpose-dependent decision making in the design of the glass fiber reinforced composites with quartz powder filler.

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