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1

Liquid heat capacity of an amorphous poly(lactic acid)

Skotnicki Marcin, Czerniecka-Kubicka Anna, Zarzyka Iwona, Pyda Marek

Polimery

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2024

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Vol. 69, nr 5

238--291

EN

The experimental and computed liquid heat capacity of an amorphous PLA was presented. The liquid heat capacity of PLA above the glass transition 333 K (60°C) is linked to the molecular motions and computed as the sum of vibrational, external (anharmonic), and conformational contributions. The largest contribution to the liquid heat capacity, Cp(liquid) of PLA comes from the vibrational motions calculated as the group and skeletal vibrational heat capacity. The external contribution to Cp(liquid) was calculated as a function of temperature from experimental data of the thermal compressibility and expansivity of the liquid state. The contribution of conformational heat capacity to the total heat capacity of an amorphous liquid PLA was calculated by fitting the experimental liquid heat capacity, after subtracting the vibrational and external parts, to the obtained heat capacity based on a one-dimensional Ising-type model with two discrete states. The parameters described in these states can characterise the macromolecule’s stiffness, cooperativity, and degeneracy. The computed and experimental data of Cp(liquid) showed good agreement at the investigated temperature region.

PL

W pracy przedstawiono eksperymentalna i obliczoną pojemność cieplną ciekłego amorficznego PLA. Pojemność cieplna cieczy PLA powyżej temperatury przejścia szklistego 333 K (60°C) jest powiązana z ruchami molekularnymi i została obliczona jako suma składników wibracyjnych, zewnętrznych (nieharmonicznych) i konformacyjnych. Największy wkład w pojemność cieplną cieczy, Cp(liquid) PLA, pochodzi z ruchów wibracyjnych, obliczonych jako pojemność cieplna wibracji grupowych i szkieletowych. Zewnętrzny wkład do Cp(liquid) został obliczony jako funkcja temperatury na podstawie danych eksperymentalnych z użyciem parametrów ściśliwości i rozszerzalności cieplnej cieczy. Wkład konformacyjnej pojemności cieplnej do całkowitej pojemności cieplnej amorficznego ciekłego PLA został obliczony przez dopasowanie eksperymentalnej pojemności cieplnej cieczy, po odjęciu części wibracyjnych i zewnętrznych, do otrzymanej pojemności cieplnej opartej na jednowymiarowym modelu typu Ising z dwoma dyskretnymi stanami. Parametry opisane w tych stanach mogą charakteryzować sztywność, kooperatywność i degenerację makrocząsteczki. Obliczone dane Cp(liquid) wykazały zgodność z danymi eksperymentalnymi w badanym zakresie temperatury.

2

Biobased poly(3-hydroxybutyrate acid) composites with addition of aliphatic polyurethane based on polypropylene glycols

Zarzyka Iwona, Czerniecka-Kubicka Anna, Hęclik Karol, Dobrowolski Lucjan, Krzykowska Beata, Białkowska Anita, Bakar Mohamed

Acta of Bioengineering and Biomechanics

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2022

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Vol. 24, no. 1

75--89

EN

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.

3

Thermally stable biopolymer composites based on poly(3-hydroxybutyrate) modified with linear aliphatic polyurethanes– preparation and properties

Zarzyka Iwona, Czerniecka-Kubicka Anna, Hęclik Karol, Dobrowolski Lucjan, Pyda Marek, Leś Karolina, Walczak Małgorzata, Białkowska Anita, Bakar Mohamed

Acta of Bioengineering and Biomechanics

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2021

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Vol. 23, no. 2

91--105

EN

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.

4

Hybrid nanobiocomposites based on poly(3-hydroxybutyrate) : characterization, thermal and mechanical properties

Zarzycka Iwona, Czerniecka-Kubicka Anna, Szyszkowska Agnieszka, Pyda Marek, Frącz Wiesław, Byczyński Łukasz, Sedlarik Vladimir

Acta of Bioengineering and Biomechanics

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2020

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Vol. 22, no. 1

97--110

EN

Poly(3-hydroxybutyrate) is a biopolymer used to production of implants in the human body. On the other hand, the physical and mechanical properties of poly(3-hydroxybutyrate) are compared to the properties of isotactic polypropylene what makes poly(3-hydroxybutyrate) possible substitute for polypropylene. Unfortunately, the melting point of poly(3-hydroxybutyrate) is almost equal to its degradation temperature what gives very narrow window of its processing conditions. Therefore, numerous attempts are being made to improve the poly(3-hydroxybutyrate) properties. In the present work, hybrid nanobiocomposites based on poly(3-hydroxybutyrate) as a matrix with the use of organic nanoclay – Cloisite 30B and linear polyurethane as a second filler have been manufactured. The linear polyurethane was based on diphenylmethane 4,4′-diisocyanate and diol with imidazoquinazoline rings. The obtained nanobiocomposites were characterized by X-ray diffraction, scanning and transmission electron microscopies, thermogravimetry, differential scanning calorimetry and their selected mechanical properties were tested. The resulting hybrid nanobiocomposites have intercalated/exfoliated structure. The nanobiocomposites are characterized by a higher thermal stability and a wider range of processing temperatures compared to the unfilled matrix. The plasticizing influence of nanofillers was also observed. In addition, the mechanical properties of the discussed nanobiocomposites were examined and compared to those of the unfilled poly(3-hydroxybutyrate). The new-obtained nanobiocomposites based on poly(3-hydroxybutyrate) containing 1% Cloisite 30B and 5 wt. % of the linear of polyurethane characterized the highest improvement of processing conditions. They have the biggest difference between the temperature of degradation and the onset melting temperature, about 100 °C.