Foaming of Poly(3-hydroxybutyrate<italic style="font-style: italic">-co-</italic>3-hydroxyvalerate) Foams with Double Melting Peaks

Ming-Hui Wu; Dan Shi; Li Zhang; Zong-Bao Wang

doi:10.1007/s10118-025-3446-z

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Foaming of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Foams with Double Melting Peaks

RESEARCH ARTICLE | Updated：2025-12-03

- Foaming of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Foams with Double Melting Peaks
- Chinese Journal of Polymer Science Vol. 43, Issue 12, Pages: 2413-2421(2025)
- Affiliations：
  
  School of Materials Science and Chemical Engineering, Key Laboratory of Impact and Safety Engineering, Ministry of Education, Ningbo University, Ningbo 315211, China
- Author bio：
  
  wangzongbao@nbu.edu.cn
- Funds：
- DOI：10.1007/s10118-025-3446-z
  CLC：
- Received：14 July 2025，
  
  Accepted：01 September 2025，
  
  Published Online：12 November 2025，
  
  Published：15 December 2025
- Accepted：
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Wu, M. H.; Shi, D.; Zhang, L.; Wang, Z. B. Foaming of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) foams with double melting peaks. Chinese J. Polym. Sci. 2025, 43, 2413–2421

Ming-Hui Wu, Dan Shi, Li Zhang, et al. Foaming of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Foams with Double Melting Peaks[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2413-2421.
Wu, M. H.; Shi, D.; Zhang, L.; Wang, Z. B. Foaming of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) foams with double melting peaks. Chinese J. Polym. Sci. 2025, 43, 2413–2421 DOI： 10.1007/s10118-025-3446-z.

Ming-Hui Wu, Dan Shi, Li Zhang, et al. Foaming of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Foams with Double Melting Peaks[J]. Chinese Journal of Polymer Science, 2025, 43(12): 2413-2421. DOI： 10.1007/s10118-025-3446-z.

摘要

Based on the characteristic that P(HB-

-HV) eutectic copolymer includes different lamellar structures

a double melting peak structure was achieved by regulating the foaming process

which significantly improved the foamability of P(HB-

-HV) and resulted in a foamed material with uniform and dense cellular structure.

Abstract

Due to environmental concerns and the oil crisis

biodegradable polymer foams have garnered increasing attention. Among all biodegradable materials

Poly(3-hydroxybutyrate

-co-

3-hydroxyvalerate) (P(HB

-co-

HV)) distinguishes itself with the advantage of being biodegradable in all natural environments. However

preparing P(HB

-co-

HV) foam with a fine cellular structure remains challenging. Herein

P(HB

-co-

HV) foams with a double melting peak structure were developed. P(HB

-co-

HV) samples were first heated briefly near the melting temperature to melt most of the crystals

followed by saturation and foaming at a lower temperature (foaming temperature). P(HB

-co-

HV) foams with cell sizes of 7.1−30.0 μm and relative densities ranging from 0.3 to 0.9 were prepared

and the foaming temperature window was as wide as 16 °C. The effect of heat treatment temperature and foaming temperature on the crystallization and cell structure was investigated through DSC and SEM. It was found that the high-melting temperature crystals generated during the saturation step significantly improved the cell structure of P(HB

-co-

HV)

since these crystals can enhance the heterogeneous cell nucleation and hinder the cell growth during foaming. The low-melting temperature crystals were formed during foaming.

In situ

WAXD analysis during heating showed that the high- and low-melting peaks c

orresponded to HV-unit-excluded and HV-unit-included PHB crystals

respectively.

关键词

Keywords

references

[Okor oafor, M. O.; Frisch, K. C., 1 - INTRODUCTION TO FOAMS AND FOAM FORMATION. In Handbook of Plastic Foams , Landrock, A. H., Ed. William Andrew Publishing: Park Ridge, NJ, 1995 , pp. 1-10..

Wang, L.; Hikima, Y.; Ohshima, M.; Yusa, A.; Yamamoto, S.; Goto, H. Development of a simplified foam injection molding technique and its application to the production of high void fraction polypropylene foams. Ind. Eng. Chem. Res. 2017 , 56 , 13734−13742..

Wang, G.; Dong, M.; Deng, H.; Ma, X.; Zhu, B.; Zhou, L.; Zhang, X.; Tan, D.; Algadi, H. Polypropylene foaming using supercritical carbon dioxide: a review on fundamentals, technology, and applications. Adv. Compos. Hybrid Mater. 2024 , 8 , 84..

[Contiero, J; Coutinho De Paula, F.; Bilia Chimello De Paula, C., Prospective biodegradable plastics from biomass conversion processes. In Biofuels - State of Development , Biernat, K., Ed. IntechOpen: Rijeka, 2018 , pp. 245–271..

Hyodo, N.; Gan, H.; Ilangovan, M.; Kimura, S.; Kasuya, K.-i.; Isobe, N.; Iwata, T. Coastal and deep-sea biodegradation of polyhydroxyalkanoate microbeads. Sci. Rep. 2024 , 14 , 10302..

Avella, M.; Martuscelli, E.; Raimo, M. Review Properties of blends and composites based on poly(3-hydroxy)butyrate (PHB) and poly(3-hydroxybutyrate-hydroxyvalerate) (PHBV) copolymers. J. Mater. Sci. 2000 , 35 , 523−545..

Kumar, V.; Sehgal, R.; Gupta, R. Blends and composites of polyhydroxyalkanoates (PHAs) and their applications. Eur. Polym. J. 2021 , 161 , 110824..

[Nofar, M.; Park, C. B., 6 - Foam injection molding of pla and its compounds. In Polylactide Foams , Nofar, M.; Park, C. B., Eds. William Andrew Publishing, 2018 , pp. 151-193..

Goel, S. K.; Beckman, E. J. Generation of microcellular polymeric foams using supercritical carbon dioxide. II: Cell growth and skin formation. Polym. Eng. Sci. 1994 , 34 , 1148−1156..

Goel, S. K.; Beckman, E. J. Generation of microcellular polymeric foams using supercritical carbon dioxide. I: Effect of pressure and temperature on nucleation. Polym. Eng. Sci. 1994 , 34 , 1137−1147..

Sauceau, M.; Fages, J.; Common, A.; Nikitine, C.; Rodier, E.New challenges in polymer foaming: A review of extrusion processes assisted by supercritical carbon dioxide. Prog. Polym. Sci. 2011 , 36 , 749−766..

Bluhm, T. L.; Hamer, G. K.; Marchessault, R. H.; Fyfe, C. A.; Veregin, R. P. Isodimorphism in bacterial poly( β -hydroxybutyrate -co- β -hydroxyvalerate). Macromolecules 1986 , 19 , 2871−2876..

[Kunioka, M.; Tamaki, A.; Doi, Y. Crystalline and thermal properties of bacterial copolyesters: poly(3-hydroxybutyrate -co- 3-hydroxyvalerate) and poly(3-hydroxybutyrate -co- 4-hydroxybutyrate). Macromolecules 1989, 22 , 694-697..

Doroudiani, S.; Park, C. B.; Kortschot, M. T. Effect of the crystallinity and morphology on the microcellular foam structure of semicrystalline polymers. Polym. Eng. Sci. 1996 , 36 , 2645−2662..

Jiang, X. L.; Liu, T.; Xu, Z. M.; Zhao, L.; Hu, G. H.; Yuan, W. K. Effects of crystal structure on the foaming of isotactic polypropylene using supercritical carbon dioxi de as a foaming agent. J. Supercrit. Fluids 2009 , 48 , 167−175..

Xu, Z. M.; Jiang, X. L.; Liu, T.; Hu, G. H.; Zhao, L.; Zhu, Z. N.; Yuan, W. K. Foaming of polypropylene with supercritical carbon dioxide. J. Supercrit. Fluids 2007 , 41 , 299−310..

Le Moigne, N.; Sauceau, M.; Benyakhlef, M.; Jemai, R.; Benezet, J. C.; Rodier, E.; Lopez-Cuesta, J. M.; Fages, J. Foaming of poly (3-hydroxybutyrate -co- 3-hydroxyvalerate)/organo-clays nano-biocomposites by a continuous supercritical CO 2 assisted extrusion process. Eur. Polym. J. 2014 , 61 , 157−171..

Luo, J.; Zhu, M.; Wang, L.; Zhou, H.; Wen, B.; Wang, X.; Zhang, Y. CO 2 -based fabrication of biobased and biodegradable poly (3-hydroxybutyrate -co- 3-hydroxyvalerate)/graphene nanoplates nanocomposite foams: toward EMI shielding application. Polymer 2022 , 253 , 125034..

Xu, J. K.; Zhang, L.; Li, D. L.; Bao, J. B.; Wang, Z. B. Foaming of poly(3-hydroxybutyrate -co- 3-hydroxyvalerate) with supercritical carbon dioxide: foaming performance and crystallization behavior. ACS Omega 2020 , 5 , 9839−9845..

Li, D. C.; Liu, T.; Zhao, L.; Yuan, W. K. Foaming of linear isotactic polypropylene based on its non-isothermal crystallization behaviors under compressed CO 2 . J. Supercrit. Fluids 2011 , 60 , 89−97..

Ding, J.; Ma, W.; Song, F.; Zhong, Q. Foaming of polypropylene with supercritical carbon dioxide: an experimental and theoretical study on a new process. J. Appl. Polym. Sci. 2013 , 130 , 2877−2885..

Wu, M.; Wu, F.; Ren, Q.; Weng, Z.; Luo, H.; Wang, L.; Zheng, W. Effect of crystalline structure on the cell morphology and mechanical properties of polypropylene foams fabricated by core-back foam injection molding. J. Appl. Polym. Sci. 2021 , 138 , 51370..

Xu, L. Q.; Huang, H. X. Foaming of poly(lactic acid) using supercritical carbon dioxide as foaming agent: influence of crystallinity and spherulite size on cell structure and expansion ratio. Ind. Eng. Chem. Res. 2014 , 53 , 2277−2286..

Taki, K.; Kitano, D.; Ohshima, M. Effect of growing crystalline phase on bubble nucleation in poly(l-lactide)/ CO 2 batch foaming. Ind. Eng. Chem. Res. 2011 , 50 , 3247−3252..

Nofar, M.; Guo, Y.; Park, C. B. Double crystal melting peak generation for expanded polypropylene bead foam manufacturing. Ind. Eng. Chem. Res. 2013 , 52 , 2297−2303..

Nofar, M.; Ameli, A.; Park, C. B. A novel technology to manufacture biodegradable polylactide bead foam products. Mater. Des. 2015 , 83 , 413−421..

Nofar, M.; Ameli, A.; Park, C. B. Development of polylactide bead foams with double crystal melting peaks. Polymer 2015 , 69 , 83−94..

Guo, Y.; Hossieny, N.; Chu, R. K. M.; Park, C. B.; Zhou, N. Critical processing parameters for foamed bead manufacturing in a lab-scale autoclave system. Chem. Eng. J. 2013 , 214 , 180−188..

[Sawayanagi, T.; Tanaka, T.; Iwata, T.; Abe, H.; Doi, Y.; Ito, K.; Fujisawa, T.; Fujita, M. Structural transition of poly (R)-3-hydroxybutyrate -co- (R)-3-hydroxyvalerate single crystals on heating as revealed by synchrotron radiation SAXS and WAXD. Macromolecules 2007, 40 , 2392-2399..

Gunaratne, L.; Shanks, R. A. Multiple melting behaviour of poly(3-hydroxybutyrate -co- hydroxyvalerate) using step-scan DSC. Eur. Polym. J. 2005 , 41 , 2980−2988..

Yoshie, N.; Asaka, A.; Inoue, Y. Cocrystallization and Phase Segregation in Crystalline/Crystalline Polymer Blends of Bacterial Copolyesters. Macromolecules 2004 , 37 , 3770−3779..

[Mitomo, H.; Morishita, N.; Doi, Y. Composition range of crystal phase transition of isodimorphism in poly(3-hydroxybutyrate -co- 3-hydroxyvalerate). Macromolecules 1993, 26 , 5809-5811..

Zhu, H.; Lv, Y.; Shi, D.; Li, Y. G.; Miao, W. J.; Wang, Z. B. A synchrotron in situ x-ray study on the multiple melting behaviors of isomorphous poly(3-hydroxybutyrate -co- 3-hydroxyvalerate) (P(HB -co- HV)) with middle HV content. Chinese J. Polym. Sci. 2020 , 38 , 1015−1024..

Zhu, H.; Lv, Y.; Duan, T.; Zhu, M.; Li, Y.; Miao, W.; Wan g, Z. In-situ investigation of multiple endothermic peaks in isomorphous poly(3-hydroxybutyrate -co- 3-hydroxyvalerate) with low HV content by synchrotron radiation. Polymer 2019 , 169 , 1−10..

Zhu, H.; Lv, Y.; Shi, D.; Li, Y.; Wang, Z. Origin of the double melting peaks of poly(3-hydroxybutyrate -co- 3-hydroxyvalerate) with a high HV content as revealed by in situ synchrotron WAXD/SAXS analyses. J. Polym. Sci., Part B:Polym. Phys. 2019 , 57 , 1453−1461..

Lv, Y.; Zhu, H.; An, M. F.; Xu, H. J.; Zhang, L.; Wang, Z. B. Multiple endothermic peaks resulted from different crystal structures in an isomorphous copolymer poly(3-hydroxybutyrate -co- 3-hydroxyvalerate). Chinese J. Polym. Sci. 2016 , 34 , 1510−1522..

Cuesta, M. S.; Martínez-Salazar, J.; Barker, P. A.; Barham, P. J. Co-crystallization of poly(3-hydroxybutyrate -co- 3-hydroxyvalerate). J. Mater. Sci. 1992 , 27 , 5335−5338..

Barker, P. A.; Barham, P. J.; Martinez-Salazar, J. Effect of crystallization temperature on the cocrystallization of hydroxybutyrate/hydroxyvalerate copolymers. Polymer 1997 , 38 , 913−919..

Scandola, M.; Ceccorulli, G.; Pizzoli, M.; Gazzano, M. Study of the crystal phase and crystallization rate of bacterial poly(3-hydroxybutyrate -co- 3-hydroxyvalerate). Macromolecules 1992 , 25 , 1405−1410..

Choi, J. B.; Chung, M. J.; Yoon, J. S. Formation of double melting peak of poly(propylene -co- ethylene -co- 1-butene) during the preexpansion process for production of expanded polypropylene. Ind. Eng. Chem. Res. 2005 , 44 , 2776−2780..

Ren, Q.; Wu, M.; Wang, L.; Zheng, W.; Hikima, Y.; Semba, T.; Ohshima, M. Light and strong poly (lactic acid)/ cellulose nanofiber nanocomposite foams with enhanced rheological and crystallization property. J. Supercrit. Fluids 2022 , 190 , 105758..

Li, W.; Ren, Q.; Zhu, X.; Wu, M.; Weng, Z.; Wang, L.; Zheng, W. Enhanced heat resistance and compression strength of microcellular poly (lactic acid) foam by promoted stereocomplex crystallization with added D-Mannitol. J. CO 2 Util. 2022 , 63 , 102118..

Mizoguchi, K.; Hirose, T.; Naito, Y.; Kamiya, Y. CO 2 -induced crystallization of poly(ethylene terephthalate). Polymer 1987 , 28 , 1298−1302..

Takada, M.; Tanigaki, M.; Ohshima, M. Effects of CO 2 on crystallization kinetics of polypropylene. Polym. Eng. Sci. 2001 , 41 , 1938−1946..

Cai, W.; Liu, P.; Bai, S.; Li, S. A one-step method to manufacture biodegradable poly(butylene adipate -co- terephthalate) bead foam parts. Polym. Adv. Technol. 2021 , 32 , 2007−2019..

Lemstra, P. J.; Kooistra, T.; Challa, G. Melting behavior of isotactic polystyrene. J. Polym. Sci., Part A-2 1972 , 10 , 823−833..

Ji, X. L.; Zhang, W. J.; Wu, Z. W. The double-melting behavior of poly(ether diphenyl ether ketone). J. Polym. Sci., Part B: Polym. Phys. 1997 , 35 , 431−436..

Pae, K. D.; Sauer, J. A. Effects of thermal history on isotactic polypropylene. J. Appl. Polym. Sci. 1968 , 12 , 1901−1919..

Wei, C.-L.; Chen, M.; Yu, F. E. Temperature modulated DSC and DSC studies on the origin of double melting peaks in poly(ether ether ketone). Polymer 2003 , 44 , 8185−8193..

Verma, R.; Marand, H.; Hsiao, B. Morphological changes during secondary crystallization and subsequent melting in poly(ether ether ketone) as studied by real time small angle x-ray scattering. Macromolecules 1996 , 29 , 7767−7775..

[VanderHart, D. L.; Orts, W. J.; Marchessault, R. H. 13C NMR determination of the degree of cocrystallization in random copolymers of poly( β -hydroxybutyrate -co- β -hydroxyvalerate). Macromolecules 1995, 28 , 6394-6400..

Yokouchi, M.; Chatani, Y.; Tadokoro, H.; Teranishi, K.; Tani, H. Structural studies of polyesters: 5. molecular and crystal structures of optically active and racemic poly (β-hydroxybutyrate). Polymer 1973 , 14 , 267−272..

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Foaming of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) Foams with Double Melting Peaks

DOI：10.1007/s10118-025-3446-z

摘要

Abstract

关键词

Keywords

references