Supermagnetic cellulose nanocrystal hybrids reinforced PHBV nanocomposites with high sensitivity to intelligently detect water vapor

https://doi.org/10.1016/j.indcrop.2020.112704Get rights and content

Highlights

  • Supermagnetic hybrids were successfully synthesized by using CNCs as templates.

  • Synergistic reinforcing effect of CNCs and Fe3O4 on PHBV performances were observed.

  • MCNC hybrids can be used as an indicator to detect water vapor.

  • MCNC reinforced nanocomposites offer a real-time monitoring method for water vapor.

  • The nanocomposites show great potentials in bioactive and smart packaging materials.

Abstract

In this work, cellulose nanocrystals (CNCs) incorporated with supermagnetic iron oxide nanoparticles (Fe3O4 NPs) as (MCNC) hybrids by the co-precipitation method have developed. High-performance nanocomposite films consisting of poly(3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) and MCNC hybrids have prepared through a simple solution casting method. The addition of CNCs in MCNC-5% hybrids improved the surface hydrophilicity of PHBV, and displayed a reduction in water vapor permeability by 68.1 %, compared with pristine PHBV. The results prove that the addition of MCNC hybrids can be acted like a sensor to detect voltage change of the nanocomposites as functions of water vapor. The existence of CNCs in the MCNC-5% hybrids caused an increase in tensile strength and Young’s modulus by 74.6 % and 120.2 %, respectively. The addition of CNCs could enhance cell-matrix interactions and thus cytocompatibility of PHBV nanocomposites. The PHBV/MCNC-5% exhibited saturation magnetization (Ms) values of 1.5 emu g−1 and displayed almost a regular and operative voltage response signal with real-time monitoring of water vapor. This work provides sustainable smart packaging materials with high sensitivity for water vapor and excellent biocompatibility.

Introduction

The recent developments on packaging materials have attracted considerable interests in the areas of nanotechnology, due to the increasing globalization of markets by consumer preferences to product quality and safety (Ghaani et al., 2016; Kuulialaab et al., 2018). Accordingly, our universal needs new functional materials to meet the progress of the food supply chain and systems for guaranteeing safety and health (Neethirajan et al., 2018; Sazvar et al., 2018). Thus, many studies have investigated emerging smart or intelligent packaging systems. Smart materials should have the ability to detect intelligently, or sense external and internal changes in the product, which would be more helpful to offer the details data for consumers (Kalpana et al., 2019; Sohail et al., 2018). The packaging materials should achieve many requirements, such as excellent biocompatibility (Díez-Pascual and Diez-Vicente, 2014), and robust mechanical properties (Abdalkarim et al., 2018; Zhang et al., 2017). Meanwhile, it should have resistance to water vapor permeability with sensory properties to protect the spoilage caused by chemical degradation or microbial growth during processing and storage durations (Caroline et al., 2018; Lin and Zhao, 2007). The combination of intelligent nanofillers and traditional polymers as smart packaging-based biosensors is still a challenge for further research (González et al., 2017; Marin-Bustamante et al., 2019).

PHBV biopolymer has attracted much consideration as a transparent biopolymer with excellent biocompatibility, and biodegradability. (Hiba et al., 2018; Koller and Martin, 2018; Zhao et al., 2013). Although PHBV offering some good properties, it still has some limitations such as large crystal size, high brittleness, poor thermal and barrier properties, and narrow processing window, which restricts their uses in many applications (Lammi et al., 2018; Abdalkarim et al., 2017; Hilliou and José, 2018). In this regard, many efforts have dedicated to enhancing PHBV performances as packaging materials by reinforcing with inorganic nanoparticles or biodegradable nanofillers (Kumar et al., 2019; Shiv et al., 2018).

Cellulose nanocrystals (CNCs) as rigid shape anisotropic and highly crystalline nanoparticles that present myriad applications. CNCs are considered promising materials in several applications due to their exciting features such as low price, renewable sources, nanometric size, and high strength (Yu et al., 2018). The CNCs have strong reinforcing effects, and previous studies have revealed their positive impact in mechanical, thermal, and barrier properties for packaging materials (Barral and Bouza, 2018, Abdalkarim et al., 2018; Malmir et al., 2019, 2018; Yu et al., 2012). Also, CNCs has used as a template for the growth inorganic nanoparticles such as zinc oxide (Díez-Pascual and Diez-Vicente, 2014), graphene oxide (Li et al., 2019a,b), silver (Yu et al., 2014; Shiv et al., 2018) and their hybrids have used as reinforcing/antimicrobial agents to improve photodegradation as well as barrier properties of PHBV nanocomposites. Nevertheless, for packaging applications, there is not enough to focus on the improvements in thermal, mechanical, antimicrobial, and barrier properties (Abdalkarim et al., 2018; Du et al., 2017; Yu et al., 2014). Thus, there still needs to produce smart PHBV nanocomposites with intelligent function, and sensor sensitivity for detecting water vapor.

Supermagnetic Fe3O4 NPs considered as only safe materials accepted by the American Food and Drug Administration (FDA) for clinical application (Shah and Dobrovolskaia, 2018; Xu et al., 2015). Fe3O4 NPs are desirable as a consequence of unique physical properties, excellent biocompatibility, and magnetic nature (Meng et al., 2018). To date, serval studies have demonstrated that Fe3O4 NPs with small nanosize and high surface area can easily aggregate. Therefore, the desperation and stability of Fe3O4 NPs in a polymer matrix will become more complicated, particularly with high nanofiller content (Dhar et al., 2016; Nypelö et al., 2014). A combination of both Fe3O4 NPs and CNCs has achieved to provide better dispersion and reduced agglomeration of Fe3O4 NPs (Zhang et al., 2019). In this regard, Liu et al. reported the successful fabrication of Fe3O4 NPs on the CNC surface by co-precipitation method as conductive coatings agent on paper anti-static packaging material (Liu et al., 2015). Tunicate CNC/ Fe3O4 hybrids have successfully used as reinforcing agents to prepare anisotropic rubber nanocomposites (Cao et al., 2019). Dhar et al. have prepared bamboo CNC templet to load Fe3O4 NPs and their nanohybrid used as nucleating agents into polylactic acid. Besides, a low magnetic field has used to provide parallel alignment for resultant anisotropic nanocomposites (Dhar et al., 2016).

By overview, the research filed of magnetic hybrids, the effect of supermagnetic Fe3O4-cellulose nanocrystals (MCNC) hybrids as intelligent function on the sensor property of PHBV matrix with other performances, biocompatibility, and water vapor sensor sensitivity have not published yet. Hence, this study highlights smart biopackaging materials based on intelligent MCNC hybrids and PHBV biopolymer. Moreover, the effects of these hybrids on real-time monitoring voltages response single as a function of water vapor have investigated. We expected that the combinations of both Fe3O4 NPs and CNCs could yield synergistic advantages of enhancing magnetic, mechanical, thermal properties, and crystallization rates of the PHBV nanocomposites. Besides, the water vapor permeability and cytocompatibility tests have evaluated to confirm the potential applications for these nanocomposites as bioactive and packaging materials.

Section snippets

Materials

Commercial PHBV (number-average molecular weight (Mn) = 5.90 × 104 Da, and the molar ratio of hydroxyvalerate (HV)=2.57 mol %) was supplied by Tianan Biological Material Co., Ltd. (Ningbo, China). Chloroform (CHCl3) was given by Guoyao Group Chemical Reagent Co., Ltd. Microcrystalline cellulose (MCC) was purchased from Sinopharm Chemical Reagent Co., Ltd. Commercial. Hydrochloric acid (HCl) was obtained by the Hangzhou Shuanglin Chemical Reagent Company. The citric acid (C6H8O7) was provided by

Characterization of MCNC hybrids

Fig. 1(a) and (b) illustrate the surface morphology structures of CNC and MCNC hybrids. Consequently, the length and diameter of individual CNCs were 235 ± 22.4 nm and 18 ± 3.1 nm, respetively. After co-precipitation reaction, uniform spherical Fe3O4 NPs with an average diameter of approximately 21 ± 1.9 nm were anchored uniformly on the CNC surface to form magnetic MCNC. The majority of Fe3O4 NPs was fully covered on the CNC surface after ultrasonication treatment. This observation suggests

Conclusions

In summary, we have successfully fabricated magnetic PHBV nanocomposite films from biopolyster PHBV and supermagnetic Fe3O4 NPs incorporated with CNCs as (MCNC) hybrids using a simple casting method. The Ms values of nanocomposites incorporated with MCNC hybrids were smaller than that of the nanocomposites with Fe3O4-5%. The synergistic reinforcing effect of CNCs and Fe3O4 (from MCNC hybrids) significantly improved the crystallization ability, mechanical and thermal properties of PHBV.

CRediT authorship contribution statement

Somia Yassin Hussain Abdalkarim: Writing - original draft, Methodology, Data curation. Yanyan Wang: Validation, Data curation. Hou-Yong Yu: Supervision, Writing - review & editing, Supervision, Conceptualization. Zhaofeng Ouyang: Writing - review & editing. Rabie A.M. Asad: Writing - original draft. Mengya Mu: Data curation, Investigation. Yujun Lu: Writing - review & editing. Juming Yao: Supervision. Lianyang Zhang: Formal analysis, Methodology.

Declaration of Competing Interest

The authors declare that they have no competing financial interest or personal relationships

Acknowledgments

The work is funded by Postdoctoral Research Project Selection Funding of Zhejiang Province [Project Number:11130031541901], Zhejiang Provincial Natural Science key Foundation of China (LZ20E030003), opening Project of Key Laboratory of Clean Dyeing and Finishing Technology of Zhejiang Province [QJRZ1905; QJRZ1910], the Fundamental Research Funds of Zhejiang Sci-Tech University (2019Q001) and the Young Elite Scientists Sponsorship Program by CAST (2018QNRC001).

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