Abstract
Polymer composites are fabricated by incorporating fillers into a polymer matrix. The intent for addition of fillers is to improve the physical, mechanical, chemical and rheological properties of the composite. This study reports on a unique polymer composite using hydrochar, synthesised by microwave-assisted hydrothermal carbonization of rice husk, as filler in polylactide matrix. The polylactide/hydrochar composites were fabricated by incorporating hydrochar in polylactide at 5%, 10%, 15% and 20 wt% by melt processing in a Haake rheomix at 170 °C. Both the neat polylactide and polylactide/hydrochar composite were characterized for mechanical, structural, thermal and rheological properties. The tensile modulus of polylactide/hydrochar composites was improved from 2.63 GPa (neat polylactide) to 3.16 GPa, 3.33 GPa, 3.54 GPa, and 4.24 GPa after blending with hydrochar at 5%, 10%, 15%, and 20%, respectively. Further, the incorporation of hydrochar had little effect on storage modulus (G′) and loss modulus (G″). The findings of this study reported that addition of hydrochar improves some characteristics of polylactide composites suggesting the potential of hydrochar as filler for polymer/hydrochar composites.
Similar content being viewed by others
Introduction
Concerns about a future scarcity of petroleum-based resources1,2 and environmental degradation caused by use of such sources3 have drawn attention towards substitution with bio-based materials in a variety of applications. The concept of blending (either by polymerization or physical4) of two materials is in practice since last two decades5. Driven by the development of polymer science and technologies6, renewable resources-based polymer composite materials are under consideration due to characteristics such as improved sustainability, carbon sequestration and energy efficiency of production, and light-weight7. The reinforcement of biomass-based materials using biochar or hydrochar as a filler for synthesis of biomass-based polymer composites is of great interest in polymer research recently. Research has been conducted for incorporation of biochar in different polymer matrices to improve their thermal, mechanical and electrical properties. Das et al.8 fabricated wood biochar polymer composites and investigated the effect of biochar loadings on the mechanical properties of the composites. It was concluded that the addition of 6 wt.% biochar did not improve the characteristics of the composite, although it was not deleterious either when compared to the properties of the control sample. Composites made by the addition of biochar at 12 wt.% and 18 wt.% were the most ductile and the most thermally stable respectively. The composite made with 24% biochar filler improved the mechanical properties i.e. moduli, flexural and tensile strengths. Although the scientific literature is replete with studies on utilizing biochar as filler in polymer matrices for synthesis of biochar/polymer composite, to date there is no any study reporting hydrochar as filler for polymer composites.
Hydrochar is a carbon-based material synthesized by hydrothermal carbonization of biomass or its derivatives at mild conditions9. Hydrothermal carbonization is a promising carbonization method as it is inexpensive, less energy intensive and, as it uses water as a reaction medium, wet biomass can be utilized in the process10. Further, chemical usage, pollution and the cost of the hydrothermal carbonization method is comparatively lower than other traditional techniques9,11. Hydrochar produced by HTC contains 80–90% of the energy content of the original feed and 55–90% mass of the original mass of biomass12. Research on hydrocar synthesis from hydrothermal carbonization is at an early stage and most studies have focused mainly on the effect of parameters used for the carbonization on the yield and the characteristics of hydrochar produced13. The applications of hydrochar include; as a carbon material’ an amendment of soil; a solid fuel, which is comparable to brown coal for production of energy; a substitute for activated carbon or carbon black; a carbon catalyst used for production of fine chemicals; a material to increase the efficiency of fuel cells, and; as an absorbent to increase fertility and productivity of soil14,15,16,17,18,19,20,21,22. More studies are focusing on its application as an adsorbent, but these incur several shortcomings. For example, low porosity and surface area of hydrochar causes low adsorption capacity due to inadequate binding sites for attaching to adsorbate23,24. The hydrochar also contains polar superficial functional groups which tend to lower the adsorption of non-polar organic matter. Furthermore, hydrochar has lower stability which suggests that hydrochar is not a long-term and recyclable adsorbent13. Therefore, this study proposes a novel application of hydrochar as filler in polymer composites.
Rice husk is considered as an agricultural residue coming from rice industry. The lignocellulosic composition of rice husk is dependent of various factors including agronomic handling, weather conditions and soil type25. The reported lignocellulosic composition of rice husk is cellulose 35%, hemicellulose 30%, lignin 18%, silica 13% and miscellaneous components upto 4%26. Around 140 million tonnes of rice husk are generated annually throughout the world, which is not properly utilized. This huge amount of rice husk is either discarded or burnt in open fields, which are environmentally hazardous strategies27. Production of hydrochar (having a number of applications) from rice husk is a way to suggest its effective utilization.
The main objective of this study was to utilize hydrochar produced from microwave hydrothermal carbonization of rice husk as filler for the development of polylactide/hydrochar biocomposites. Polylactide/hydrochar composites were prepared using extrusion techniques at various loadings (5%, 10%, 15% and 20%) of hydrochar in polylactide. The neat polylactide and polylactide/hydrochar biocomposite were analysed for mechanical, thermal, structural and rheological properties. The thermal properties were measured using thermogravimetric analysis (TGA) and modulated differential scanning calorimetry (MDSC), the mechanical properties were analysed through an Instron 4467 universal testing machine, the structural characterization were carried out using scanning electron microscopy (SEM), Fourier transform infra-red (FTIR) spectroscopy, and x-ray diffraction (XRD) analysis and an advanced rheometric expansion system (ARES) was used for rheological testing of polylactide/hydrochar composite.
Results and Discussion
SEM analysis of polylactide/hydrochar bio-composites
The SEM images of the tensile fractured surfaces of neat polylactide and polylactide/hydrochar composites are presented in Fig. 1(a–e). It can be observed that the neat polylactide had a smooth surface whereas the polylactide/hydrochar composites showed fractured surfaces with irregular voids and cracks. The porous structure of char particles allows some of the polymer matrix to penetrate into the char pores28. The fracture of composites resulted due to load transfer from polylactide to char particles29. From images of polylactide/hydrochar composites, it is observed that the polymer flows through pores of the hydrochar (Fig. 1(d,e)) causing a network of mechanical bonding which results in improved mechanical properties of the composite30,31. A high degree of mechanical interlocking/bonding suggests that the char particles are evenly distributed in the polymer matrix32. Das et al.33 also witnessed the mechanical interlocking between polypropylene and biochar. Further, the char particles were well-embedded in the polylactide causing an enhancement in the modulus of the composites. This is attributed to the small particle size of the char and the superior compatibility properties of the char with the polylactide.
XRD analysis of polylactide/hydrochar bio-composites
XRD analysis aids in the analysis of crystalline regions present in the sample. The XRD analysis patterns for neat polylactide and polylactide/hydrochar composites are presented in Fig. 2. Polylactide is a bio-based polymer; therefore it contains random arrangement of both the crystalline and amorphous phases34,35. Several peaks are observed at 2θ for neat polylactide which are attributed to the crystalline phase regions existing in polylactide36,37. The crystalline structure of the polylactide/hydrochar composites is not altered even at higher hydrochar loadings suggesting that the hydrochar is not modifying the crystalline phases of polylactide and the crystallinity of the composite is mostly conferred by the parent polymer38. Further, the peak intensity was decreased by addition of hydrochar and the reduction in peak intensity was greater at higher loadings of hydrochar. This is attributed to the increase of proportion of hydrochar (an amorphous component) and decline of polylactide (a crystalline component) resulting in an increase in the degree of amorphousity in the polylactic polymer29,38. The crystallization component of polymer decreases when increasing the amount of char particle in the composite39.
FTIR analysis of polylactide/hydrochar bio-composites
The FTIR analysis of polylactide/hydrochar composites was carried out to investigate the chemical linkage of hydrochar to polylactide matrix through any copolymerization reaction. The FTIR spectra spectra in the range of 4000–550 cm−1 for both the neat polylactide and polylactide/hydrochar composites are shown in Fig. 3. It is evident from Fig. 3 that all the samples had similar spectra and there were neither new peaks formed nor peaks removed in the composites suggesting that chemical interaction did not occur31 and only physical mixing occurred. Further, it reveals that the hydrochar addition doesn’t have any particular effect on the molecular structure of the polylactide. Similar results for the FTIR spectra for biochar/polypropylene composites are reported in the literature40.
The neat polylactide and polyactide/hydrochar biocomposites exhibited a peak at 1750 cm−1, which is attributed to ‒C=O of ester groups41. This peak corresponds to strong stretching vibration of ester carbonyl groups42 and it is assigned to ‒C=O present in the amorphous phase of polylactide. Moreover, it is noted that the peak at 1750 cm−1 is broadening slightly at increasing hydrochar loading suggesting that complexation occurs between polylactide matrix and filler43. A peak was observed at 1452 cm−1 for neat polylactide and polylactide/hydrochar composites which represents a typical CH3 symmetrical bend44. The neat polylactide had peaks at 1037, 1085, 1128 and 1182 cm−1 which are associated to C-C and C-O stretching. All polylactide/hydrochar blends has peaks at similar positions (with 3 cm−1). The peaks detected in the range of 1200-950 cm−1 are attributed to stretching of C-O-C, C-O, and C-OH functional groups45.
TGA analysis of polylactide/hydrochar bio-composites
Thermal degradation behaviour is considered as an important and easy tool to measure thermal stability of polymers and their composites during thermal processing46. Thermogravimetric analysis (TGA) is generally used to determine the thermal stability and degradation temperature of composite materials47,48. TGA analysis curves of polylactide/hydrochar composites are represented in Fig. 4. It is evident from Fig. 4 that the neat polylactide has higher degradation temperature than polylactide/hydrochar composites. Further, it is observed that the composites with higher hydrochar loadings have lower decomposition temperature. It was anticipated that the thermal degradation of composites would start at higher temperatures due to the higher thermal stability of hydrochar. However, this early degradation may be attributed to presence of greater amounts of polylactide in composite8. The maximum thermal degradation rate of neat polylactide was at about 390 °C, which decreased to lower temperatures at around 350 °C for all the biocomposite samples. Although degradation temperature of PLA/hydrochar composites was slightly lower than that of neat PLA, they will remain stable in the processing and application ranges of i.e. 30–240 °C of neat PLA without risking thermal degradation49,50. All the PLA/hydrochar composites possessed thermal degradation temperature in the range of 350–375 °C (Fig. 4b).
It can be seen from Fig. 4 that neat polylactide left the least residue yield whereas the composites yielded higher amounts of residue which may be attributed to the presence of thermally stable hydrochar in the composite. Ikram et al.30, studied the thermal stability behaviour of neat polypropylene and polypropylene\biochar composites and found similar results - that the neat polypropylene left lower residue yield than polypropylene/biochar composites after completion of thermal treatment. Another study also reported that the weight percentage of residue increased by increasing the char content in the composites, indicating that the chars may exhibit a condensed phase flame retardant mechanism46. The residue produced after the temperature cycle is proportional to the amount of char loaded in the composite, thus the addition of biochar in composites is beneficial when the amount of residue is the main concern31.
MDSC analysis of polylactide/hydrochar bio-composites
MDSC analysis determines several characteristics of polymers including cold crystallization temperature (Tc), enthalpy of crystallization (∆Hc), melting temperature (Tm), melting enthalpy (∆Hm), change of heat capacity (∆Cp), and percentage crystallinity (Xc)51. The results of MDSC analysis of neat polylactide and polylactide/hydrochar composites are listed in Table 1. It can be seen from Table 1 that the neat polylactide has a crystallization temperature at 93 °C, which slightly increased after addition of hydrochar due to the nucleation effect of hydrochar particles40. It is reported that these particles can act as nucleation sites causing crystal growth, which results in enhancement of the crystallization temperature30,31. An increment in the number of particles of char supports earlier crystallization of the polymers31. Similar observations have been reported where addition of different types of biochars produced from various feedstocks caused a shift in crystallization temperature to higher values than that of the neat polymer matrix31. Crystallization enthalpy was decreased with increasing hydrochar content.
The melting temperature for neat polylactide and polylactide/hydrochar composites at different loadings (5%, 10%, 15%, and 20%) was found to be 168.01 °C, 167.02 °C, 166.25 °C, 166.13 °C and 166.70 °C, respectively suggesting that the hydrochar incorporation in polylactide matrix had little effect on melting temperature. The results of the current study are in agreement to a previous study that biochar addition does not have significant effect on melting temperature52. Melting enthalpy of neat polylactide was 41.60 J/g, which was significantly reduced to 15.99 J/g, 12.78 J/g, 10.99 J/g, and 10.44 J/g at 5%, 10%, 15% and 20% loadings of hydrochar, respectively. The variation in melting enthalpy at different hydrochar loadings may be linked to a transformation of crystalline properties of the composite53.
The total crystallinity was significantly reduced by addition of the hydrochar in the polylactide matrix, further it was noted that at higher hydrochar loading lower total crystallinity was observed. The decreased total crystallinity of polylactide/hydrochar composites compared to neat polylactide is attributed to the agglomerating nature of hydrochar. The agglomerating nature of the char does not allow free movement of polymer chains, deterring polylactide segments to be packed orderly into an organized crystal form54.
Mechanical characteristics of polylactide/hydrochar bio-composites
Mechanical performance of the composites is dependent on several factors such as adhesion between filler and polymer matrix, aspect ratio of reinforcing filler particles, crystallinity of the matrix, and volume fraction and orientation of fibers (mostly lignocellulosic and its derivatives)55. Figure 5(a–c) shows the mechanical properties of neat polylactide and polylactide/hydrochar composites. It can be observed from Fig. 5(a) that the tensile strength decreases by incorporating hydrochar in the polylactide matrix. Decrement in tensile strength of polylactide/hydrochar composite may be attributed to poor interfacial bonding between polylactide and hydrochar. This also might be due to weak regions of polymer matrix-hydrochar filler, where loops of various chains are in close proximity but are not entangled with each other56. Such aggregates of chain ends may cause occurrence of micro-cracks at interfaces lowering the interaction between matrix and filler57. Further, a higher rate of decrease in tensile strength is noted at higher loadings of hydrochar. The tensile strength of neat polylactide was found to be 43.69 MPa, which decreased to 41.12 MPa, 40.03 MPa, 38.98 MPa and 36.82 MPa at 5%, 10%, 15% and 20% loading of hydrochar respectively. Lower tensile strength at higher loadings of hydrochar is possibly due higher concentration of hydrochar resulting in the presence of higher amounts of hydrochar interfaces with the polymer matrix58. Relatively greater particle distribution of char and low adhesion within polymer matrix resulted in decreased tensile strength at higher loadings of char59. The tensile strength can be improved through compatibilization between polymer matrix and char particles44. A decline in tensile strength of polypropylene/biochar composite is reported in literature40.
The tensile modulus of polylactide/hydrochar composites exhibited an increasing trend with hydrochar loadings as shown in Fig. 5(b). It can be observed that neat polylactide has lower tensile modulus which increases gradually with an increasing content of hydrochar. According to Das et al.33 a higher modulus of biochar/polymer composite is endorsed by the high surface area of the biochar, which boosted stress transfer between biochar particles and polymer matrix consequently decreasing the deformability of the polymer and improving the modulus. A higher modulus also might be attributed to improved adhesion between the polymer matrix and filler resulting in less and smaller gaps between interfacial surfaces60. Nan et al.59, suggests that an improvement in tensile modulus of a composite is due to higher rigidity of the biochar filler. The gradual increase in tensile modulus of biochar/polypropylene biocomposite with increasing biochar content in the polymer matrix has been reported in literature40,61. The elongation at break is illustrated in Fig. 5(c), which reveals that the elongation at break for neat polylactide is higher than polylactide/hydrochar composites. Further, elongation at break decreases with increase in hydrochar loading which is due to aggregation of nonintercalated fillers in the composites enhancing embrittlement58. Thellen et al.62, reported that incorporation of filler into plastics will significantly decrease the elongation.
Rheological analysis of polylactide/hydrochar biocomposites
Rheological characteristics of the polymers and their composites tend to differentiate the degree of dispersion51. The rheological testing was carried out based on dynamic frequency sweep tests at 170 °C and 0.05–100 rad/s. The storage modulus (G′), the loss modulus (G″), and the ratio of loss modulus (G″) to storage modulus (G′) i.e. (tan δ) were obtained from rheological measurements and shown in Fig. 6(a–c). Figure 6(a) represents the relationship between angular frequency (ω) and storage moduli (G′) of neat polylactide and polylactide/hydrochar composites at 5%, 10%, 15% and 20% hydrochar loading. It is observed that the storage modulus (G′) of the polylactide/hydrochar composites is slightly higher than that of the neat polylactide which may be attributed to the formation of a filler-polymer network40. Further, it is noted that the storage modulus (G′) increases when increasing the hydrochar content in composites because the hydrochar clusters tend to reduce the mobility of polymer chains and thus increases resistance to flow63. The trend for G′ in the low frequency range shows that the storage modulus is higher for the composites than PLA, while in the high frequency range the difference in G′ is not significant. An increment in the storage modulus (G′) of composites is not significant, as expected, due to the impure nature of the hydrochar and the weak interaction between hydrochar and polymer. A weak adhesion or interaction between polymers and fillers have been observed in previous studies including biochar composites and highly engineered carbon composites40,64. Similar behaviour for loss modulus (G″) was also observed for all the composites with a higher loss modulus (G″) than that of the neat polymer as shown in Fig. 6(b). Tan δ is generally used to determine the viscoelasticity of the materials, which is more sensitive to relaxation changes than the storage modulus and loss modulus65. Figure 6(c) represents the frequency dependence of loss tangent (tan δ) by plotting the data of (tan δ) vs. frequency for neat polylactide and polylactide/hydrochar composites. It is noted that the (tan δ) of neat polylactide was higher at low frequency than that of the polylactide/hydrochar composites, whereas the (tan δ) of both the neat polylactide and polylactide/hydrochar composites was similar at higher frequencies. A decrease in tan δ at higher frequency is the typical characteristic of a viscoelastic liquid65. Further, the tan δ is decreasing at higher hydrochar loadings, which is attributed to a polymer-filler network63. Similar results for tan δ of biochar/polypropylene composites have been reported in the literature40.
Potential applications of char-added composites
A major challenge for any manufacturing industrial system is to decrease the production cost as well as to achieve sustainability and better properties of the product. The incorporation of renewable materials to produce advanced materials promotes environmental sustainability considering that the renewable material will not generate any further waste33. Therefore, utilization of chars as filler for synthesis of polymeric composites is an efficient way of waste utilization together with producing an innovative material66. The char, being obtained from waste residues, demonstrates an effective waste management strategy to reduce landfill pressure from dumping of wastes. In addition, the reinforcement of char in polymers improves mechanical, thermal, rheological, electrical and other properties of the composites, consequently allowing different applications for the char/polymer composites. Inclusion of char in a polymer matrix addresses waste utilization, reduces the use of synthetic materials, enhances the properties of the product and potentially reduces cost61.
Due to the adsorption characteristics, moisture control, and higher anti-microbial characteristics of the char, the char/polymer composite may have potential application in the food packaging industry29. As char can be used to control humidity, regulate moisture and absorb radiation from the environment - char based polymer composite may be used to line wine cellars66. The inherent thermal stability of chars supports the application of char based composites as flame retardant materials44,67. Therefore, char/polypropylene biocomposites can potentially be used in the interior of automobiles and aeroplanes providing fire-resistant and light-weight material properties31. The char/polymer biocomposites possessing acceptable stiffness and fire resistance properties have potential applications in aviation, packaging and playground structures33. Future research should focus on investigating various sources of chars and to alter various parameters of char including ash content, particle size, and surface chemistry in order to improve its characteristics and make a more competitive filler68. The processing conditions for production of char also can affect the physico-chemical properties of the resulting materials69. Therefore, more research is needed to investigate that how these factors affect the properties of composites prepared with char particles.
Conclusion
This study addressed an issue of waste utilization by addition of hydrochar in polymer matrix for synthesis of polymer/hydrochar composites. The higher porosity of hydrochar supports infiltration of polymers into the pores of hydrochar resulting in some better properties. Thus the hydrochar was utilized in polylactide in this study. The polylactide/hydrochar composites were prepared through melting and mixing of neat polylactide and hydrochar using a Haake rheomix at 5%, 10%, 15% and 20% loading of hydrochar.
The findings of the study suggest that addition of hydrochar in polylactide improved the thermal, mechanical, and rheological properties. When tested by TGA, the residue yield of neat polylactide was higher than that of polylactide/hydrochar composites due to the presence of the thermally stable hydrochar in the composites. The tensile moduli of the polylactide/hydrochar composites were greater than that of the neat polylactide. The neat polyalctide had lower storage modulus and loss modulus as compared to the polylactide/hydrochar composites. Further, the SEM analysis showed that the polymer infiltrates through hydrochar pores causing mechanical bonding between polymer matrix and hydrochar which results in improved mechanical properties of the composite such as higher tensile modulus at higher loadings of hydrochar. The hydrochar/polymer composites may have potential application in food packaging industry, aviation, packaging and playground structures, line wine cellars, and as flame retardant material in the interior of automobiles and aeroplanes providing fire-resistant and light-weight material properties.
Experimental
Materials
Polylactic acid (PLA- 4032D Nature-Works,) molecular weight Mw - 155,000 g/mol70, density- 1.24 g/cm3) supplied from Sigma Aldrich was used in this study. The hydrochar used in this study was synthesized through microwave hydrothermal carbonization of rice husk and was characterized using techniques previously developed71. Rice husk used for hydrochar synthesis was received from Dowens Rice Hulls Pty. Ltd., Victoria, Australia. The rice husk was washed distilled water to remove dirt and impurities, dried in an oven at 105 °C for 24 h and ground to 1–3 mm before using for the experiments. Both rice husk and synthesized hydrochar were characterized and reported in previous work71.
Preparation of polylactide/hydrochar composites
The polylactide/hydrochar composites films were prepared by incorporating hydrochar in polylactide matrix at four different concentrations as shown in Table 2. The percentage of hydrochar loading in polylactide was based on previous study, which suggested that less than 5% and higher than 15% of char loadings do not show any significant effect on phyico-mechanical properties of biocomposites31. The hydrochar and polylactide were physically mixed through hopper of Haake Rheomix, which was used to melt-blend the samples at 170 °C and 40 rpm for 5 min. The samples were coded as polylactide/hydrochar-5 wt%, polylactide/hydrochar-10 wt%, polylactide/hydrochar-15 wt%, and polylactide/hydrochar-20 wt% in which the number denoted the concentration (wt%) of hydrochar in polylactide.
Characterisation of polylactide/hydrochar biocomposites
The morphology of fractured surfaces of neat PLA and polylactide/hydrochar biocomposite was studied by a Philips XL30 SEM. All the SEM images were acquired at accelerating voltage of 15 kv, at magnification of 2000×, at high vacuum mode. The samples were then sputter coated with layer of gold, about 20 nm in 60 sec to control charging. XRD patterns for polylactide/hydrochar biocomposite were obtained by using a Bruker D4 Endeavor X-ray diffractometer in the angular range of 6–90° (2θ) at 40 kV voltages and 35 mA current. The functional groups on the surface of polylactide/hydrochar composites were determined through FTIR spectroscopic studies using a PerkinElmer FTIR spectrophotometer at 4000 to 450 cm−1wavelength, 32 scans per sample at a resolution of 4 cm−1. The thermal stability of polylactide/hydrochar biocomposites was analysed using a STA 6000, (Perkin-Elmer). The samples were heated from 30 °C to 600 °C at 10 °C min−1 heating rate. The samples were held for a minute at both the initial and final temperatures. The testing was repeated three times and sample weight percentage was plotted as a function of temperature.
A DSC-2920 Modulated DSC (TA Instruments) was used to study the thermal properties of the polylactide/hydrochar biocomposites. Initially, the instrument was standardized with indium at 35 ml/min flow rate of nitrogen. An empty aluminium pan wrapped with lid was used as reference. Approximately 7–10 mg of polylactide/hydrochar biocomposite samples were encapsulated in the aluminium pan. For first heating cycle, the samples were heated in the range of −20 °C to 220 °C at 20 °C/min heating rate and then cooled at 2.00 °C/min to −20.00 °C. This scan removed any earlier thermal history of the polylactide/hydrochar biocomposites. For the second heating cycle, the samples were heated from −20 °C to 220 °C at 2 °C/min heating rate and were modulated +/− 0.50 °C every 40 seconds. The lower heating rate for the second heating cycle was employed for accurate tracing of small transitions. The samples were left for five mins at both the initial and final temperatures in both cycles. The degree of crystallinity (Xc) of neat polylactide and polylactide/hydrochar biocomposites was calculated through Eq. (1):
Where ∆Hm denotes the melting enthalpy, ∆Hc refers to the cold crystallisation enthalpy, \({{\rm{\Delta }}H}_{{\rm{m}}}^{{\rm{c}}}\) is the enthalpy of pure polylactide (93 Jg−1)72,73 and WPLA is the weight fraction of the polylactide in polylactide/hydrochar biocomposites.
For mechanical testing, the samples were compression-moulded into dog-bone shaped ASTM D638 mechanical testing specimens at 180 °C compression moulding temperature for 5 min while 80 kN of compression force was applied. Further, the moulding press was cooled down to 50 °C with the help of cooling water. The mechanical testing of the samples was conducted through an Instron 4467 universal testing machine according to ASTM D638M at 1 mm/min speed rate. Rheological studies of the polylactide/hydrochar bio-composites were studied by a strain-controlled ARES (TA instruments) rheometer. The bio-composites were tested through a force transducer with 0.2–200 g-cm torque range and 25 mm diameter parallel-plate fixture. Measurements were carried out at 170 °C temperature. Zero gap calibrations were checked at 170 °C before running each test. Linear viscoelastic regions (LVR) of the composites were examined through strain sweep experiments at 1 rad/s frequency and 0.1–100% strain. Further, dynamic frequency sweep tests were conducted again on fresh samples in LVR at 0.05–100 rad/s frequency range for understanding hydrochar loadings effect on storage (G′), loss modulus (G″) and complex viscosity (η*) of the polylactide/hydrochar biocomposites.
References
Baloch, H. A. et al. Recent advances in production and upgrading of bio-oil from biomass: A critical overview. Journal of Environmental Chemical Engineering (2018).
Rezakazemi, M., Sadrzadeh, M., Matsuura, T. J. P. I. E. & Science, C. Thermally stable polymers for advanced high-performance gas separation membranes. 66, 1–41 (2018).
Baloch, H. A. et al. Sub-supercritical liquefaction of sugarcane bagasse for production of bio-oil and char: Effect of two solvents. Journal of Environmental Chemical Engineering (2018).
Rezakazemi, M., Vatani, A. & Mohammadi, T. J. R. A. Synergistic interactions between POSS and fumed silica and their effect on the properties of crosslinked PDMS nanocomposite membranes. 5, 82460–82470 (2015).
Rezakazemi, M., Shahidi, K. & Mohammadi, T. J. I. J. O. H. E. Hydrogen separation and purification using crosslinkable PDMS/zeolite A nanoparticles mixed matrix membranes. 37, 14576–14589 (2012).
Rezakazemi, M., Vatani, A., Mohammadi, T. J. J. O. N. G. S. & Engineering. Synthesis and gas transport properties of crosslinked poly (dimethylsiloxane) nanocomposite membranes using octatrimethylsiloxy POSS nanoparticles. 30, 10–18 (2016).
Väisänen, T., Das, O. & Tomppo, L. A review on new bio-based constituents for natural fiber-polymer composites. Journal of Cleaner Production 149, 582–596 (2017).
Das, O., Sarmah, A. K. & Bhattacharyya, D. A novel approach in organic waste utilization through biochar addition in wood/polypropylene composites. Waste management 38, 132–140 (2015).
Lei, Y., Su, H. & Tian, F. A Novel Nitrogen Enriched Hydrochar Adsorbents Derived from Salix Biomass for Cr (VI) Adsorption. Scientific reports 8, 4040 (2018).
Nizamuddin, S. et al. Advanced Nanomaterials Synthesis from Pyrolysis and Hydrothermal Carbonization: A Review. Current Organic Chemistry 22, 446–461 (2018).
Nizamuddin, S. et al. An overview of effect of process parameters on hydrothermal carbonization of biomass. Renewable and Sustainable Energy Reviews 73, 1289–1299 (2017).
Yan, W., Acharjee, T. C., Coronella, C. J. & Vásquez, V. R. Thermal pretreatment of lignocellulosic biomass. Environmental Progress & Sustainable Energy 28, 435–440 (2009).
Han, M. et al. Bio-butanol sorption performance on novel porous-carbon adsorbents from corncob prepared via hydrothermal carbonization and post-pyrolysis method. Scientific reports 7, 11753 (2017).
Berge, N. D., Kammann, C., Ro, K. & Libra, J. Environmental Applications of Hydrothermal Carbonization Technology: Biochar Production, Carbon Sequestration, and Waste Conversion. Sustainable Carbon Materials from Hydrothermal Processes, 295–340 (2013).
Du, Z. et al. Cultivation of a microalga Chlorella vulgaris using recycled aqueous phase nutrients from hydrothermal carbonization process. Bioresource technology 126, 354–357 (2012).
Funke, A. & Ziegler, F. Hydrothermal carbonization of biomass: a summary and discussion of chemical mechanisms for process engineering. Biofuels, Bioproducts and Biorefining 4, 160–177 (2010).
Kang, S., Li, X., Fan, J. & Chang, J. Characterization of hydrochars produced by hydrothermal carbonization of lignin, cellulose, D-xylose, and wood meal. Industrial & engineering chemistry research 51, 9023–9031 (2012).
Kleinert, M. & Wittmann, T. Carbonisation of biomass using hydrothermal approach: State-of-the-art and recent developments. Vortrag zur 17 (2009).
Libra, J. A. et al. Hydrothermal carbonization of biomass residuals: a comparative review of the chemistry, processes and applications of wet and dry pyrolysis. Biofuels 2, 71–106 (2011).
Parshetti, G. K., Kent Hoekman, S. & Balasubramanian, R. Chemical, structural and combustion characteristics of carbonaceous products obtained by hydrothermal carbonization of palm empty fruit bunches. Bioresource technology 135, 683–689 (2013).
Rillig, M. C. et al. Material derived from hydrothermal carbonization: effects on plant growth and arbuscular mycorrhiza. Applied Soil Ecology 45, 238–242 (2010).
Nizamuddin, S. et al. An overview of microwave hydrothermal carbonization and microwave pyrolysis of biomass. Reviews in Environmental Science and Bio/Technology, 17(4), 813–837 (2018).
Sevilla, M., Maciá-Agulló, J. A. & Fuertes, A. B. Hydrothermal carbonization of biomass as a route for the sequestration of CO2: Chemical and structural properties of the carbonized products. Biomass and Bioenergy 35, 3152–3159 (2011).
Ahmaruzzaman, M. Adsorption of phenolic compounds on low-cost adsorbents: a review. Advances in colloid and interface science 143, 48–67 (2008).
Elaigwu, S. E. & Greenway, G. M. J. F. P. T. Microwave-assisted hydrothermal carbonization of rapeseed husk: a strategy for improving its solid fuel properties. 149, 305–312 (2016).
Islam, M. S., Kao, N., Bhattacharya, S. N., Gupta, R. & Choi, H. J. J. C. J. O. C. E. Potential aspect of rice husk biomass in Australia for nanocrystalline cellulose production. 26, 465–476 (2018).
Lin, L. et al. Dye adsorption of mesoporous activated carbons produced from NaOH-pretreated rice husks. 136, 437–443 (2013).
DeVallance, D. B., Oporto, G. S. & Quigley, P. Investigation of hardwood biochar as a replacement for wood flour in wood–polypropylene composites. Journal of Elastomers & Plastics 48, 510–522 (2016).
Ho, M.-P., Lau, K.-T., Wang, H. & Hui, D. Improvement on the properties of polylactic acid (PLA) using bamboo charcoal particles. Composites Part B: Engineering 81, 14–25 (2015).
Ikram, S., Das, O. & Bhattacharyya, D. A parametric study of mechanical and flammability properties of biochar reinforced polypropylene composites. Composites Part A: Applied Science and Manufacturing 91, 177–188 (2016).
Das, O., Bhattacharyya, D., Hui, D. & Lau, K.-T. Mechanical and flammability characterisations of biochar/polypropylene biocomposites. Composites Part B: Engineering 106, 120–128 (2016).
Zhang, Q., Yi, W., Li, Z., Wang, L. & Cai, H. Mechanical Properties of Rice Husk Biochar Reinforced High Density Polyethylene Composites. Polymers 10, 286 (2018).
Das, O., Kim, N. K., Sarmah, A. K. & Bhattacharyya, D. Development of waste based biochar/wool hybrid biocomposites: flammability characteristics and mechanical properties. Journal of cleaner production 144, 79–89 (2017).
Mukherjee, T. et al. Improved dispersion of cellulose microcrystals in polylactic acid (PLA) based composites applying surface acetylation. Chemical Engineering Science 101, 655–662 (2013).
Lin, N., Chen, G., Huang, J., Dufresne, A. & Chang, P. R. Effects of polymer-grafted natural nanocrystals on the structure and mechanical properties of poly (lactic acid): A case of cellulose whisker-graft-polycaprolactone. Journal of Applied Polymer Science 113, 3417–3425 (2009).
Furuhashi, Y. & Yoshie, N. Stereocomplexation of solvent-cast poly (lactic acid) by addition of non-solvents. Polymer International 61, 301–306 (2012).
Chen, X., Kalish, J. & Hsu, S. L. Structure evolution of α′-phase poly (lactic acid). Journal of Polymer Science Part B: Polymer Physics 49, 1446–1454 (2011).
Das, O., Sarmah, A. K., Zujovic, Z. & Bhattacharyya, D. Characterisation of waste derived biochar added biocomposites: chemical and thermal modifications. Science of the Total Environment 550, 133–142 (2016).
Chew, K., Ng, T. & How, Z. Conductivity and microstructure study of PLA-based polymer electrolyte salted with lithium perchloride, LiClO4. Int J Electrochem Sci 8 (2013).
Poulose, A. M. et al. Date palm biochar-polymer composites: An investigation of electrical, mechanical, thermal and rheological characteristics. Science of The Total Environment 619, 311–318 (2018).
Garcia, N. L. et al. Biodegradable materials from grafting of modified PLA onto starch nanocrystals. Polymer Degradation and Stability 97, 2021–2026, https://doi.org/10.1016/j.polymdegradstab.2012.03.032 (2012).
Lin, N., Huang, J., Chang, P. R., Feng, J. & Yu, J. Surface acetylation of cellulose nanocrystal and its reinforcing function in poly(lactic acid). Carbohydrate Polymers 83, 1834–1842, https://doi.org/10.1016/j.carbpol.2010.10.047 (2011).
Lin, N., Chen, G., Huang, J., Dufresne, A. & Chang, P. R. Effects of polymer-grafted natural nanocrystals on the structure and mechanical properties of poly(lactic acid): A case of cellulose whisker-graft-polycaprolactone. Journal of Applied Polymer Science 113, 3417–3425, https://doi.org/10.1002/app.30308 (2009).
Das, O., Sarmah, A. K. & Bhattacharyya, D. Biocomposites from waste derived biochars: mechanical, thermal, chemical, and morphological properties. Waste Management 49, 560–570 (2016).
Nizamuddin, S. et al. Synthesis and characterization of hydrochars produced by hydrothermal carbonization of oil palm shell. The Canadian Journal of Chemical Engineering 93, 1916–1921, https://doi.org/10.1002/cjce.22293 (2015).
Ahmetli, G., Kocaman, S., Ozaytekin, I. & Bozkurt, P. Epoxy composites based on inexpensive char filler obtained from plastic waste and natural resources. Polymer Composites 34, 500–509 (2013).
Liu, X. et al. Thermal degradation and stability of starch under different processing conditions. Starch-Stärke 65, 48–60 (2013).
Zakikhani, P., Zahari, R., Sultan, M. & Majid, D. Extraction and preparation of bamboo fibre-reinforced composites. Materials & Design 63, 820–828 (2014).
Arrieta, M. P. et al. Multifunctional PLA–PHB/cellulose nanocrystal films: Processing, structural and thermal properties. 107, 16–24 (2014).
Das, K. et al. Crystalline morphology of PLA/clay nanocomposite films and its correlation with other properties. 118, 143–151 (2010).
Takkalkar, P. et al. Preparation of Square-Shaped Starch Nanocrystals/Polylactic Acid Based Bio-nanocomposites: Morphological, Structural, Thermal and Rheological Properties. Waste and Biomass Valorization, 1–15 (2018).
Doh, G.-H., Lee, S.-Y., Kang, I.-A. & Kong, Y.-T. Thermal behavior of liquefied wood polymer composites (LWPC). Composite structures 68, 103–108 (2005).
Hu, F., Lin, N., Chang, P. R. & Huang, J. Reinforcement and nucleation of acetylated cellulose nanocrystals in foamed polyester composites. Carbohydrate polymers 129, 208–215 (2015).
Chen, J., Li, X. & Wu, C. Crystallization behavior of polypropylene filled with modified carbon black. Polymer journal 39, 722 (2007).
Masirek, R., Kulinski, Z., Chionna, D., Piorkowska, E. & Pracella, M. Composites of poly (L-lactide) with hemp fibers: Morphology and thermal and mechanical properties. Journal of applied polymer science 105, 255–268 (2007).
Landel, R. F. & Nielsen, L. E. Mechanical properties of polymers and composites. (CRC press, 1993).
Karabulut, M. Production and characterization of nanocomposite materials from recycled thermoplastics, METU (2003).
Narimissa, E., Gupta, R. K., Choi, H. J., Kao, N. & Jollands, M. Morphological, mechanical, and thermal characterization of biopolymer composites based on polylactide and nanographite platelets. Polymer Composites 33, 1505–1515 (2012).
Nan, N., DeVallance, D. B., Xie, X. & Wang, J. The effect of bio-carbon addition on the electrical, mechanical, and thermal properties of polyvinyl alcohol/biochar composites. Journal of Composite Materials 50, 1161–1168 (2016).
Qian, S., Wang, H., Zarei, E. & Sheng, K. Effect of hydrothermal pretreatment on the properties of moso bamboo particles reinforced polyvinyl chloride composites. Composites Part B: Engineering 82, 23–29 (2015).
Das, O., Bhattacharyya, D. & Sarmah, A. K. Sustainable eco–composites obtained from waste derived biochar: a consideration in performance properties, production costs, and environmental impact. Journal of cleaner production 129, 159–168 (2016).
Thellen, C. et al. Influence of montmorillonite layered silicate on plasticized poly (l-lactide) blown films. Polymer 46, 11716–11727 (2005).
Ren, D. et al. Formation and evolution of the carbon black network in polyethylene/carbon black composites: Rheology and conductivity properties. Journal of Applied Polymer Science 131 (2014).
Lee, S. H., Cho, E., Jeon, S. H. & Youn, J. R. Rheological and electrical properties of polypropylene composites containing functionalized multi-walled carbon nanotubes and compatibilizers. Carbon 45, 2810–2822 (2007).
Xu, Z. et al. Morphology, rheology and crystallization behavior of polylactide composites prepared through addition of five-armed star polylactide grafted multiwalled carbon nanotubes. Polymer 51, 730–737 (2010).
Das, O., Sarmah, A. K. & Bhattacharyya, D. Nanoindentation assisted analysis of biochar added biocomposites. Composites Part B: Engineering 91, 219–227 (2016).
Schmidt, H. The use of biochar as building material-cities as carbon sinks. Journal for terrior-wine and biodiversity (2013).
Peterson, S. C. Evaluating corn starch and corn stover biochar as renewable filler in carboxylated styrene–butadiene rubber composites. Journal of Elastomers & Plastics 44, 43–54 (2012).
Xie, X., Goodell, B., Qian, Y., Peterson, M. & Jellison, J. Significance of the heating rate on the physical properties of carbonized maple wood. Holzforschung 62, 591–596 (2008).
Sungsanit, K., Kao, N., Bhattacharya, S. & Pivsaart, S. Physical and rheological properties of plasticized linear and branched PLA. Korea-Australia Rheology Journal 22, 187–195 (2010).
Nizamuddin, S. et al. Upgradation of chemical, fuel, thermal, and structural properties of rice husk through microwave-assisted hydrothermal carbonization. Environmental Science and Pollution Research. https://doi.org/10.1007/s11356-018-1876-7 (2018).
Turner, J., Riga, A., O’Connor, A., Zhang, J. & Collis, J. Characterization of drawn and undrawn poly-L-lactide films by differential scanning calorimetry. Journal of Thermal Analysis and Calorimetry 75, 257–268 (2004).
Mathew, A. P., Oksman, K. & Sain, M. The effect of morphology and chemical characteristics of cellulose reinforcements on the crystallinity of polylactic acid. Journal of Applied Polymer Science 101, 300–310, https://doi.org/10.1002/app.23346 (2006).
Author information
Authors and Affiliations
Contributions
N.M. Mubarak and Gregory Griffin designed the research; Sabzoi Nizamuddin performed experimental work, Humair Ahmed Baloch, M.T.H. Siddiqui, Srinivasan Madapusi and Akshat Tranksale analysis data. Ankit Jadhav, Sundus Saeed Qureshi and Mohd Imran Ahamed have helped in scientific discussion to revise manuscript. N.M. Mubarak, Gregory Griffin and Sabzoi Nizamuddin wrote the manuscript.
Corresponding author
Ethics declarations
Competing Interests
The authors declare no competing interests.
Additional information
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Nizamuddin, S., Jadhav, A., Qureshi, S.S. et al. Synthesis and characterization of polylactide/rice husk hydrochar composite. Sci Rep 9, 5445 (2019). https://doi.org/10.1038/s41598-019-41960-1
Received:
Accepted:
Published:
DOI: https://doi.org/10.1038/s41598-019-41960-1
This article is cited by
-
Production of hydrogen using plastic waste via Aspen Hysys simulation
Scientific Reports (2024)
-
Biochar from pyrolysis of rice husk biomass—characteristics, modification and environmental application
Biomass Conversion and Biorefinery (2024)
-
Preparation and characterization of potato peel derived hydrochar and its application for removal of Congo red: a comparative study with potato peel powder
International Journal of Environmental Science and Technology (2024)
-
Palm oil mill effluent-derived biochar-filled high-density polyethylene composites: processability and physico-mechanical properties evaluation
Journal of Material Cycles and Waste Management (2024)
-
Concrete Made with Partial Substitutions of Wheat Straw Ash: A Review
International Journal of Concrete Structures and Materials (2023)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.