Composites Part B 287 (2024) 111857

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Sustainable engineering polymer composites fabricated using delignified

bamboo fiber as reinforcement and walnut shell powder as filler
Le Li a,b, Shouqing Liu c , Guanben Du a,b,c , Shuyang Jiang a,b, Jing Yang b,c , Jianli Zhang c ,
Taohong Li a,b,c,*
a
The Yunnan Provincial Key Lab of Wood Adhesives and Glued Products, Southwest Forestry University, Kunming, 650224, China
b
International Joint Research Center for Biomass Materials, Southwest Forestry University, Kunming, 650224, China
c
The Key Laboratory of State Forestry and Grassland Administration on Highly-efficient Utilization of Forestry Biomass Resources in Southwest China, Southwest Forestry
University, Kunming, 650224, China

A R T I C L E I N F O A B S T R A C T

Handling Editor: Dr Hao Wang Developing sustainable engineering materials using renewable resources and agro-wastes represents an effective
method for reducing carbon emissions and environmental pollution. In this study, a novel approach to fabri­
Keywords: cating high-performance biomass-based polymer composites was presented. Specifically, partially delignified
Delignified bamboo fiber bamboo fiber (DBF) and walnut shell powder (WSP) were incorporated into the matrix, namely melamine-
Reinforcement
hexamethylenediamine-urea (MHU) resin which was previously known for its excellent interfacial compati­
Walnut shell
bility. Mechanical property investigations show that the DBF, acting as the reinforcement, provided the hybrid
Hybrid composites
composites with high flexural and tensile strength up to 220 and 120 MPa, respectively, greatly surpassing those
of commercial wood-plastic composites, wood-based composites, and natural wood, making them promising
structural materials. As the filler, walnut shell powder endowed the composites with high hardness (Shore D >
90) and an appealing mirror-like surface gloss. Owing to the protection provided by the MHU matrix, the
composite containing 38 % MHU exhibited outstanding flame retardancy (UL 94-V0 grade), which was further
supported by cone calorimeter test (CCT) results. An unexpected and intriguing finding is that the composites
exhibited fluorescence under UV irradiation. The rare silvery-grey fluorescence color imparted self-
anticounterfeiting property to the composites. This study demonstrated the significant potential of bamboo
fiber and walnut shell in the development of sustainable engineering materials.

1. Introduction repurposing agro-wastes and transforming them into high-performance,

high value-added materials would offer substantial environmental and
Composite materials in engineering are extensively utilized across economic benefits.
various industries owing to their beneficial features such as lightweight, Walnut shell is one of the bulky agro-wastes. According to recent
high strength, and exceptional environmental durability [1]. However, statistics [5], global walnut production reached 2.31 million tons in
mounting concerns regarding environmental pollution and the depletion 2022, and approximately 67 % of the walnut mass, predominantly in the
of fossil resources have sparked increased interest in the development of form of shells, is either discarded into the environment or incinerated.
sustainable composite materials [2]. In particular, the reinforcements Due to its substantial lignin content (32–44 %) [6], relatively high
and fillers derived from biomass have demonstrated considerable po­ density, and a unique interlocked packing polylobate sclereid cell
tential in the creation of environmentally friendly composites [3]. microstructure, walnut shells possess high hardness and stiffness [7,8].
Among various bioresources, agro-wastes have come to the forefront. As such, walnut shells are well-suited as biomass reinforcement or filler
Global agricultural production yields billions of tons of agro-wastes for composites, whether in particle or powder form. Several studies have
annually [4]. Due to the absence of efficient utilization strategies, demonstrated that the incorporation of ground walnut shells enhanced
these agro-wastes are typically either incinerated or disposed of in the thermal insulation capacity of both thermoplastic and thermosetting
landfills, leading to severe environmental pollution. Consequently, matrices [9], while also increasing stiffness and hardness [10].

* Corresponding author. The Yunnan Provincial Key Lab of Wood Adhesives and Glued Products, Southwest Forestry University, Kunming, 650224, China.
E-mail address: [email protected] (T. Li).

https://doi.org/10.1016/j.compositesb.2024.111857
Received 24 February 2024; Received in revised form 8 September 2024; Accepted 19 September 2024
Available online 19 September 2024
1359-8368/© 2024 Elsevier Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
L. Li et al. Composites Part B 287 (2024) 111857

However, the addition of walnut shell fillers often leads to a significant Pharmaceutical Co., Ltd. All chemical reagents were used as received
decrease in tensile and flexural strength [11], as well as reduced impact without further purification. Walnut shell (Juglans regia L.) flour
resistance [11]. This decline in mechanical properties can be attributed (100–200 mesh) and bamboo were procured from the local market. The
to the non-continuous structure of the shell particles, which undermines bamboo stem was cut into strips measuring 20 mm × 350 mm and with a
the load-bearing ability of the matrices. Therefore, incorporating fiber thickness of 4–6 mm for subsequent use.
reinforcements presents a promising strategy for improving mechanical
properties, as fibers can provide a robust and continuous backbone for 2.2. Synthesis of MHU resins
the composites.
Bamboo is recognized as one of the most abundant sources of The MHU resin was synthesized using a two-step method based on
biomass owing to its rapid growth and global distribution. The excep­ our recent study [16]. Initially, melamine (M), molten hexamethylene­
tional mechanical properties of bamboo stem from its high content of diamine (H), and NH4Cl (6 % weight percentage of M) were combined in
solid cellulose macrofibres, featuring thick cell walls comprised of a three-necked flask equipped with a magnetic stirrer and an Allihn
aligned semicrystalline lignocellulosic microfibrils [12]. These microfi­ condenser. The molar ratio of M to H was maintained at 1:4. Subse­
brils exhibit exceptional strength with a theoretical tensile strength of quently, the flask was placed in an oil bath and heated to 200 ◦ C, while
5–7.5 GPa [13]. Nevertheless, the macrofibres are embedded within a ammonia gas released during the reaction was absorbed by a water bath
matrix of hollow parenchyma cells, which are significantly less robust trap. After the mixture became clear and transparent, the reaction was
and held together by lignin and hemicelluloses. A recent study showed maintained for additional 2 h. The mixture was then cooled to 80 ◦ C, and
the selective extraction of highly robust macrofibres from natural urea (U) was added to the flask, maintaining the molar ratio of M:H:U at
bamboo by removing the majority of lignin and hemicelluloses. The 1:4:3. The reaction temperature was increased to 120 ◦ C and held for
extracted macrofibres possess a high aspect ratio, with a tensile strength 2–3 h until the mixture viscosity significantly increased. The resulting
of approximately 1.9 GPa and a Young’s modulus of 91.3 ± 29.7 GPa resin, denoted as MHU, was then cooled to room temperature for sub­
[14]. This mechanical strength is comparable to that of synthetic carbon sequent use. Notably, structural characterizations were not repeated in
fiber. Despite the revelation of the excellent mechanical properties of this study, and comprehensive elucidations of MHU polymers can be
delignified bamboo fiber, converting it into bulk engineering materials seen in Ref. [16].
remains a great challenge. One of the obstacles is the inability to weave
delignified bamboo fiber (DBF) like glass and carbon fiber due to its 2.3. Preparation of delignified bamboo fibers
limited length. Although meticulous manual work might be possible, it
is highly inefficient. A peracetic acid solution was prepared by combining H2O2 (30 %)
In the fabrication of polymer-based composites, epoxy resin is pre­ with CH3COOH in a 1:1 vol ratio. Sulfuric acid, constituting 0.5 % of the
dominantly used as the matrix, owing to its advantages such as high total volume of H2O2 and CH3COOH, was incorporated as a catalyst.
mechanical strength and excellent processability [15]. However, its Subsequently, bamboo strips (Bambusa emeiensis) were fully immersed
drawbacks, including high viscosity, intrinsic brittleness (once cured), in the prepared peracetic acid solution. The solution was then heated to
and relatively poor thermal stability, restrict its applications in certain 80 ◦ C and maintained at this temperature for 1–2 h until the bamboo
areas. Specifically, when used with powder fillers, its high viscosity fibers turned white. Subsequently, the lignin-removed bamboo strips
impedes the uniform dispersion of the filler, and the use of toxic diluents were rinsed with deionized water to achieve neutral pH and then dried
raises health and environmental concerns. Recently, our team developed in an oven at 80 ◦ C for future use.
a novel thermosetting polymer synthesized using melamine (M), hex­
amethylenediamine (H), and urea (U) as monomers, employing a 2.4. X-ray diffraction (XRD) characterizations on the bamboo fibers
one-step, solvent-free strategy [16]. The resulting MHU resin exhibited
exceptional mechanical properties (strong and tough) and displayed Rigaku SmartLab SE XRD (Tokyo, Japan) was used to characterize
outstanding adhesion strength towards metals, glass, carbon fibers, and the raw bamboo fiber (RBF), DBF, MHU and MHU-BF. All samples were
wood substrates, indicating excellent interfacial compatibility. More­ grinded into powders before examination. The crystallinity of the sam­
over, the solid MHU resin exhibits good solubility in a water-ethanol ples was calculated by equation (1) [17] under the conditions of Cu as
solvent and possesses low viscosity, allowing for filler immersion. Sub­ the ray source (λ = 1.54406 nm). The scanning range of 2θ was 5–50◦ at
sequently, the solid matrix-filler composite powder can be obtained after scanning speed of 5◦ /min.
solvent removal. During the hot-press process, the melted resin can wet
Crystallinity index, Crt (%) = I002 − Iam /I002 (1)
both the filler and fibrous reinforcement and then undergo curing at
higher temperatures. Employing this approach, a series of hybrid com­ I002 is the maximum diffraction intensity of the 002 plane; The
posites were fabricated in this study using delignified bamboo fiber diffraction intensity at which Iam is 2θ = 18◦ , the diffraction intensity of
(DBF) as reinforcement and walnut shell powder (WSP) as filler. During the amorphous region.
fabrication, WSP and DBF were alternately layered. The resulting hybrid
composites exhibit an attractive wooden appearance, mirror-like gloss, 2.5. 13C CP/MAS nuclear magnetic resonance spectroscopy (13C CP/
and excellent flame retardancy. Notably, the mechanical strength of MAS NMR)
these hybrid composites surpasses that of most commercial or reported
plastics/wood and wood-based composites. Solid-state cross-polarization/magic angle spinning (CP/MAS)
characterization of RBF and DBF was performed using an Agilent 600
2. Materials and methods DD2 spectrometer (Agilent, USA, magnetic field strength 14.1 T).

2.1. Materials 2.5.1. Scanning electron microscopy (SEM) and energy-dispersive

spectroscopy (EDS)
Melamine (M, AR), 1,6-hexanediamine (H, AR), and glacial acetic The morphology of RBF, DBF and hybridized composites was
acid (CH3COOH, AR) were acquired from Chengdu Chron Chemicals analyzed using a Czech TESCAN MIRA LMS scanning electron micro­
Reagent Co., Ltd. Urea (U, AR) and ammonium chloride (NH4Cl, AR), scope at an accelerating voltage of 3 kV. At the same time, the surface
hydrogen peroxide (H2O2) (30 %, wt%), and anhydrous ethanol elemental distributions of the fractured cross sections of the materials
(CH3CH2OH, AR) were obtained from Sinopharm Chemical Reagent Co., were probed using an energy spectrometer (EDS) (OXFORD XPLORE30,
Ltd. Sulfuric acid (H2SO4) was provided by Yunnan Yanglin Shandian UK).

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L. Li et al. Composites Part B 287 (2024) 111857

Fig. 1. The procedures for fabrication of the hybrid composites.

2.6. Preparation of the hybrid composites

Table 1
The compositions of the hybrid compositesa.
The preparation of the hybrid composites involves three main steps:
1) Preparation of MHU-WSP composite powder (CP); 2) Paving of Hybrid MHU/ MHU/ WS/WSP- D-BF/ R–BF/
composite WSP- WSP-BF- BF-MHU WSP-BF- WSP-BF-
bamboo fiber and CP; 3) Hot-press molding of the final composites.
MHU (%) MHU (%) (%) MHU (%) MHU (%)
In the initial step, MHU resin was mixed with an aqueous ethanol
WSP-C-a-1 35 35 65 0 0
solution (with a volume ratio of ethanol to deionized water set at 2.5:1)
WSP-C-a-2 45 45 55 0 0
and heated to 60 ◦ C. Once the MHU resin fully dissolved, this solution RBFb-1 45 38 45 0 17
was blended with walnut shell powder under a magnetic stirrer for 20 RBFb-2 45 35 42 0 23
min. The resulting mixture was then dried in an oven at 120 ◦ C for 1 h to RBFb-3 45 32 40 0 28
remove the solvent. This process resulted in a range of raw composite DBFc-1 35 24 45 31 0
DBFc-2 40 28 41 31 0
powders containing 35 %, 40 %, 45 %, and 50 % MHU by theoretical DBFc-3 45 31 38 31 0
mass fraction, respectively. Subsequently, the raw composite powder DBFc-4 50 34 35 31 0
underwent vacuum oven treatment at 140 ◦ C for 1.5 h under − 0.08 MPa DBFd-1 35 25 47 28 0
to eliminate unreacted monomers and small polymers. After cooling to DBFd-2 40 29 43 28 0
DBFd-3 45 32 40 28 0
room temperature, the mixture was ground into composite powder.
DBFd-4 50 36 36 28 0
In the second step, the composite powder and bamboo fibers (RBF or DBFe− 1 35 26 49 25 0
DBF) were layered alternately in a size 120 mm × 120 mm × 12 mm DBFe− 2 40 30 45 25 0
stainless-steel mold. As shown in Fig. 1, fibers were paved in five layers DBFe− 3 45 34 41 25 0
in cross-ply (0◦ /90◦ ) orientations between the powder layers. Subse­ DBFe− 4 50 38 37 25 0

quently, the mold, with a cover, was placed in a hot-pressing machine a

WSP-C (Fiber-free), RBF-HC (RBF-reinforced) and DBF-HC (DBF-reinforced)
and preheated at 120 ◦ C for 30 min under no applied pressure. The composites.
pressure was then gradually increased to 4 MPa in steps. At each 1 MPa
increment, the hot-press was maintained for 30 min, with intermittent

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L. Li et al. Composites Part B 287 (2024) 111857

Fig. 2. Characterizations for RBF, DBF and MHU：(a) Comparison of the appearance between RBF and DBF; (b) XRD spectra for RBF, DBF, MHU and MHU-DBF; (c)
13
C CP/MAS NMR spectra of DBF and RBF.

decompressions to release any gas produced. When the pressure reached 2.9. Acid and alkali resistance test
4.0 MPa, hot-pressing at 160 ◦ C was sustained for 6 h. After cooling to
room temperature, the final composite was obtained. Additionally, The samples were immersed in 10 % (wt%) HCl and 10 % (wt%)
composites without bamboo fibers were prepared for comparison. NaOH solutions for 24 h and then the samples were rinsed with deion­
Following this procedure, various composites were prepared by ized water. After wiping away the residue water, the weight change and
altering the fiber fractions in the total weight of the composite. The exact thickness expansion rate of the samples were calculated.
mass fractions of MHU, WSP, and fiber in the total weight of the final
composites were calculated and are listed in Table 1. 2.10. Dynamic mechanical analysis (DMA)

Thermomechanical properties of the hybrid composites (10 mm ×

2.7. The Shore D hardness measurements
50 mm × 4 mm) were analyzed using DMA Q800 instrument (TA In­
struments, USA) with a temperature range of 50–250 ◦ C at a heating rate
The hardness tests of WS, MHU, WSP-C and DBF-HC surfaces were
of 5 ◦ C/min and a deformation amplitude of 60 μm.
carried out using Shore Hardness Tester (Yueqing Handpi Instrument
Co., Ltd., China). 5 samples were tested in each group and the average
value was taken. 2.11. Heat deflection temperature (HDT)

According to GB/T1634.3–2004, the under-load thermal mechanical

2.8. Water resistance tests behaviors of the hybrid composites (10 mm × 80 mm × 4 mm) was
tested by HT-8802-BA (Hangzhou Jinmai Instrument Co., LTD, Hang­
The water resistance tests were carried out by referring to the stan­ zhou, China) Vicat instrument with a load of 1.8 MPa and a heating rate
dard ASTM D570-22. After soaking the samples in distilled water at 23 of 2 ◦ C/min.
± 1 ◦ C for 24 h, the water absorption rate (Wa, %) and the thickness
swelling (Ts, %) were calculated by Eqs (2) and (3): 2.12. Flame retardancy tests
Wa = (m2 − m1 ) / m1 × 100% (2)
The flammability of the composites was measured by referring to
Ts = (h2 − h1 ) / h1 × 100% (3) vertical burning test method described in standard ASTM D3801.

where m1 is the mass of the sample before immersion (g); m2 is the mass 2.13. Conical calorimetry
of the sample after immersion (g); h1 is the thickness of the sample
before immersion (mm); h2 is the thickness of the specimen after im­ Cone calorimeter tests (CCT, VOUCH 6810) were carried out on the
mersion (mm). basis of the ISO 5660-1 standard. The sample size was 100 mm × 100

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L. Li et al. Composites Part B 287 (2024) 111857

Fig. 3. SEM characterizations for bamboo fiber: (a) images for RBF; (b) images for DBF; (c) images for the cross-section of DBF containing cured MHU resin.

mm × 4 mm and the selected external heat flux was 35 kW/m2. to the load increment ΔP.

2.14. Mechanical strength tests for the hybrid composites

2.15. Fluorescence observation
The HK-316 servo tensile testing machine (purchased from Dong­
The MHU, WSP, CP powders and the final composites were irradiated
guan Huakai Testing Equipment Co., Ltd., China) was used to test the
by a 365 nm UV light and the pictures were recorded using an iPhone 14
mechanical properties of the hybrid composites. For each type, at least 5
Pro Max.
samples were tested and mean and standard deviation were calculated.
According to ASTM D790-03, the flexural strength of the composites was
tested at room temperature, and the three-point bending test was carried 3. Results and discussion
out at a speed of 1 mm min− 1. The maximum flexural strength (FS ),
strain to failure (εf ) and flexural modulus (Ef ) was calculated by using 3.1. The hybrid composites design and fabrication strategy
Eqs (4)–(6):
/ Fig. 1 illustrates the design and fabrication strategy for the hybrid
FS = 3PL 2bh2 (4) composites. Leveraging the solid state of MHU resin at room tempera­
/ ture and its excellent solubility in water-ethanol solutions, a solid
εf = 6Sh L2 (5) composite powder (CP) consisting of WSP and MHU was formed through
a sequence of mixing, solvent removal, and vacuum treatment. This
/
Ef = L3 ΔP 4bh3 ΔS (6) approach enables the fabrication of the final composites to be conducted
under dry conditions, and the composite powder can be conveniently
where P is the peak load (N); L is the support span length (mm); b is the stored separately, reflecting a distinguishing technique within this work.
specimen width (mm); h is the thickness of the specimen (mm); S is the Such a procedure is unfeasible for conventional formaldehyde-based
deflection at the midpoint of the span of the pattern; ΔP is the load thermosets (e.g., urea-formaldehyde and phenol-formaldehyde resins)
increment of the initial straight segment on the load-deflection curve; Δ due to premature curing during solvent removal and vacuum treatment
S is the deflection increment at the midpoint of the span corresponding at elevated temperatures.

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L. Li et al. Composites Part B 287 (2024) 111857

Fig. 4. (a) The appearances and processibility of the hybrid composite; (b) Comparison of surface hardness between hardness the hybrid composite and some re­
ported biomass reinforced composites.

Utilizing the delignification method developed by Hu et al. [14],

Table 2
original bamboo culms, ranging from 40 to 60 cm in length (depending
The apparent density and water resistance test results.
on the distance between two joints), can be directly treated. However,
for this study, peroxyacetic acid was utilized instead of peroxyboric acid. Hybrid Apparent density Thickness swelling Water absorption
composite (g/cm3) (%) (%)
This decision stemmed from the fact that delignification in a peroxyboric
acid solution at mild conditions (approximately 50 ◦ C) requires 12 h or WSP-C-a-1 1.28 3.29 5.64
WSP-C-a-2 1.27 2.05 2.78
longer, while higher temperatures (around 80 ◦ C) result in a violent
RBFb-1 1.28 3.65 3.79
reaction. Conversely, the use of peroxyacetic acid solution allowed RBFb-2 1.27 4.74 5.05
delignification to be completed within 2.0 h, yielding high-quality RBFb-3 1.22 4.80 7.40
macrofibres ranging from 30 to 50 cm in length. In Fig. 2(a), the DBFd-1 1.30 6.16 6.31
appearance of RBF was compared to that of the DBF. Evidently, at the DBFd-2 1.30 4.81 5.27
DBFd-3 1.33 3.75 4.94
same weight, the DBF exhibited smaller volume, more uniform size, and
DBFd-4 1.31 2.04 3.34
appeared denser than the RBF, attributed to the delignification process.
To investigate the potential impact of delignification and the fiber-resin
interaction on crystallinity, XRD characterizations were conducted. The macrofibres composed of densely packed microfibrils intact. This
results, presented in Fig. 2(b), indicate that the delignified fiber (DBF) outcome is similar to the findings of Hu’s study [14], in which perox­
exhibited 11 % higher crystallinity than the untreated fibers (RBF), yboric acid was utilized. Fig. 3(c) illustrates the SEM images of the fibers
suggesting that a portion of amorphous microfibrils tend to crystallize immersed in an MHU solution and cured at 140 ◦ C. The cross-section of
after lignin removal. Furthermore, the DBF containing cured resins the fibers clearly reveals that the resin has penetrated the fibers and
(MHU-DBF) displayed similar crystallinity to delignified fibers, implying filled most of the gaps between the macrofibres.
that the resin-fiber interaction did not significantly affect crystallinity.
The solid-state NMR spectra of RBF and DBF, depicted in Fig. 2(c),
3.2. Basic properties of the hybrid composites
indicate that the broad peaks at 124–158 and 59 ppm in the RBF spec­
trum, representing aromatic carbons and methoxy of lignin, largely
Fig. 4(a) depicts the appearance of the final composites. Surprisingly,
diminished in the DBF spectrum, suggesting the substantial removal of
the panel surface appeared dark and possessed a slight gloss, contrary to
lignin. Furthermore, the signals at 24 and 174 ppm corresponding to the
expectations. The dark color may be attributed to the reaction between
characteristic carbons of hemicellulose weakened or disappeared, indi­
MHU resin and the reductive carbohydrates in walnut powder, specif­
cating potential removal of a portion of hemicellulose. Conversely, the
ically the Maillard reaction [18] or Aldehyde-Amine reaction, which
characteristic signals of cellulose in the C1–C6 regions remained robust,
generates dark reaction products. Following careful polishing, the panel
indicating that cellulose was not degraded during the delignification
exhibited an attractive mirror-like gloss, rendering it promising for
process. This observation aligns with the findings of the XRD tests.
house decoration or as a material for furniture manufacturing. Pro­
The differences at a microscopic level can be further supported by the
cessability tests revealed that the composites can be drilled or cut into
SEM examination. Fig. 3(a) displays the SEM images of the untreated
different shapes. Notably, the material exhibited high surface hardness.
fibers, which exhibit highly aligned macrofibres that were separated by
As illustrated in Fig. 4(b), driving a steel nail into the panel proved
hollow parenchyma cells. After treatment with peroxyacetic acid (Fig. 3
difficult. Shore D Hardness tests indicated high hardness for both MHU
(b)), the parenchyma cells were almost eliminated, leaving the
and WS, measuring at 83 and 75, respectively. The combination of these

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Fig. 5. Acid and alkali resistance tests. Photos of the appearance of DBFd-3 composite samples before (a), during (b) and after (c) immersion in the acid and alkali
solution, respectively; (d) Thickness swelling and mass change of hybrid composites after acid and alkali resistance testing.

components conferred the materials with a higher hardness (>90), the MHU resin, while the matrices (PE, PP, and PVC) used in WPC are
surpassing that of most reported biomass-reinforced polymer compos­ highly hydrophobic. Another contributing factor is the use of bamboo
ites [19–25]. fiber, which contains highly hydrophilic microfibrils composed of cel­
The apparent densities of the composites in Table 2 fall within the lulose. To further enhance the water resistance of the hybrid composites,
range of 1.22–1.30 g/cm3, similar to certain commercial wood-plastic edge-sealing treatment can be considered.
composites (WPC). Owing to their relatively high density and the pro­ To investigate the durability of the composites in acid and alkali
tective quality of MHU resin, the composites exhibit excellent water environment, the specimens cut from DBFd-3 were soaked in 10 % (wt
resistance, with thickness swelling rates (Ts) ranging from 2 to 6%. This %) HCl and NaOH solution for 24 h. It can be seen from the appearances
is lower than those of typical wood-based composites such as fiberboard of the samples before, during and after soaking shown Fig. 5(a)–(c), that
(5–20 %, ISO 16983) and particle board (≤12 %, JIS A 5908-2003). It is the humid acid or alkali environment did not cause serious corrosion to
worth noting that a higher resin content corresponds to improved water the surfaces. Note that the HCl solution in which the samples were
resistance. Furthermore, fiber-free composites (WSP–C-a-1 and WSP-C- soaked remained colorless, suggesting HCl did not lead to decomposi­
a-2) demonstrate superior water resistance compared to fiber-included tion of the components. The NaOH solution appeared to be faint yellow,
composites. A similar trend is observed for water absorption rates. which could be attributed to hydrolysis of the lignin of WS in alkali
Surely, the water resistance of the hybrid composites is slightly inferior condition. The results in Fig. 5(d) showed 6–7% weight increase for the
to that of wood-plastic composites, which typically have a 72 h Ts of less soaked samples which is slightly higher than the water absorption rate of
than 3 %. This can be attributed to the somewhat hydrophilic nature of 4.94 % (Table 2). Correspondingly, the thickness swelling rate of

Fig. 6. (a) The DMA results for DBFd-3 composite; (b) The HDT test result for DBFd-3 composite.

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Fig. 7. (a) The flame retardancy test results for DBFd-4: (a)–(b) the vertical burning tests; (c)–(f) CCT test results; (g) The proposed mechanism for flame retardancy.

6.5–7.5 % is also higher than that of water-soaking samples. These governed by the Tg, the heat deflection temperature (HDT) plays a
changes caused by HCl and NaOH should be attributed to different crucial role in determining the working temperature of a reinforced
mechanisms. As residue amino groups may remained in the cured MHU, composite due to the interaction between the matrix and reinforcement.
a portion of HCl that penetrate MHU could have reacted with them and Fig. 6(b) illustrates a significant decrease in deflection starting at
formed salt which were not rinsed out. As for NaOH, it is a well-known approximately 210 ◦ C, which is considerably higher than the Tg. This
agent that is commonly used for cellulose solution preparation because suggests that the composite’s short-term service temperature is at least
it can penetrate cellulose chains and therefore swell the fibers. Never­ around 200 ◦ C.
theless, the changes of weight and thickness smaller than 8 % suggested As flame retardancy is crucial for engineering materials, in this
satisfied acid and alkali durability of the composite. study, the hybrid composites were subjected to the vertical burning test
DMA analysis provides insights into the thermal mechanical prop­ method described in ASTM D3801. Fig. 7(a) and (b) depict the results for
erties of a polymer composite’s matrix. Fig. 6(a) depicts the DMA out­ two selected samples, DBFd-4 and DBFe− 4, which have the MHU resin
comes for the selected representative composite DBFd-3. The storage contents of 36 % and 38 %, and fiber contents of 28 % and 25 %,
modulus curve exhibits a rapid decline in modulus starting at approxi­ respectively. Both samples ceased burning within 10 s of flame with­
mately 90 ◦ C. The peak value of the loss factor indicates that the matrix’s drawal. However, during the second ignition, DBFd-4 continued to burn
glass transition temperature (Tg) is around 117 ◦ C, which is lower than after the flame was withdrawn, while DBFe− 4 immediately stopped
the previously determined Tg for neat MHU resin (134 ◦ C) [16]. While burning, emitting only minimal smoke. These findings confirm that
the service temperature of neat polymeric materials is primarily DBFe− 4 meets the UL94-V0 grade for flame retardancy.

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Table 3 flame retardants, and even lower than that of the materials using
Comparison of pHRR of DBFe− 4 with that of some recently reported biomass- MMT/ZnMPA, TEF/PEG flame retardants. To better understand the fire
based composites. safety of the DBF-HC composite, a retardancy mechanism was proposed
Year Sample Flame retardant pHRR Ref in Fig. 7(g). In such mechanism, use of the MHU matrix that contains
(kW/m2) retardant units (melamine) plays a crucial role.
2022 WPC/ Phytic acid-tyramine salt (PATA) 415 [26]
PATA 3.3. Mechanical properties of the hybrid composites
2023 22%WPC Intumesce flame retardant (IFR) 407.1 [27]
2024 WF/ 2D/2D montmorillonite/Zn2+- 443.1 [28]
PPMZ-5 melamine-phytic acid (MMT/ Fig. 8 presents the results of the flexural and tensile strength tests
ZnMPA) conducted on the RBF reinforced composites. The RBFb-2 composite,
2024 TW/PEG/ Triethyl phosphate (TEP) and 640.96 [29] comprising 35 % MHU, 42 % WS, and 23 % RBF, exhibited the highest
TEP polyethylene glycol (PEG) average flexural strength of 75.47 MPa as depicted in Fig. 8(a) and (b).
2024 DBFe− 4 No extra additions 417.68 This
work
In contrast, the RBFb-3 composite, characterized by the lowest MHU
content (32 %) and the highest RBF content (28 %), demonstrated the
lowest strength of 67.46 MPa. The flexural modulus followed a similar
To further evaluate the fire safety of the composites, the burning trend. Therefore, the strength of a composite is not solely determined by
property of DBFe− 4 was analyzed using a cone calorimeter. It can be its fiber content; the content of matrix resin also plays a crucial role in
seen from Fig. 7(c), that the material has a high ignition threshold with a terms of adhesion and load transfer. Insufficient matrix content weak­
time to ignition of 161 s, which could be attributed to the high ther­ ened the adhesion between the fillers and the reinforcement, resulting in
mostability of MHU matrix. It can be seen from the heat release rate a reduced contribution of the fillers to flexural strength. The stress-strain
(HRR) curve, that the material has two exothermic peaks, the first peak curves in Fig. 8(b) indicate the occurrence of jagged load fluctuations
was generated by the partial decomposition and combustion of the during tensile tests. This phenomenon can be attributed to the step-wise
matrix resin MHU, with a peak heat release rate (pHRR) of 417.68 kW/ or intermittent failure of layered bamboo fibers. As shown in Fig. 8(c)–
m2. The second peak was much smaller than the first peak, which is (d), in contrast to flexural strength, tensile strength was highly influ­
mainly due to the released inert gases (from decomposition of mel­ enced by fiber content, with RBb-3 exhibiting significantly higher tensile
amine) which diluted the flammable gases around the sample. More­ strength compared to the other two composites. These findings imply
over, thermal decomposition of MHU formed a stabilized carbon layer that achieving the desired mechanical properties necessitates meticu­
which has a shielding effect. The high density of WSP is also help for lous structural design, which relies on an optimized composition for a
combustion delay. Fig. 7 (d) and (e) show that the total heat release hybrid composite consisting of three components.
(THR) of DBFe− 4 was measured to be 104.65 MJ/m2 while the smoke Fig. 9(a)–(c) display the results of the flexural strength tests con­
production was only 0.036 m2/s. The photo in Fig. 7(f) indicates that the ducted on the composites reinforced with delignified bamboo fibers. As
residual carbon of DBFe− 4 was well preserved and structurally intact. the MHU content in the composite powder increased from 35 % to 45 %,
To further evaluate the fire safety of DBF-HC composites, the pHRR of the strengths of the three groups of composites significantly rose from
DBFe− 4 was compared in Table 3 with that of those recently reported 80 MPa to 188–222 MPa. However, the use of composite powder con­
wood-plastic composites [26–28] and biomass-based composites [29], taining 50 % MHU did not lead to any further increase in strength,
which involved various additional flame retardants. With no any addi­ instead, a slight decrease was observed. A similar trend was noticed for
tional flame retardants added, the pHRR value of the DBFe− 4 composite the flexural modulus as well. These results reinforce the significance of
is comparable to that of the materials with the addition of PAPA, IFR an appropriate amount of matrix MHU resin for achieving high flexural

Fig. 8. The mechanical strength of the RBF-reinforced hybrid composites: (a) The flexural strength and modulus; (b) The stress-strain curves for the samples in
flexural strength tests; (c) The tensile strength and modulus; (d) The stress-strain curves for the samples in tensile strength tests.

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L. Li et al. Composites Part B 287 (2024) 111857

Fig. 9. The flexural strength tests for delignified bamboo fiber reinforced hybrid composites: (a) The camera image for a sample in flexural strength test; (b) The
flexural strength; (c) The flexural modulus; (d) The stress-strain curves for the samples in flexural tests.

Fig. 10. Comparison of mechanical strengths between fiber-free (WSP–C), RBF-reinforced (RBF-HC) and DBF-reinforced (DBF-HC) composites: (a) The flexural
strength and modulus; (b) The flexural stress-strain curves; (c) The tensile strength and modulus; (d) The tensile stress-strain curves.

strength. Among all the composites, the DBFd-3 group, which consisted increase in strain (small slope), which aligns with the satisfactory
of 28 % delignified fiber, exhibited the highest strength. This finding toughness demonstrated in Fig. 9(a).
emphasizes that the highest fiber content does not necessarily corre­ To highlight the reinforcing effects of bamboo fiber, we compared
spond to the highest flexural strength. The strain-stress curves presented the mechanical strengths of composites without fiber, composites rein­
in Fig. 9 (d) indicate a relatively gradual increase in stress with an forced with representative RBF, and composites reinforced with DBF in

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Fig. 11. Comparison of flexural strength (a) and modulus (b) between the hybrid composites and wood-based [30–39], wood-plastic composites [40–43], as well as
some natural wood [44].

Fig. 12. (a) Camera image of a fractured specimen in tensile test; (b) SEM image of the fractured cross-section; (c) SEM image of a pulled-out fiber; (d) SEM-EDS
images of the matrix-filler phase; (e) SEM-EDS images of the pulled-out fiber.

Fig. 10(a) and (b) show the contrasting flexural strengths and stress- after removing the loose and hollow parenchyma cells. Lastly, the
strain curves, respectively. The strength and modulus of the DBF rein­ absence of parenchyma cells allows for easier densification of the
forced composite are 3–4 and 4–6 times higher than those of the fiber- macrofibres through hot-pressing.
free and RBF reinforced composites, respectively. Fig. 10(c) also dem­ Fig. 11 compares the flexural strength and modulus of the hybrid
onstrates the significant advantages of DBF reinforced composites in composites with those of wood-based composites [30–39], wood/plastic
terms of tensile strength and modulus. Notably, Fig. 10(d) reveals that composites [40–43], and some natural wood [44]. Currently, the flex­
the DBF reinforced composites have a tensile strain (elongation rate at ural strength of most wood-based composites (commercialized or re­
break) of approximately 6 %, which is much higher than that of the ported) is below 50 MPa, which is why they are generally unsuitable for
fiber-free (2–2.5 %) and RBF reinforced composites (3.5 %). This in­ structural materials. Among wood/plastic composites, only fiberboard
dicates the significantly greater toughness of DBF reinforced composites. exhibits strength above 76 MPa. Certain species of natural wood, such as
Evidently, delignification of bamboo fiber is a highly efficient method Cathaya argyrophylla Chun et Kuang and Dalbergia hupeana Hance, with
for unlocking its potential. Three aspects can explain the remarkable high density, possess flexural strength above 140 MPa. In contrast, the
enhancement effects of delignification. Firstly, removing lignin in­ hybrid composites fabricated in this study demonstrate significantly
creases the effective strength per unit volume or weight of bamboo fiber. higher strength (>220 MPa), highlighting the success of the reinforcing
In other words, the delignified fiber has much higher strength than the strategy using delignified bamboo fiber. Their high flexural modulus
raw fiber when comparing the same volume or weight. Secondly, the (>15 GPa), comparable to that of high-density hardwood, makes them
fiber-fiber and fiber-filler adhesion strength can be greatly improved highly suitable for load-bearing structural materials, particularly for use

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L. Li et al. Composites Part B 287 (2024) 111857

Fig. 13. The fluorescent property of the hybrid composite: (a) The appearances of the MHU, WSP and CP powders under daylight and 365 nm UV irradiation; (b) The
appearances of the composite surface under daylight and UV irradiation; (c) Demonstration of the fluorescence-based self-anticounterfeiting function of the
hybrid composite.

in building and construction applications. compound [45]. Interestingly, the corneous walnut shell powder
Fig. 12(a) shows the image of a failed specimen in tensile strength exhibited grey-blue fluorescence, which is likely caused by the excita­
test. Clearly, the majority of the fibers were fractured when they were tion of a natural luminescent compound present in walnut shell. More
partially pulled out, indicating high bonding strength between matrix intriguingly, the composite of MHU and WSP generated a silvery-grey
and fibers. The presence of exposed fibers suggests that the failure of the fluorescence in the composite powder (CP). Consequently, the surface
matrix phase occurred prior to the failure of the fibers. The SEM image of of the composite panel (Fig. 13(b)) also exhibited silvery-grey fluores­
the fractured cross section (Fig. 12(b)) reveals that the fibers aligned cence. This interesting property has potential applications in anticoun­
along the load direction (longitudinal) were broken, while the trans­ terfeiting measures. Since the MHU resin is a phosphor, its solution can
versal fibers remained intact. Fig.12 (c) shows the SEM image of a be used as fluorescent ink. Therefore, we designed a simple
fractured fiber in which the macrofibres were firmly tight by the MHU anti-counterfeiting logo and applied it to the surface of the composite
matrix. The area circled in yellow for matrix-filler phase was magnified board. Under UV irradiation, the blue logo is clearly visible against the
in Fig. 12 (d). The highly rough surface is consistent with the excellent silvery-grey background. Thus, the hybrid composite developed in this
toughness previously observed in the MHU resin [16]. To demonstrate study possesses self-anticounterfeiting functionality. Furthermore, the
the homogeneity of the distribution of the MHU matrix and filler, EDS fluorescent property of the composite material may be applied to the
analysis was performed. The elements C, N, and O uniformly distributed anticounterfeiting of other products, as the silvery-grey fluorescence is
in this phase, especially the N element from MHU distributed in the same unique and indeed very rare.
pattern as O from WSP，suggesting the filler was evenly dispersed in the
matrix. Similarly, the fiber image magnified from the area circled in red 4. Conclusions
(Fig.12 (c)) and corresponding elemental map in Fig.12 (e) confirmed
the uniform distribution of MHU on fiber surface. In this study, biomass-based hybrid composites were fabricated by
combining partially delignified bamboo fiber (DBF) and walnut shell
3.4. The fluorescent property of the hybrid composite powder (WSP) with melamine-hexamethylenediamine-urea (MHU)
thermosetting resin. In these composites, DBF served as the fiber rein­
It is fascinating and unexpected that the composite’s brown or dark forcement while WSP acted as the filler. The composites exhibited
surface appears silvery-grey under 365 nm UV irradiation. This is a clear excellent processability, mechanical strength, flame retardancy, and
indication of fluorescence. In order to understand this property, we also intriguing fluorescent properties. The primary conclusions are as
examined the MHU resin powder, WSP, and the composite powder follows.
under 365 nm UV light. The appearance of these materials under
daylight and UV light can be seen in Fig. 13(a). The blue fluorescence of 1) The combination of MHU with WSP imparted high surface hardness
the MHU resin is attributed to melamine, a well-known fluorescent to the composites. The Shore D Hardness exceeding 90 surpassed that

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The authors declare that they have no known competing financial kenaf/jute fabric hybrid laminated microwave-processed composites. J Ind Text
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the work reported in this paper.
powder in the basalt fiber reinforced polyethylene hybrid composites: a sustainable
approach towards green composites. Polym Compos 2023;44:3952–63. https://
Data availability doi.org/10.1002/pc.27368.
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[22] Hariprasad K, Ravichandran K, Jayaseelan V, Muthuramalingam T. Acoustic and
Acknowledgments mechanical characterisation of polypropylene composites reinforced by natural
fibres for automotive applications. J Mater Res Technol-JMRT 2020;9:14029–35.
This work was supported by the Agriculture Joint Research Program https://doi.org/10.1016/j.jmrt.2020.09.112.
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