BioRecourses1423651 36672019
BioRecourses1423651 36672019
BioRecourses1423651 36672019
net/publication/337029705
European Pallets Fabricated with Composite Wood Blocks from Tropical Species
Reinforced with Nanocrystalline Cellulose: Effects on the Properties of Blocks
and Static Flexure of th...
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Contact information: a: Escuela de Ingeniería Forestal, Instituto Tecnológico de Costa Rica [Costa Rica
Tech], Cartago, Costa Rica, P.O. Box 159-7050; b: Laboratorio Nacional Nanotecnología (LANOTEC)
[National Laboratory of Nanotechnology], Centro Nacional de Alta Tecnología (CeNAT), San José, Costa
Rica; c: Escuela de Ingeniería en Construcción [Costa Rica Tech], Instituto Tecnológico de Costa Rica,
Cartago, Costa Rica; *Corresponding author: rmoya@itcr.ac.cr
INTRODUCTION
Cellulose is the most abundant organic compound on the planet (Thakur et al.
2013). It is a naturally formed polymer in all plants, together with other important
components such as lignin, hemicelluloses, and waxes (Li et al. 2009). Cellulose can be
found all over a plant, although it is mostly concentrated in the stem (Lavoine et al. 2012)
to support the plant (Morán et al. 2008).
As a renewable material, and because of its physical and chemical characteristics,
cellulose has been of great interest for manufacturing over the last decade (Poletto et al.
2014). With dimensions of 20 nm in diameter and 100 nm to 400 nm in length,
nanocrystalline cellulose (NCC) can be obtained from cellulose (Morán et al. 2008).
Alternatively, microfibrillated cellulose (MFC) can be prepared by mechanical treatment,
often supplemented by chemical or enzymatic treatments. Both MFC and NCC have been
studied and used as reinforcements and filling in various polymers (Poletto et al. 2014;
EXPERIMENTAL
Materials
The NCC was provided by the Laboratorio Nacional de Nanotecnología
(LANOTEC, San José, Costa Rica). It was extracted from pineapple (Ananas comosus)
peel through a two-stage acid hydrolysis process. The NCC sizes were between 20 nm and
40 nm in diameter, and its concentration was 0.066 g·mL-1. The details of the extraction
and characterization can be found in Camacho et al. (2017) and Rigg-Aguilar et al. (2019).
Two adhesive types were employed: polyvinyl acetate (PVAc) and urea
formaldehyde (UF). The PVAc (Resistol™ MR 850; Henkel, Düsseldorf, Germany)
technical product description indicates that the resin is water-based PVAc, with 54.5% to
55% solid contents and a viscosity between 1.6 Pa.s and 2.0 Pa.s. The UF (Resina CR-560
U-F; Química Centroamericana, Quibor, S.A., Managua, Nicaragua) is also water-based,
with four components: resin (51%), water (26%), wheat flour as agglutinant (20%), and
ammonium sulfate as catalyzer (3%). The technical description indicates that the pure resin
contains 64% to 65% solid contents and has a viscosity of 650 cP to 900 cP. The total solid
content of the complete adhesive with the four components is 48%.
The wood used to evaluate the effects of nanocellulose in the two adhesives came
from three tropical plantation species in Costa Rica: Gmelina arborea Roxb. (melina),
Vochysia ferruginea Mart. (botarrama), and Cordia alliodora Ruiz & Pav. (laurel). These
three are commonly used for pallet fabrication (Barrantas and Ugalde 2017) and are
commercially prevalent in Costa Rica (Tenorio et al. 2016).
The wood utilized came from plantations with ages ranging between 7 y and 9 y.
The C. alliodora came from CATIE-Turrialba (09° 53’ 00” N, 83° 38’ 01” W, 602 m a.s.l.,
9-years-old), the G. arborea came from Bonifacio, Limón (09° 46’ 43” N, 82° 54’ 59” W,
42 m a.s.l., 8-years-old), and the V. ferruginea came from Búfalo, Limón (10° 00’ 21” N,
83° 10’ 23” W, 25 m a.s.l., 7-years-old). Approximately 7 to 8 trees per species were felled.
For the pallets fabricated with solid wood, the G. arborea was utilized.
CWB manufacturing
The CWB were 10 cm × 10 cm × 10 cm, and were composed of wood particles
from V. ferruginea, C. alliodora, and G. arborea, employing the NCC-modified adhesive.
First, chips were obtained from 60 logs (1-m-long and of varying diameter) of the three
species. The chips were ground, and the material was sieved to obtain sizes between 3 mm
and 10 mm, with moisture contents between 2% and 4%.
Next, 550 g of dry particles were mixed with 100 g of NCC-modified adhesive
(18% of total chip weight) for UF and 66 g (12% of total chip weight) for PVAc. The
adhesive was slowly added to the particles while stirring over 4 min. The glued particles
were placed into a mold and pressed for 5 min with a 60 ton capacity universal testing
machine (model: Super L60; Tinius Olsen, Horsham, PA, USA). The mold was then heated
to 180 °C, while the pressure was applied for 60 min to 75 min to obtain the CWB. Lastly,
the CWB were conditioned to a 12% moisture content for two weeks.
A total of 72 CWB (2 adhesives × 2 concentrations (1% and 0%) × 9 blocks per
pallet × 2 samples) were fabricated to manufacture the pallets for each species, with the
same number of blocks (2 adhesives × 2 concentrations (1% and 0%) × 9 blocks per pallet
× 2 samples) to perform the tests with the composite wood with the modified adhesive.
Methods
Internal bond and perpendicular tension resistance in CWB
A total of five different CWB fabricated with the two adhesives and modified with
1% NCC were cut according to Fig. 2c, obtaining four samples of 5 cm × 5 cm × 10 cm
per block. Thus, 20 samples per treatment were obtained (two adhesives: NCC-modified
and NCC-unmodified). The internal bond test was performed in accordance with the
ASTM D1037-12 (2018) standard. The bonding strength of the CWB was compared with
the grain-perpendicular tension strength of the SWB (Fig. 1d). For this purpose, SWB in
green condition for European pallets were obtained from Maderas Bosque Verde S.A.
(Cartago, Costa Rica). The SWB were cut according to Fig. 1b, and eight samples of 5 cm
Water absorption
Samples sized 5 cm × 5 cm × 2.54 cm were obtained from the five conditioned
CWB per treatment (Fig. 1e). The samples were vertically placed into trays with water
covering the bottom up to 2.54 cm for 24 h, in accordance with the ASTM D1037-12 (2018)
standard. The weight was recorded before placement into water and after 24 h. Water
absorption was calculated for each of the samples according to the ratio of the weight of
the water absorbed to the weight of the sample before the absorption test, and expressed as
a percentage.
Pallet fabrication
The pallets were fabricated at Maderas Bosque Verde S.A. (Cartago, Costa Rica).
The European pallets were 1.10-m-long, 0.98-m-wide, and 0.15-m-high (Fig. 1a). The
upper boards were 10.1-cm-wide and 1.8-cm-thick; seven boards were placed. In both
cases, G. arborea was utilized. The pallets were nailed employing a 6 bar pressure
pneumatic pistol (Unicorn Fasteners Co., Ltd., Tianjin, China), 2 nails per board (5-cm-
long, 12.5 caliber, and 32º angle spiral). The lower side of the pallet featured three G.
arborea boards supporting the blocks and three boards perpendicular to the first three,
measuring 8.3-cm-wide and 1.8-cm-thick. Each block was nailed with two nails to the
lower boards.
Fig. 1. (a) Dimensions and aspect of the pallet fabricated with composite wood; (b) pallet flexural
test; cutting patterns to obtain the samples for tests: (c) internal bond, (d) perpendicular tension in
SWB, and (e) water absorption
Statistical analysis
Assumptions of normal data distribution were evaluated by the Shapiro–Wilk test,
with the variance homogeneity evaluated by Levene’s test and the InfoStat software
(InfoStat Company, version 2017, Buenos Aires, Argentina). Then, to determine
differences among the means of the tests, an analysis of variance (ANOVA) test was
applied, where the tests performed were the response variables, and the NCC concentration
was the independent variable. Then, this analysis was accompanied by the Tukey test at
99% reliability to determine the differences between both NCC concentrations within the
species per adhesive. As the internal bond and water absorption tests did not meet the
assumptions, non-parametric tests were used: the Kruskal–Wallis test to determine
differences between NCC concentrations and Steel’s test to compare the CWB with the
control (SWB).
CWB with PVAc 0.0 0.06B (0.028) 251.5B (27.25) 246.9B (71.0) 82.7B (25.6) 9.28 0.55
C. alliodora adhesive 1.0 0.06B (0.013) 240.8B (17.99) 393.5A (96.5) 131.1B (21.0) 8.19 0.57
CWB with UF 0.0 0.05A (0.030) 120.0A (9.43) 464.1A (114.3) 285.6B (63.7) 10.20 0.60
adhesive 1.0 0.22B (0.058) 164.1B (17.96) 308.0AB (57.0) 192.3AB (49.4) 7.47 0.61
SWB 2.00A (0.654) 64.9A (14.07) 437.3A (125.4) 222.5A (72.3) 40.87 0.39
CWB with PVAc 0.0 0.01B (0.003) 151.6B (31.88) 107.3B (36.6) 40.2B (12.4) 11.00 0.56
G. arborea adhesive 1.0 0.03B (0.009) 176.7B (27.26) 154.5B (38.2) 65.7B (20.4) 7.88 0.58
CWB with UF 0.0 0.10B (0.032) 67.5AB (3.81) 251.0B (48.7) 186.7A (47.4) 10.83 0.62
adhesive 1.0 0.45A
(0.064) 100.6B
(8.70) 223.6B
(56.3) 173.5A
(43.5) 8.24 0.63
Values in parentheses represent standard deviations; average values identified with different letters are statistically different at α = 0.01%
Rigg-Aguilar et al. (2019). “Composite blocks and nanocellulose,” BioResources 14(2), 3651-3667. 3657
PEER-REVIEWED ARTICLE bioresources.com
In contrast, in the CWB fabricated with UF adhesive and modified with 1% NCC,
the internal bond resistance increased significantly in relation to the CWB fabricated with
unmodified adhesive (Table 1).
Meanwhile, the analysis between NCC concentrations of the CWB for each species
per adhesive showed that, for C. alliodora and G. arborea with PVAc adhesive, nail
extraction resistance increased in both sections with 1% NCC, which was statistically
different only for the lateral section in C. alliodora (Table 1). In the rest of the cases, neither
reinforcement from NCC nor statistical differences were observed in most of the
comparisons.
The CWB of V. ferruginea and C. alliodora glued with 1% NCC presented
resistances to nail extraction that were statistically equivalent to SWB of V. ferruginea and
C. alliodora, both laterally and transversely, with the exception CWB with 1% NCC of C.
alliodora, which had a lower transverse resistance than the SWB (Table 1). However, there
was a slight increase in the resistance to nail extraction in the CWB without NCC with both
types of adhesives, but this increasing was not statistically significant. There were
exceptions, where CWB with PVAc adhesive without NCC had statistically lower lateral
and transverse resistances than the SWB for C. alliodora, as well as lower lateral and
transversal resistance than the SWB for V. ferruginea. In G. arborea, the SWB showed the
greatest values of resistance to nail extraction compared to the CWB bonded with both
adhesives, while the CWB with PVAc were statistically different from the control
treatment.
Strength in the CWB is affected by varying aspects (Hoadley 2000; Carvalho et al.
2003), one of which is the size of the product. In this case, the blocks were 10 cm × 10 cm
× 10 cm, which is rather large to be densified by compression. Vital et al. (1974) and Leng
et al. (2017) mention that the strength of the products increases if the material is adequately
densified, especially if performed by compression, as were the blocks in this project.
Furthermore, densification by compression at temperatures above 100 °C facilitates
plasticization of the wood particles (Hunt et al. 2017), thus increasing the internal bond
strength. However, the CWB cannot achieve the values observed for SWB (Rangel et al.
2017).
The increases in the internal bond resistances of the CWB with NCC-modified UF
adhesive in the three species (Table 1) is supported by the works of Veigel et al. (2011)
and Zhang et al. (2011), who found increases in the internal bond strength of UF adhesive
with added NCC. Kwon et al. (2015) mentions that the increase in the strength of NCC-
modified adhesives is due to the fact that the cellulose fibers in the glue line merge with
the adhesive inside the wood cavities, allowing better penetration; consequently, greater
strength is needed to separate two wood pieces. Likewise, the reinforcement effect of the
wood-adhesive interface is the result of the formation of a network between the NCC and
the polymer chains of the adhesives (Grishkewich et al. 2017). Ramires and Dufresne
(2012) and de Almeida Mesquita et al. (2018) explain that NCC’s high contact area, high
resistance to traction, and rigidity allow the formation of a crystal network that interacts
with the adhesive, increasing its mechanical resistance.
Meanwhile, in thermoplastic adhesives such as PVAc, the addition of NCC can
improve the low rigidity of the polymers, as well as adhesion in the glue line (Gindl-
Altmutter and Veigel 2014). Different adhesion mechanisms occur within the interface of
wood particles and adhesives, as the adhesive can penetrate the wood, allowing interlinking
and greater internal adhesion. Moreover, internal strength within the adhesive allows the
adhesive layer in the interface to remain bonded, improving the interactions and increasing
Water Absorption
The CWB compared to SWB presented greater water absorption, being statistically
equivalent in the CWB with UF without NCC in the three species (Table 1). No statistical
differences were observed in water absorption among the CWB with the PVAc adhesive.
Contrastingly, the CWB with UF adhesive in V. ferruginea and C. alliodora presented
statistical differences between NCC concentrations, as water absorption was greater with
1% NCC concentration.
The hydrophobic nature and porous structure of the wood favor water absorption,
as wood particles have a greater contact area (Salari et al. 2013). Moreover, neither of the
two adhesives present good performance against water (Yang et al. 2006), so greater water
absorption in the CWB compared to SWB was expected (Table 1).
However, the addition of NCC to the PVAc adhesive did not improve block
performance against water absorption. These results disagreed with Chaabouni and Boufi
(2017) and Jani and Izran (2013), who report that the decrease in water absorption in
products using PVAc is explained by the interlinking between the OH groups and the
adhesive matrix, preventing water intrusion inside the polymer matrix. In contrast, the same
result cannot be obtained with the UF adhesive due to the reduced interaction between the
NCC-modified adhesive and the wood particles, which deteriorates the adhesion forces and
prevents the formation of an adhesive barrier against water absorption, resulting in an
increased amount of absorbed water (De Almeida Mesquita et al. 2018).
Notably, CWB are affected by moisture absorbed from the environment, which
impairs the performance of the composite, as moisture penetration can weaken the internal
bonds of the wood particles (Rofii et al. 2016). The CWB, once compressed, are extracted
from the mold completely dry. During their conditioning, the CWB absorb humidity from
the environment, especially in a tropical region such as Costa Rica. Due to water
absorption, the CWB expand slightly, weakening the internal bonds of the adhesive or the
wood-adhesive interface, or the resistance to nail extraction (Gerhards 1982).
Figure 2 shows the behavior of the load applied to the pallets fabricated with the
different types of blocks (SWB or CWB) relative to deflection. In most of cases, the load-
deflection curves of the SWB pallets were below the load-deflection curves of the pallets
constructed with CWB glued with the two adhesives (PVAc and UF) modified with
nanocellulose. This result means that the pallets fabricated with these blocks manufactured
with PVAc or UF modified with nanocellulose will present less deflection compared to the
pallets built of SWB, for the same load magnitude. Furthermore, these load-deflection
curves also showed that there was less deflection when using the UF adhesive in CWB than
in CWB glued with PVAc in G. arborea (Fig. 2b). However, the CWB with UF showed
greater deflection than the CWB with PVAc in the same species (Fig. 2b). For V. ferruginea
wood (Fig. 2c), the CWB with UF showed greater deflection than the CWB with PVAc
and the load-deflection curves showed that there was less deflection when using the UF
adhesive in the CWB. Meanwhile, the deflection for the same load in the wooden blocks
of C. alliodora was similar for the two adhesives tested (Fig. 2a).
The pallets constructed with CWB of the three species presented the same failures
shown by SWB pallets. There were four failure types. In type I, upper boards detached at
the corners of the pallets, both from the lower boards and from the blocks themselves (Figs.
4a and 4b). In type II, the upper boards were broken (Fig. 3c). In type III, failure was caused
by tension in the lower boards of the central block of the pallet (Fig. 3d). In type IV, internal
block bonding failed (Fig. 3e).
Fig. 2. Load curves vs. deflection in the flexural test for pallets fabricated with CWB of Cordia
alliodora (a), Gmelina arborea (b), and Vochysia ferruginea (c) with two different wood adhesives
Fig. 3. Failure types in pallet flexural tests: Type I, upper boards detached (a and b); Type II,
upper board broken (c); Type III, failure due to tension (c); Type IV, upper boards were broken
(d); and failure in internal block bonding (e)
Although it was observed that CWB has much lower internal bonding resistance,
the pallets fabricated with CWB, the load at the limit of proportionality and the maximum
load increased, while deflections were lower, compared with SWB. NCC-modified
adhesives indicate that the increase in the resistance of is because the cellulose fibers in the
glue line merge with the adhesive inside the wood cavities, allowing better penetration;
consequently, greater strength is needed to separate two wood pieces (Kwon et al. 2015;
Grishkewich et al. 2017). Then pallets fabricated with CWB jointed with nails showed the
improvement of the proprieties of wood composites.
Finally, the pineapple wastes present the possibility of extracting NCC from the
pineapple fibers for reinforcing wood composites and joint with wood residues produced
in a sawmill can be converted into lignocellulosic composites, generally achieving better
properties than solid wood. Then such composites can substitute for solid blocks from
sawlogs, and they can be used in high-value products. Composite blocks for pallets are
commonly used in pallet fabrication, and its equipment and technology are widely
development. Thus, it is possible to fabricate pallets with wood composites having a high
beneficial effect of NCC.
CONCLUSIONS
1. The addition of 1% NCC to PVAc and UF adhesives for fabrication of CWB with
Vochysia ferruginea, Cordia alliodora, and Gmelina arborea wood produced an
increase in the internal bonding and in the nail extraction test of the blocks. Therefore,
ACKNOWLEDGMENTS
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Article submitted: December 30, 2018; Peer review completed: March 9, 2019; Revised
version received: March 12, 2019; Accepted: March 14, 2019; Published: March 19,
2019.
DOI: 10.15376/biores.14.2.3651-3667