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PII: S2352-4928(20)32311-4
DOI: https://doi.org/10.1016/j.mtcomm.2020.101300
Reference: MTCOMM 101300
Please cite this article as: Ranjbaran S, Nazerian M, Kermanian H, Garmaroody ER, Koosha
M, High strength papers impregnated with urea/melamine formaldehyde resin/nanosilica
nanocomposite coatings: the effects of paper type, blend ratio and nano-content, Materials
Today Communications (2020), doi: https://doi.org/10.1016/j.mtcomm.2020.101300
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Abstract
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The aim of this work was to study mechanical properties of two types of papers impregnated
(mechanical or Kraft), nanosilica content (0,2,4%) and UF:MF weight ratio (60:40, 75:25 and
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90:10) on the mechanical properties of the coated papers. The tensile index (TI), breaking length
(BL) and tear index of the mechanical papers were not affected significantly by addition of
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nanosilica to the resin while the Kraft paper was more responsive to nanosilica and showed
higher mechanical properties. Kraft paper coated with UF:MF 60:40 resin containing 4%
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nanosilica showed the highest TI, BL and tear index in machine direction among the samples.
The microstructure of the mechanical and Kraft papers impregnated with this nanocomposite
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coating was further characterized by FTIR, XRD, SEM/EDX and AFM. FTIR spectra proved the
formation of chemical bonds between the resin and nanosilica in Kraft paper. SEM/EDX and
XRD patterns revealed that nanosilica was well dispersed in the nanocomposite coating without
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any aggregation. The findings of this study suggest that naonsilica can be used as a promising
Keywords: Kraft paper; Mechanical paper; Melamine formaldehyde resin; Nanosilica; Tensile
index;
1. Introduction
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Laminate surfaces are conventional materials of choice for many applications in wood and paper
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industries [1]. Nowadays, many wood-lignocellulosic based products such as medium density
fiberboards and particleboards are coated by paper sheets impregnated with synthetic
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aminoplastic resins to improve the surface protection and decoration of the panels. These
features can be combined with high resistance to water and humidity absorption, elimination of
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nocuous gas emission (such as formaldehyde) and low cost. It is well-known that production of
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the impregnated papers is divided into two steps: in the first step, the paper is impregnated with
urea formaldehyde (UF) resin and then in the second step the impregnated paper is coated with
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melamine formaldehyde (MF) resin. The final saturated paper is dried to a final moisture content
of 6–9% [2, 3]. Due to the lower cost of UF, its addition to MF resins is very attractive. Blending
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UF and MF resins can modify the characteristics of the coating adhesive [4]. Amino groups
present both in melamine and urea have good compatibility due to the similarity in the molecular
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structure. The effect of melamine/urea ratio on the structure of different MUF resins has been
studied by thermal and spectroscopic methods [5]. Higher melamine content provides higher
moisture resistant and thermal stability to the resins due to formation of a tighter resin network.
In a recent work, the effect of a starch based extender on the thermo-mechanical properties of
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MUF resins is also evaluated [6]. There are also other attractive researches on the preparation,
characterization and properties of the resin-impregnated papers in the past years [7-9].
To enhance the properties of the resin coated papers, usually additives are added to the resin. The
type and content of the resin and the additive as well as manufacturing process factors can affect
the final quality of the impregnated paper [10]. Addition of fillers at the nano-scale for producing
impregnated papers is a new approach which results in a suitable distribution of the resin in the
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surface and bulk of the paper. Nano-fillers can modify the mechanical and physical properties of
the resins. Generally, increasing the content of nano/micron sized fillers increases the strength of
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the matrix but on the other hand, stress concentration caused by the agglomerated fillers reduces
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the ductility and sometimes the impact strength. Using nano-fillers with a good dispersion in the
matrix can reduce the stress concentration, enhance the mechanical properties and maintain or
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even improve the ductility. The high surface area per unit volume of the platelets of some
inorganic nanomaterials such as nanoclay and nanosilica can result in a higher degree of
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chemical and physical interactions between the polymer chains creating superior properties so
that with the same amount of the filler, the properties of the nano-composite material can be
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functionalized to improve its compatibility with organic matrices [18, 19]. The impact of
nanosilica content on the thermal properties of UF resins has been previously studied [20]. It was
shown that addition of nanosilica increased the thermal stability of UF resin due to the chemical
and physical interactions created between macromolecules of the resin and silica particles. The
other beneficial effect of nanosilica addition in UF resins is the reduction of free formaldehyde
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percentage in the modified resin. The effect of nanoclay and nano TiO2 on the volatile organic
studied [21]. The results showed that these nanomaterials can effectively decrease the
formaldehyde and VOC emission from wood-based panels coated with melamine impregnated
paper. A similar study showed that addition of TiO2-SiO2 nanocomposite aerogel into melamine-
impregnated paper results in high smoke suppression and formaldehyde degradation [22].
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As mentioned, the intrinsic properties of the UF/nanosilica nanocomposites have been evaluated
previously in the literature however, to the best of our knowledge, impregnation of different
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types of papers with nanosilica/UF/MF nanocomposite resins have been rarely studied. In this
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work, mechanical (newsprint) and Kraft papers were impregnated with nanosilica modified
blends of UF/MF resins and the mechanical properties of the coated papers were examined. The
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effect of type of the paper (mechanical or Kraft), UF/MF weight ratio and nanosilica content on
the mechanical properties of the coated papers such as tensile strength and tearing strength were
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reported. The optimum sample was selected based on the mechanical properties data. The
interactions of nanosilica with UF/MF resin and its dispersion in the matrix in the optimum
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sample was studied by scanning electron microscopy (SEM)/energy dispersive X-ray scattering
(EDX), atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR) and x-
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ray diffraction (XRD) techniques. Finally, the thermal properties of the impregnated papers were
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Samples of mechanical papers (40 g/m2 with 0.4 mm thickness, Newsprint grade, Mazandaran
Wood and Paper Industries) and Kraft papers (40 g/m2 with 0.2 mm thickness) were purchased
from Iran for using as base paper for impregnating with resin and coating purposes. MF and UF
resins were kindly supplied by Pars Neopan (Tonekabon, Mazandaran, Iran) and Amol adhesive
(Amol, Mazandaran, Iran) companies, respectively. The composition and physical properties of
the resins used are presented in Table 1. Hydrophilic nanosilica was supplied from Sigma
Aldrich, 637238 (Germany) having a specific surface area of 210 m2/g, SiO2 content >99.5%,
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density of 0.011 g/mL and average particle size of 20 nm.
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Table 1. The composition and physical properties of the resins used for impregnation.
Resin type Specific Gravity @ 20°C Gel time Viscosity Solid Content U/M:F molar ratio
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(s) (cP) (%)
(g/cm3)
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The samples of the coated papers were prepared according to an experimental design. According
to the design of experiments (DOE) (full factorial design, Table 2), an evaluation of the effects of
paper type, weight ratio of MF to UF resin and nano-SiO2 loading on the properties of the paper
were investigated. The first variable was the type of paper. The second investigated variable was
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UF:MF weight ratio with the selected values of 60:40, 75:25 and 90:10. The amount of
nanosilica was used as the third variable at 3 levels of 0, 2 and 4% (based on oven dry weight of
resin).
The coatings were prepared by blending two types of aminoplastic resins MF and UF. The resins
were mixed together with the ratios mentioned in the experimental design (Table 2) by a
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mechanical stirrer. For preparation of nanocomposite resins containing nanosilica, after mixing
the two types of resins, nanosilica was added and stirred at 1000 rpm for 2 min. Then, distilled
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water was added to the mixtures so that the solid content of resins was equal to 50%. In order to
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better disperse the nanoparticles in the resin solution, the UF/MF/nano-SiO2 mixtures were
stirred magnetically for 5 min before use. For impregnation of the papers, a two-stage process
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was applied. In the first stage, each paper was saturated with pure UF resin with a solid content
of 50% containing 1% NH4Cl as hardener and then dried in an oven at 120 °C for 120 s. A
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laboratory gravure roll coater was employed for impregnating the raw paper with UF resin. In the
second stage, the UF resin coated paper was impregnated with MF/UF or MF/UF/nano-SiO2
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resin using the laboratory gravure roll coater. The solid content of all of the resins was 50% and
1% NH4Cl was used as hardener. The resin impregnated papers of this stage were also dried in
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an oven at 120 °C for 120 s. Finally, all of the samples were conditioned at 20 °C and 65% RH
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for 48 h so the final moisture content of the coated papers reached at around 9%. The total resin
pick-up of the papers was measured gravimetrically by weighting the papers before and after
coating. The total resin pick-up was 50% and 60% for the coated Kraft and mechanical papers,
respectively. The samples of the coated papers were cut into 30×30 cm according to the
industrial formats, stored in plastic bags at room temperature and 65% humidity for further use.
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Table 2. Specifications of the samples prepared based on the experimental design.
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A1B2C2 Mechanical 2% 75:25
A1B3C2 Mechanical 4% 75:25
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A1B1C3 Mechanical 0% 60:40
A1B2C3 Mechanical 2% 60:40
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A1B3C3 Mechanical 4% 60:40
A2B1C1 Kraft 0% 90:10
A2B2C1 Kraft 2% 90:10
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A2B3C1 Kraft 4% 90:10
A2B1C2 Kraft 0% 75:25
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Tensile index (TI) in the longitudinal machine direction (MD), tearing index (Tin) both in MD
and cross MD (CD) directions and breaking length (BL) of the coated papers as responses of the
experimental design were measured according to TAPPI 494 OM-01 (1998), TAPPI T 414 OM-
04 (1998), TAPPI 403 OM-02 (1996) standards, respectively [23, 24]. In each experiment, 6
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specimens were used. For the tensile strength test, the papers were cut into 180×25 mm, fixed
between the grips of the device (Gotech GT-7010-D2EP micro-computer tensile strength tester,
China) equipped with a load cell of 5 kN) and extended at a rate of 25 mm/min up to the
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where F is the force of breakage (N), b is the width of the sample (0.025 m) and R is grammage
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of the paper (40 g/m2). To measure the tearing strength, the samples were cut into 10×3 cm and
tested in MD and CD directions. The results were divided by the grammage of the paper.
2.5. Characterization
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From the results of mechanical tests, the samples A1B3C3 and A2B3C3 showed the best
mechanical properties and were selected for further characterization. The chemical structures of
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the original papers (mechanical and Kraft) and the coated papers were separately investigated
using Fourier transform infrared spectrometer (FTIR) (Nexus 470, Thermo Nicolet, USA). The
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spectra were obtained in ATR mode at room temperature with 20 scans from 4000 to 400 cm−1 at
the resolution of 8 cm−1. Each sample was tightly fixed to the ATR accessory in order to ensure
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sufficient contact of the infrared light with the surface of the sample. A scanning electron
microscope (SEM) (Hitachi, Japan) was used to observe the morphology of the nanocomposite
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resin coated and uncoated papers. In order to detect the dispersion of nanosilica in the coatings,
distribution of Si atoms was mapped by energy dispersive X-ray spectroscopy (EDX) using
Ametex EDX device. Thermogravimetric Analysis (TGA) test was performed to study the effect
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Thermograms were obtained by a thermogravimetric analyzer (Bahr STA503, Germany) from
30°C to 500°C with a heating rate of 10 °C/min under nitrogen atmosphere. The X-ray
diffraction (XRD) patterns of the samples were carried out by an Equinox 3000 (INEL, France)
wide angle X-ray diffractometer using a CuKα radiation source with a wavelength of λ=0.154
nm.
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Analysis of variance (ANOVA) and Duncan multiple range tests (DMRT) (at 95% confidence
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3. Results
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3.1. Mechanical properties
The averages of the mechanical properties such as tearing index in the longitudinal and cross
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directions of paper machine, BL and TI of mechanical (Newspaper) and chemical (Kraft) papers
coated with different blend ratios of UF/MF containing different contents of nanosilica are given
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in Table 3. Based on the ANOVA results, significant differences between the group averages are
Table 3. Average mechanical properties of the coated papers and statistical analysis of the
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A1B1C3 29±1 fg 3±0.07 d 20±2 d 19±2 fg
A1B2C1 12±1 gh 1±0.03 e 21±2 cd 20±1 e
A1B2C2 35±3 f 3±0.2 d 20±5 d 20±2 e
A1B2C3 43±4 f 4±0.9 d 20±1 d 20±3 e
A1B3C1 3±1 h 1±0.7 e 21±2 cd 19±4 fg
A1B3C2 8±1 h 3±0.1 d 19±3 ef 19±1 fg
A1B3C3 42±3 f 5±1 d 20±3 d 23±2 bc
A2B1C1 116±8 e 12±1.3 c 22±1 bc 20±1 e
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A2B1C2 150±10 13±1.1 bc 20±4 d 21±1 d
A2B1C3 bcd
141±7 d 14±1.9 bc 19±5 ef 22±3 cd
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A2B2C1 145±11 cd 13±2 bc 23±2 ab 25±1 a
A2B2C2 153±18 14±2.1 bc 22±1 bc 24±2 b
bcd
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A2B2C3 165±8 abc 14±0.9 bc 20±3 d 23±3 bc
A2B3C1 158±18 13±3.1 bc 24±5 a 23±1 bc
bcd
A2B3C2 167±8 ab 15±1.2 ab 23±1 ab 22±2 cd
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A2B3C3 184±9 a 17±0.9 a 24±1 a 21±1 d
*
MD is the direction of the paper movement on the machine during manufacture.
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TI. Kraft paper coated with UF:MF 60:40 resin containing 4% nanosilica showed the highest TI.
From the results of Table 3 and figure 1, it was found that the effect of nanosilica on the TI of the
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coated papers is very sensitive to the type of paper as well as MF:UF ratio. Addition of
nanosilica to Kraft paper, increased TI in all UF:MF ratios while in mechanical paper, when MF
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content was 10% and 25%, TI was decreased with increasing the nanocontent. In contrast, when
the amount of MF was 40%, addition of nanosilica increased the TI of the coated mechanical
papers. Generally, the results show that using higher contents of MF and nanosilica both in
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Figure 1- TI of Kraft and mechanical papers coated with different amounts of MF:UF weight
BL of the sheets resulted in similar trend of improvement to those of the TI with the addition of
papers as illustrated in Figure 2. Simultaneously, impregnated chemical paper had the higher BL
in all samples compared to the mechanical papers. At the same level of MF resin for Kraft paper,
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the BL values increased with the higher nanocontent. However, for mechanical paper, BL
decreased with increasing the amount of nanosilica when a lower content of MF (10%) in resin
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was used.
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Figure 2- BL of Kraft and mechanical papers coated with different amounts of MF:UF weight
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Results of Tin. MD are shown in Figure 3. As can be seen, for the mechanical paper Tin. MD of
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the samples was not affected significantly by addition of nanosilica and melamine while for the
Kraft paper, it was increased by addition of nano-SiO2 in all MF:UF ratios. In contrast, addition
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of melamine reduced this parameter in the chemical paper except the samples with 4% nano-
SiO2. Maximum Tin. MD value obtained by adding 4% nanosilica into the resin with the highest
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content of MF for the impregnated chemical paper. According to Figure 1, addition of nanosilica
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Figure 3- Tin. (MD) of Kraft and mechanical papers coated with different amounts of MF:UF
In contrast with Tin. MD, by comparing the Tin. CD (Figure 4) of the mechanical and chemical
papers, it could be observed that Tin. CD of chemical papers increases with nano-SiO2 addition
up to 2% and then decreases. Adding 10% MF results in higher Tin. CD which is still higher than
those of the papers impregnated with resin containing 25% and 40% MF. Meanwhile, the
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replacement of resin by SiO2 nanoparticles at 4% in mechanical papers produced impregnated
paper with highest Tin. CD with respect to the increment of MF content to 40% in resin. By
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comparing Tin. CD of chemical papers, it is seen that when nanosilica is not present in the resin
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formulation, addition of MF into UF resin increases the Tin. CD. In contrast, when the nanosilica
exists in the resin formulation, increasing the MF (at 2 and 4%) decreases the Tin. CD of the
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samples. Presence of MF increases the strength of UF/MF network by forming crosslinks while
addition of nanosilica to the network can increase the stress concentration and lower the Tin CD.
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Figure 4- Tin. CD of Kraft and mechanical papers coated with different amounts of MF:UF
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According to the results of the mechanical properties, the papers coated with UF/MF 60:40 resin
containing 4% nanosilica (A1B3C3 and A2B3C3) showed the best performance. Thus, these
samples were used for further characterization. FTIR spectroscopy was used to study the
interactions of the resin with lignocellulosic compounds of the paper. Figure 5 shows the FTIR
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spectra and characteristic bands of original and impregnated papers. The FTIR spectra of the
mechanical and Kraft papers show the characteristic bands of lignocellulosic compounds present
in Kraft and mechanical pulps [25, 26]. The OH stretching vibrations of the lignocellulosic
compounds present in the papers (Figure 5-A) were observed at around 3325 and 2895 cm-1
while the intensity for the Kraft paper is higher than mechanical paper mainly because it is
produced through chemical pulping process which eliminates most of the lignin present
originally between the wood fibers. The peaks observed for both types of papers are nearly the
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same except the peaks at 1726, 1502, 1510 and 1266 cm-1 which are present in mechanical paper
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while they are absent in the Kraft paper. These peaks are related to the vibrations of the aromatic
skeleton of the lignin, which exists in higher amounts in the mechanical paper [27].
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In the spectrum of the impregnated papers (Figure 5-B), several broad overlapping bands were
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observed in the region 2600-3500 cm-1 due to stretching vibrations of OH, NH and CH groups in
accordance with previous literature [14, 28]. In the spectrum for the coated Mechanical paper,
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the primary amine vibrations were observed with sharp peaks at 3466, 3413, 3321 and 3118 cm-
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. In case of the coated Kraft paper, these peaks were broader with small changes in the
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frequency. The sharp peaks observed in this region may be related to the unreacted primary
amine groups of melamine [29-31]. These peaks indicate that the curing reaction was not
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complete because the thermal treatment performed in this study was 120 s at 120 °C [29, 31]. By
comparing the spectrum for the coated papers, it can be concluded that the resin coated on the
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Kraft paper was more crosslinked. C-H stretching vibrations were observed at 2968 cm-1 for both
coated papers. In the fingerprint region, the sharp absorption bands at 1643, 1531 and 810 cm-1
are related to the triazine ring which is characteristic of MF resins. The peaks at 1660 and 1628
cm-1 are due to the carbonyl group stretching vibrations of primary amides of the crosslinked and
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un-crosslinked resins [32]. The absorption bands at around 1244, 1120 and 773 cm-1 are related
to the stretching vibrations of Si-O-C, Si-O-Si and Si-O groups, respectively [33]. Crosslinking
between organic molecules and the surface of nanosilica results in formation of Si-O-C bonds.
Presence of the band at 1244 cm-1 is related to the formation chemical bonds between the resin
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Figure 5- FTIR spectra of neat Kraft and mechanical papers (A) and the papers impregnated with
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3.3. XRD results
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The morphology of the impregnated and unimpregnated samples in this study is characterized by
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XRD analysis. The powder X-ray diffraction profiles of mechanical paper, Kraft paper,
mechanical and craft papers containing 4% nano-SiO2 in the range of 2θ = 5–40 are presented in
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Figure 6 (A-B). As shown in Figure 6-A, the XRD patterns of pure nano-SiO2 consists of a broad
diffraction peak at only 2θ=23°, showing that the structure of the nanosilica used in this work is
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dominantly amorphous. According to Arafa et al. [34] and Liu et al. [35], the XRD profiles of
aminoplastic resins display relatively sharp peaks at a wide angular range. Broad and finger print
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diffraction peak at 23° in impregnated papers along with the peak at 2θ=18° and three sharp
peaks at 2θ= 26.4°, 29° and 30° present the crystalline structures of the cured UF/MF resin
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(Figure 2-B). Broad diffraction peaks at 2θ~16° and smooth peak at 2θ~23° in unimpregnated
Kraft and mechanical papers are the typical of the cellulose crystalline patterns [36]. According
to the XRD patterns of the samples, it seems that presence of nano-SiO2 can change the
appearance of the patterns as amorphisation of the resin was increased. The XRD patterns of the
blended UF/MF/SiO2 impregnating mechanical paper and Kraft paper at 2θ = 26.4°, 29° and 30°
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are very similar, which are composed of intense peaks due to UF/MF peaks superimposed on the
broad peak of nano-SiO2. Besides, a broad diffraction peaks at 2θ~16° was disappeared because
of partial degradation of structural components of the fibers during curing of UF/MF resin and
facilitating the formation of OH bonds which can result in a higher crystallinity [37]. The XRD
patterns of the samples confirm the fact that the impregnated papers formulations are mainly
crystalline. It can be seen that the diffraction peaks at 2θ= 26.4◦, 29° and 30° disappear
completely in unimpregnated papers while impregnated samples have sharp narrow diffractions
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at these peaks that may be assigned to crystalline UF/MF domains (Figure 2-B). Moreover,
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addition of nanosilica to pure resin causes a slightly broader diffraction peak at 2θ= 23° [34]. It
can be due to the presence of nano-SiO2 and the higher amorphous structure of the nanosilica.
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Appearance of the peak patterns cannot be changed due to presence of nanosilica while
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sharpness and broadness of the peaks can be changed because of amorphous structure of silica
nanoparticles [38].
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Figure 6- XRD patterns of nanosilica (A), uncoated Kraft and mechanical papers and the papers
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AFM images of the neat and impregnated Kraft and mechanical papers are presented in figure
7,A-D. By comparing figure 7-A and B, it can be seen that mechanical paper has a smoother
surface than Kraft paper. Presence of lignin between the fibers of the mechanical paper results in
a smoother surface, because in Kraft paper the fibers are almost lignin-free. When the papers
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were coated, the same result was observed (figure 7-C,D). SEM images of the coated and
uncoated papers are presented in figure 8-A-D. The results are in accordance with AFM images.
In Kraft paper (figure 8-B), individual fibers can be better observed compared to mechanical
paper (figure 8-A). In mechanical pulping process, wood chips are ground in a refiner by
applying intensive shearing forces. The heat generated from grinding softens the lignin bound to
the fibers and the mechanical forces separate the fibers. As this process leaves lignin within the
fibers, the separated fibers may aggregate into bundles after the process. Though, the fibers
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observed in SEM image of mechanical paper have aggregated structure. In chemical pulping
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process, wood chips are cooked with chemicals under high pressure. This process removes lignin
and separates intact cellulose fibers as can be seen from figure 8-B. Figure 8(C,D) shows the
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SEM images from the surface of the coated papers. In mechanical paper, the resin is uniformly
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distributed on the surface of the paper while in Kraft paper, impregnation was not complete in
Figure 9 shows the SEM images from the cross section of the uncoated and coated papers. In the
images of the uncoated papers (figure 9-A,B), the smoothness of the surface can be observed for
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the mechanical paper compared to Kraft paper. The images of the resin coated papers show the
diffusion of the resin into the paper. The thickness of the resin layer on each paper was different.
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In mechanical paper, the distribution of the resin on the surface of the paper was not uniform and
had a higher thickness than Kraft paper. Due to presence of lignin, mechanical paper has a more
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hydrophobic surface compared to Kraft paper. In contrast, Kraft paper has a more hydrophilic
surface which is enriched with hydroxyl groups. The UF/MF resin used for coating is also
hydrophilic which can interact with hydroxyl groups of Kraft paper. By comparing the cross
section image of mechanical and Kraft papers (figure 9-C,D), it can be seen that UF/MF resin
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has a uniform distribution and diffused perfectly to the bulk of Kraft paper with a smoother film
formation on the surface while the resin is more agglomerated on the surface of the mechanical
paper with a lower penetration into the bulk of the paper. UF/MF resin has a weaker interaction
with the surface of mechanical paper due to hydrophobic nature of lignin present between the
fibers. This limits the diffusion of resin into the bulk of mechanical paper resulting in a thicker
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In order to characterize the distribution of nanosilica in the coating, Si atoms were mapped in the
resin coated papers. As can be seen from figure 10, nanosilica is uniformly distributed in the
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resin without any aggregation or agglomeration. Si atom is detected with a high intensity (figure
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10-C,F) in accordance with the literature data [14] proving the presence of nanosilica particles in
Figure 7- AFM images from the surface of uncoated mechanical (A) and Kraft (B) papers and
Figure 8- SEM images from the surface of uncoated mechanical (A) and Kraft (B) papers and
Figure 9- SEM images from the cross section of uncoated mechanical (A) and Kraft (B) papers
Figure 10- results of EDX mapping for the resin coated Kraft (A,B,C) and mechanical (D,E,F)
papers.
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The results of TGA for the mechanical and Kraft papers as well as the papers coated with
UF:MF 60:40 resin containing 4% nanosilica are presented in figure 11 (A,B). For both of the
unimpregnated papers, the mass% is reduced after increasing the temperature to 100°C due to
evaporation of water. The mass% was nearly constant up to 260°C and started to decrease with a
high rate after this temperature. In this step, degradation of cellulose fibers initiates and is
continued up to around 350°C. The reduction of mass is continued with a lower rate after this
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temperature. In case of nanocomposite resin coated papers, the mass of the samples was stable
up to around 300°C then decreased in two steps. The mass% was reduced with a high rate from
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300 to 350°C and then with a lower rate up to 600°C. The temperatures of 10%, 50% and 70%
reduction in mass% as well as the ash content of the samples are presented in table 4. Kraft paper
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has a higher T10 compared to mechanical paper due to higher hydrogen bonding interactions
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between the fibers. T50 did not differ between Kraft and mechanical papers. In contrast, T70 was
higher for mechanical paper due to higher amount of lignin. When the papers were coated with
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nanocomposite resin, T10 was reduced while T50, T70 and ash content were significantly
increased comparing to the uncoated papers. Reduction of T10 may be due to the hydrophilicity
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of the resin which absorbs humidity of the environment and release it when heated. Meanwhile,
the results of table 4 show that impregnation of Kraft and mechanical paper with nanocomposite
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coating significantly improves the thermal stability of the papers. Similar results were reported
Figure 11- TGA thermograms of uncoated and coated Kraft (A) and mechanical papers (B).
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Table 4- Temperature of 10, 50 and 70% reduction in mass% of the coated and uncoated paper as
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Kraft 313 345 410 7.6
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Kraft-coated 263 356 546 25.0
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4. Discussion
Results of mechanical properties of the resin coated papers in this work revealed that mechanical
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and Kraft papers show different behavior toward addition of nanosilica into the resin. As seen, TI
and BL of the mechanical papers coated with nanocomposite resin were lower than that of Kraft
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papers. There are several parameters that are important in determining the quality of the resin
impregnated papers. These factors can be related to the paper or resin coating as well as
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interaction of resin with fibers of the paper. Parameters such as paper density, flexibility and
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reactivity with the coating resin are affected by the type of paper. Properties of the coating resin
properties can affect the processing and quality of the final product [2]. Flow properties of the
resin at the surface of the paper conducts film formation and surface properties of the coated
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paper. Higher diffusion and more uniform films can result in higher mechanical performance for
It was mentioned that mechanical papers have higher lignin contents within the fibers. This
results in a more hydrophobicity which reduces the penetration of the hydrophilic resin and film
formation on the surface of the fibers. It is proved that addition of nanosilica increases the
viscosity of the UF resins [40]. Higher viscosity prevents penetration of the resin into the fibers
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and film formation as observed by SEM images (figure 9). From the other side, due to higher
hydrophobicity of the mechanical paper, interaction of the resin with surface of the fibers
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reduces due to lower number of hydrogen bonds formed between the resin and fibers.
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Accordingly, the mechanical properties of the mechanical paper at MF:UF ratios of 10:90 and
25:75 was reduced by addition of nanosilica. In contrast, addition of nanosilica to the resin
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significantly resulted in superior mechanical properties in most cases.
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5. Conclusions
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Increasing MF content in UF/MF resin mixtures resulted in the improvement of the mechanical
properties due to formation methylene crosslinks in the network structure. UF/MF resin with
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40% MF and 4% nanosilica showed the highest TI, Tin MD Tin CD and BL. Diffusion of the
resin into the Kraft paper was higher due to lower lignin content and hydrogen bonding
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interactions between the resin and hydroxyl groups present at the surface of the cellulosic fibers.
SEM images showed that the resin diffused well and formed a uniform film on the surface of
Kraft paper while the film had a non-uniform surface on the surface of mechanical paper.
According to the SEM/EDX results, the nano-SiO2 was dispersed well in the matrix without
aggregation. The results of this work suggest that nanosilica can be used as an effective additive
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for improving the mechanical properties of UF/MF resin coated papers specially, when the
Declarations
Not applicable
Funding
There was no financial support for this research
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There is no conflict of interests related to this manuscript.
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Conflict of interests
There is no conflict of interests
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Figure 1- TI of Kraft and mechanical papers coated with different amounts of MF:UF
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weight ratio and nanosilica.
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Figure 2- BL of Kraft and mechanical papers coated with different amounts of MF:UF
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Figure 3- Tin. (MD) of Kraft and mechanical papers coated with different amounts of
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MF:UF weight ratio and nanosilica.
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Figure 4- Tin. CD of Kraft and mechanical papers coated with different amounts of
MF:UF weight ratio and nanosilica.
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Figure 5- FTIR spectra of neat Kraft and mechanical papers (A) and the papers
impregnated with UF:MF 60:40 resin containing 4% nanosilica (B).
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Figure 6- XRD patterns of nanosilica (A), uncoated Kraft and mechanical papers and the
papers coated with UF:MF 60:40 resin containing 4% nanosilica (B).
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Figure 7- AFM images from the surface of uncoated mechanical (A) and Kraft (B) papers
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Figure 8- SEM images from the surface of uncoated mechanical (A) and Kraft (B) papers
and resin coated mechanical (C) and Kraft (D) papers.
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Figure 9- SEM images from the cross section of uncoated mechanical (A) and Kraft (B)
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papers and resin coated mechanical (C) and Kraft (D) papers.
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Figure 10- Results of EDX mapping for the resin coated Kraft (A,B,C) and mechanical
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(D,E,F) papers.
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Figure 11- TGA thermograms of uncoated and coated Kraft (A) and mechanical papers
(B).
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