See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/277942391

Reduction of Formaldehyde Emission from Particleboard by Phenolated Kraft

Lignin

Article  in  The Journal of Adhesion · May 2015

DOI: 10.1080/00218464.2015.1046596

CITATIONS READS
23 188

3 authors, including:

Hamed Younesi-Kordkheili A.Pizzi Pizzi

Semnan University University of Lorraine
24 PUBLICATIONS   264 CITATIONS    924 PUBLICATIONS   17,855 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

characterization of algerians oak wood by x-ray tomographic scanner and free software image-j View project

lignin- based wood adhesives View project

All content following this page was uploaded by Hamed Younesi-Kordkheili on 22 January 2016.

The user has requested enhancement of the downloaded file.

This article was downloaded by: [Antonio Pizzi]
On: 07 June 2015, At: 10:51
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

The Journal of Adhesion

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/gadh20

Reduction of Formaldehyde Emission from

Particleboard by Phenolated Kraft Lignin
a b c
Hamed Younesi-Kordkheili , Antonio Pizzi & Ghorban Niyatzade
a
Department of Wood and Paper Science, Faculty of Natural Resource, Semnan University,
Semnan, Iran
b
LERMAB, University of Lorraine, Nancy, France
c
Department of Chemistry, Islamic Azad University, South Tehran Branch, Tehran, Iran
Accepted author version posted online: 21 May 2015.

Click for updates

To cite this article: Hamed Younesi-Kordkheili, Antonio Pizzi & Ghorban Niyatzade (2015): Reduction of Formaldehyde
Emission from Particleboard by Phenolated Kraft Lignin, The Journal of Adhesion, DOI: 10.1080/00218464.2015.1046596

To link to this article: http://dx.doi.org/10.1080/00218464.2015.1046596

Disclaimer: This is a version of an unedited manuscript that has been accepted for publication. As a service
to authors and researchers we are providing this version of the accepted manuscript (AM). Copyediting,
typesetting, and review of the resulting proof will be undertaken on this manuscript before final publication of
the Version of Record (VoR). During production and pre-press, errors may be discovered which could affect the
content, and all legal disclaimers that apply to the journal relate to this version also.

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.

This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Reduction of Formaldehyde Emission from Particleboard by Phenolated Kraft
Lignin

Hamed Younesi-Kordkheili1, Antonio Pizzi2, Ghorban Niyatzade3

1
Department of Wood and Paper Science, Faculty of Natural Resource, Semnan
University, Semnan, Iran, 2LERMAB, University of Lorraine, Nancy, France,
3
Department of Chemistry, Islamic Azad University, Tehran, Iran

Corresponding author: Hamed Younesi-Kordkheili, Department of Wood and Paper

Science, Faculty of Natural Resource, Semnan University, Semnan, Iran. E-mail:
Younesi1363@gmail.com

Abstract
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

The aim of this study was the reduction of formaldehyde emission from particleboard by

phenolated Kraft Lignin. For this purpose, the lignin was extracted from black liquor and

then modified by phenolation. During the UF resin synthesis different proportions of

unmodified and phenolated Kraft lignins (10, 15 and 20%) were added at pH=7 instead of

the second urea. Physicochemical properties and structural changes of resins so prepared,

as well as the internal bond (IB) strength and formaldehyde emission associated with the

panels bonded with them were measured according to standard methods. The Fourier

transform infrared (FTIR) analysis of lignin indicated that the content of O-H bonds

increased in phenolated lignin while the aliphatic ethers C-O bonds decreased markedly

in the modified lignin. Since both synthesis of UF resins and lignin phenolation are

carried out under acid conditions, phenolation is an interesting way of modifying lignin

for use in wood adhesive. The panels bonded with these resins showed significantly

lower formaldehyde emission compared to commercial UF adhesives. The UF resin with

20% phenolated lignin exhibited less formaldehyde release without significant

differences in internal bond strength and physicochemical properties compared to an

1
 unmodified UF resin. XRD analysis results indicated that addition of phenolated lignin

decreased the crystallinity of the hardened UF resins.

KEYWORDS: Kraft lignin, Phenolation, Urea formaldehyde resin, Formaldehyde

emission, Wood ashesives

1. INTRODUCTION

About 90% or more of the world’s board production is bonded with urea formaldehyde
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

(UF) resins [1]. UF resins have many advantages such as low cost, ease of use under a

wide variety of curing conditions, the fastest reaction time in the hot press, water

solubility, low cure temperatures, resistance to microorganisms, excellent thermal

properties and they are colorless [1,2]. However, the main defect of wood based panels

bonded with UF resins is formaldehyde emission [3]. Formaldehyde is a dangerous gas as

even in small amounts it can cause serious health problems. The formaldehyde emission

from wood-based panels depend on numerous factors such as wood species, type of

adhesive, additives, moisture content, board composition, pressing conditions, subsequent

treatment and the age of the material [4]. Thus, the reduction of formaldehyde emission

from wood based panels has been pursued by researchers in the adhesive and wood-based

materials industries for many years [5–7]. So far several ways has been reported for

reducing formaldehyde emission from wood-based materials bonded with UF resins such

as use of modified urea-formaldehyde resins, optimization of the manufacturing

parameters (wood species, layers of the panel, moisture, pressing conditions), application

of a diffusion barrier, subsequent treatment of the material with formaldehyde-binding

2
 systems and storage of the wood-based materials [8,9]. However one of the best reported

methods for reduction formaldehyde emission from wood based panels is the addition of

formaldehyde scavengers to the resin. Several researchers have tried a number of

different materials as formaldehyde scavengers for UF resins [7–10]. Phenolic materials

(such as phenol and resorcinol) are an important group of UF resins scavengers [11].

Addition of phenol appears to significantly decrease formaldehyde emission of the

particleboard made from UF resin [12].

Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

Conversely, Lignin is one of the major components of lignocellulosic materials which are

a complex heterogeneous phenolic polymer presenting structure. The lignin molecule can

be used in composites, fuels and chemicals production [13–15]. This fact in combination

with the actual environmental pressure on synthetic resins might be the chance for a more

acceptable use of lignin as an extender or component in adhesives. In the present research

work, for the first time, lignin has been used for the reduction of formaldehyde emission

from wood based panels.

Although the sources of lignin are different such as wood or bark, the pulp and paper

industry is the main source of lignin. More than 50 million tons lignin is produced

annually in the pulp and paper industry [16]. Since technical lignins (Soda, Kraft, Sulfite

and organosolve) originate from different sources and separation processes, they are

different from each other to a significant extent. Previous study indicated that alkali

lignins (soda and Kraft) among the various resources of lignins yielded better results than

synthetic wood adhesives [17]. Because Kraft lignin is the one produced in larger

3
 amounts in the world, this type of lignin has been selected as a UF resins scavenger in

this work.

The main obstacle to using lignins in synthetic resins is related to their sites being less

reactive than those of phenol and resorcinol [18]. Some efforts have been made to

improve the reactivity of lignin molecules [19,20]. Phenolation (adding –phenolic groups

to lignin by reaction with phenol in the presence of catalyst) was reported as one of the

most interesting modification methods of lignin for use in wood adhesive [18].
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

It must be noted that different lignins have different physico-chemical properties

influencing resin properties differently when incorporated into them. Our previous study

indicated that glyoxalated Soda Bagasse lignin significantly decreased formaldehyde

emission of plywood panels bonded with a UF resin [21]. There are some works that have

reported the properties of using phenolated lignin with phenol formaldehyde resin (PF)

resins [22,23]. However, there is no information about the effect of phenolated Kraft

lignin on formaldehyde emission of the panels made with UF resins. The aim of this

research, therefore, was the reduction of formaldehyde emission from particleboard by

using phenolated Kraft lignin as new scavenger.

2. MATERIAL AND METHODS

2.1. Lignin

Kraft black liquor with pH=12 and 90% solid content as source of lignin was prepared by

Choka Company (Talesh, Iran). Black liquor was acidified to pH=7 by 1mol/L

4
 hydrochloric acid (HCL) in order to achieve a pH of the lignin comparable with UF

resins.

2.1.1. Phenolation Of Lignin

A flask provided with thermocouple, mechanical stirrer and condenser was charged with

100 gr melted phenol. 20 g of Kraft lignin (with 50% solid content) was added slowly to

flask. Oxalic acid as a catalyst was added to mixture. The reaction mixture was heated up

to the reaction temperature (130 ◦C) in an oil bath at a reaction time of 50 min. Then the
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

mixture was refluxed at temperature for 1h. Finally, the samples were collected

throughout the phenolation reaction and was acidified to pH=7 by 1mol/L HCL.

2.1.2. FTIR Spectroscopy

Structural changes in phenolated lignin were determined by Fourier Transform Infrared

spectrometry (FTIR). The unmodified and phenolated lignins were oven-dried and then

reduced to powder by milling before testing by FTIR. FTIR spectra were obtained from

potassium bromide (KBr) pellets with 1 % of the powdered lignins at wave numbers

between 400 and 4000 cm-1.

2.2. Synthesis Of UF Resins Modified By Lignin (LUF) And By Phenolated Lignin

(PLUF)

After tests of several versions the following method was selected for the preparation of

LUF and PLUF resins:

5
 A 500 ml flat bottom flask equipped with a condenser, thermometer and a magnetic

stirrer bar was charged with formalin (37% formaldehyde solution). The pH was adjusted

to the range of 7.5 - 8.5 by adding a few drops of sodium hydroxide (45% concentration).

Then the first urea was added to the solution. After stirring for 30 minutes at 40 ◦C, the

temperature was slowly increased to 90◦C under reflux over a period of 30 minutes; this

temperature was kept constant for 60 minutes. The condensation reaction was started by

adding few drops of formic acid and reducing the pH to 5.0–5.5. After reaching the

intended viscosity the solution was neutralized by sodium hydroxide (40%). Then various
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

portions (10, 15, and 20 mass based on total weight of urea) of unmodified lignin or of

phenolated lignin (instead of a usual addition of second urea when preparing UF resins)

was added to the mixture. The temperature was again increased to 90◦C and the mixture

was refluxed for 90 minutes. Distillation of the mixture was performed using a laboratory

vacuum pump and equipment at 60◦C for one hour. Finally, urea was added at 40◦C.

In this research the pH value of the various resins prepared was adjusted to the same

value (7.5– 8.0). Also the solid content of prepared resins was adjusted to 53% .The

molar ratio of formaldehyde to urea was 1.3 and three resins depending on lignin type

(modified or unmodified) and replacement rate (10, 15, and 20%) were prepared for each

condition.

2.3. UF Resin

6
 A commercial UF resin was prepared from Northern Pars Company, Amol, Iran. The

different properties of the resin prepared are reported in Table 1. The formaldehyde to

urea molar ratio of this UF resin was 1:1.3.

2.4. Physicochemical Tests

The solid content of the adhesives was determined according to ASTM D 4426–93. The

density of the liquid resin was obtained by density hydrometer. The viscosity of the resins

was measured at 25◦C using a Ford Cup. pH values were measured with a Hanna pH
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

meter (Romany). In order to determine the gel time, 5 grams of the resin were introduced

into a dry glass beaker. Then 0.5 grams of a 20% aqueous NH4CL solution was added to

the resin. The beaker was then immersed into boiling water and the time until hardening

was measured. Two replicates for each sample were made. The content of free

formaldehyde of the resins was measured by the sulfite method immediately after resin

preparation [24].

2.5. Particleboard Manufacturing

A forming mold frame (35×35×1cm) was placed on a stainless steel caul plate to control

thickness. Surfaces of each plate were sprayed with a mineral oil releasing agent to

render adhesion with the surface of the composite. Dried particles were then blended with

prepared resins in a rotating drum-type mixer fitted with a pneumatic spray gun. Then

compounded material was poured into the frame and spread to fill the frame evenly.

When forming was complete, the top caul plate was placed on the top of the mat, and the

entire assembly was placed into an oil-heated press that was used for compression

7
 molding. The temperature of the press plates was maintained at 180 ºC at 25 bar pressure.

Pressing the compound material was carried out respectively in two stages by hot and

cold presses for 5 min. A 5cm wide edge of each board was trimmed to remove the low

density and poor bonding areas of boards. To provide reproducibility, three panels were

manufactured for each formulation. The nominal thickness and density of manufactured

panels was 16 mm and 0.8 g/cm3, respectively. Preparation of the samples for internal

bond and water absorption measurement was started 24 hours after pressing.
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

2.6. Internal Bond Strength

internal bond strength of the manufactured panels were measured according to ASTM D

906-98.The samples were conditioned at a temperature of 23°C±2°C and a relative

humidity of 60%±5% for two weeks. Five specimens were tested for each resin.

2.7. Free Formaldehyde Release

The subsequent formaldehyde emission from the particleboard panels was done using the

flask method according EN 717-3. The Free formaldehyde values were measured after 48

h later than cutting panel.

2.8. XRD Analysis

UF resin containing 20% phenolated lignin was selected for further analysis by XRD.

Wide angle X-ray analysis (XRD) was carried out in order to investigate any change in

the crystalline structure of the synthesized resins. XRD samples of UF, LUF and PLUF

resins were hardened by addition of ammonium chloride at 100 °C in an oven and then

8
 were powdered by milling and mounted on a Philips XRD powder diffractometer for

analysis. XRD patterns were taken with a Philips X pert MPD diffractometer (Eindhoven,

Netherlands) with Co radiation at a wave length of 1.78897 A0, at 40 kW and 40 mA.

Powder samples were scanned over a range of diffraction angle 2θ= 10-60°, with a scan

speed of 1°/min at room temperature.

3. RESULTS AND DISCUSSION

3.1. FTIR Spectroscopy

Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

The infrared spectra obtained from unmodified and phenolated Kraft lignin are reported

in Fig. 1. The peak assignment of FTIR spectra of lignin is summarized in Table 1. A

comparison between the IR spectra of unmodified and phenolated Kraft lignin indicates

that few main peaks varied or appeared when lignin had been modified. In the phenolated

lignin, the intensity of the peak at 3420cm-1 band, which is related to O-H stretching,

clearly increases. This is because of the phenolic hydroxyl groups of lignin could be

increase significantly by phenolation. Compared to unmodified lignin, the 1330 cm-1 band

related to the C-O bond in aliphatic ethers decreased markedly in the modified resin.

Cleavage of ether bonds decreases the average molecular weight of lignin [18]. The FTIR

results indicated that, in general, the amount of ethylene bridges in the cross-linked

network structures of the cured PLUF resin was markedly lower than for the UF resin.

Moreover, a new peak at 880 cm-1 band was detected for phenolated lignin when

compared to the UF resin spectrum. This band probably is due to the reaction between the

ortho and para sites of phenol and the hydroxyl groups in the side chain of lignin.

9
 3.2. Properties of the Synthesized Resins

The physicochemical properties of the various synthesized resins are reported in Table 2.

The incorporation of Kraft lignin (both unmodified and phenolated lignins) into the UF

resin increased the gel time. The UF resin containing 20% unmodified lignin exhibited

the longest gel time (85s) among all synthesized resins. Increase in gel time of the resins

containing lignin probably can be attributed to lower free formaldehyde. So far several

researchers have indicated that compared to synthetic polymers, lignins have a longer gel

time [25]. Thus, the long gel time of lignin can influence the gel time of the synthesized
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

resins. Increase in gel and press times of resins by addition of lignin has been reported by

several researchers [22, 25, 26]. This results in a decrease in the rate of crosslink

formation, leading to longer gel times. Table 2 also indicated that the viscosity of the

synthesized resins decreased continuously by addition of unmodified and phenolated

lignin up to 20%. Regarding the solid content of the resins, at constant values, the

reduction in UF resin viscosity by addition of lignin is mainly related to chemical effects.

The density of the resin decreases by incorporating lignin into a UF resin. The highest

and the lowest density value among synthesized resins respectively can be observed in

the UF resin (1.238) and the LUF resin with 20% lignin (1.215). From Table 2 it can be

seen that the UF resin with 20% phenolated lignin exhibited the lowest content of free

formaldehyde. The free formaldehyde content of the UF resin was 0.4%. Reduction in

free formaldehyde in the PLUF resin can be related to the lignin component which works

as a formaldehyde scavenger in the resin. Our previous study indicated that lignin can

significantly decrease formaldehyde emission of wood based panels [21].

10
 Table 2 also indicates that the PLUF resin exhibits faster gel time, lower free

formaldehyde and higher SPG and viscosity values compared to a LUF resins at constant

solid content. This is because of more reactive groups (phenolic –OH) incorporated into

lignin after phenolation. The higher reactivity of lignin modified by phenolation when

compared to unmodified lignin has been reported by several authors [18–22].

Finally it can be concluded that several chemical reactions probably occur in the

synthesized PLUF resin: I) The reaction of UF–CH2OH with the hydroxyl groups of
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

lignin; II) The reaction of the -OH group of prephenolated lignin with the –NH2 and –

NH- groups of the UF; III) The reaction of free formaldehyde with both the UF resin and

the lignin.

3.3. Internal Bond Strength

The internal bond strength of the panels made from the synthesized resins is presented in

Fig. 2. This Figure indicates that the panels bonded with the modified UF resin exhibit

weaker internal bond strength than those bonded with UF resin. It can also be seen that

the samples prepared from phenolated lignin (PLUF) exhibited higher internal bond

strength value than those made from unmodified lignin (LUF). Among the modified UF

resins, the PLUF resin containing 10 % phenolated lignin exhibited the highest internal

bond strength (1.88MPa) and the LUF resin containing 20% of unmodified lignin

exhibited the weakest internal bond strength (1.21 MPa). This is supported by the

differences in physicochemical properties of PLUF resins compared to LUF resins (Table

2). Adhesive penetration plays an important role in wood adhesion, since wood is a

11
 porous material. The degree of penetration mostly depends on wood factors, resin type,

physicochemical properties of the resin and the processing parameters [27]. The wood

species and the processing parameters used were identical for all panels, hence the

differences in the panels made from LUF and PLUF resins can be attributed to

differences in resin properties. Several researchers indicated that the viscosity and the

resins molecular size are important factors influencing mechanical strength of wood

based panels [28]. Compared to LUF resins, PLUF resins have higher viscosity and

density which prevented too much penetration of the resin into the wood surface. Fig. 2
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

also indicates that there are no significant differences between the internal bond strength

results of the panels prepared with PLUF resins containing 10% phenolated lignin and

unmodified UF resins. Previous researches have shown that particleboards prepared from

PF resins with up to 30% phenol substituted by phenolated lignin showed similar

physical and mechanical properties than those made from commercial PF resins [22].

3.4. Subsequent Formaldehyde Emission From Particleboard

The formaldehyde emission value from the particleboards is reported in Fig. 3.

Formaldehyde emission differs greatly among the cured resins. It can be observed that if

lignin is incorporated into the UF resin, the formaldehyde emission from the panels

decreases independently if the lignin component as such is modified or not (Fig. 3).

Lignin addition, leading to lower F/U ratio, significantly decreases formaldehyde

emission from the panels. Theoretically, releasable formaldehyde can exist in several

different states in the board. For example: as monomeric formaldehyde entrapped in

voids or adsorbed into wood, and as monomeric formaldehyde hydrogen-bonded to the

12
 wood. However, a common theory on feasible causes of formaldehyde emission from

particleboard is that the cured UF resin gradually undergoes hydrolytic degradation [29].

Lower formaldehyde emission from the panels made from UF resin modified with lignin

is due to methylene bridges involving completely or partially phenolic moieties being

more stable than pure UF methylene bridges against hydrolysis. The physicochemical

properties of the synthesized resins indicated also that the free formaldehyde content of

the resins modified with lignin is lower than for the control resin (UF resin). For these

reasons, the lignin based resins yield lower formaldehyde emissions compared to UF
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

resins.

The results also indicate that the panels made from PLUF resins exhibited lower

formaldehyde emission than those made from LUF and UF resins, respectively. This is

because of the presence of more reactive sites in phenolated lignin which can react with

free formaldehyde in the resins.

The structural changes of UF resin containing 20% phenolated lignin compared to UF

resin was analyzed by XRD.

3.5. XRD Analysis

X-ray diffractograms of cured UF and PLUF resins are illustrated in Fig. 4. As shown,

the UF resin has a single sharp peak at a 2θ angle of about 21˚. Compared to the UF resin,

the PLUF resin exhibited a weaker peak at 19˚. In addition, wide peak appeared in the

PLUF resin, indicating different crystalline regions for these types of resin. The height of

13
 the peaks (intensity) in the UF resin depends upon a number of factors [30]. The

crystallinity is the main factor influencing the height of the peaks. A comparison

between UF and PLUF resins indicated that the crystallinity of the cured PLUF resin is

lower than that of the UF resin. The measured decrease in the PLUF resin crystallinity is

probably related to the amorphous structure of the lignin incorporated into the UF resin

[31]. The previous study indicated that the crystalline regions of cured UF resins with

lower F/U mole ratio contribute partially to the improved hydrolytic stability of the cured

resin [24].
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

4. CONCLUSIONS

The aim of this research was to reduce formaldehyde emission from particleboard bonded

with UF resin by phenolated Kraft lignin. In summary, the following conclusions can be

drawn from the results-mentioned above:

According to the FTIR spectra, compared to Kraft lignin spectra, a new peak at a

920 cm-1 band was detected for phenolated lignin. The phenolated lignin exhibited also

higher amounts O-H bonds and lower C-O bonds compared to unmodified lignin.

It is possible to partially (20%) replace second urea in the UF synthesis by

phenolated Kraft lignin (adjusted to pH=7).

The physicochemical several tests (gel time, viscosity and free formaldehyde

content) of the lignin based resins indicate that the reactivity of lignin in UF resins

significantly increases by phenolation.

14
 The panels made from the phenolated Kraft lignin resin presented lower

formaldehyde emission and higher internal bond strength than those made from the

unmodified Kraft lignin resin.

XRD analysis indicated that the crystallinity of the UF resin decreased with

addition of phenolated lignin.

Finally it can be concluded that since both synthesis of UF resins and lignin

phenolation are carried out under acid conditions, phenolation is an interesting way of

modifying lignin. Besides, unreacted phenol would not need to be removed from the
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

phenolated product. It would be incorporated in to the UF formulation.

REFERENCES

[1] Boran, S., Usta, M., and Gumuskaya, E., Int. J. Adhes. Adhes. 31, 674–678 (2011).

[2] Zhang, J., Wang, X., Zhang, S., Gao, Q., and Li, J., Bioresource. 8, 5500-5514

(2013).

[3] Salem, M.Z.M., Bohm, M., Berankova, J., and Srba, J., Environ. 46, 1946-1953

(2011).

[4] Roffael, E., Johnsson, B., and Engstrom, B. J., Taiwan. Inst. Chem. E. 45, 2029-2038

(2014).

[5] Uchiyama, S., Matsushima, E., Kitao, N., Tokunaga, H., Ando, M., and Ostubo, Y.,

Atmos Environ. 41, 8825-8830 (2007).

[6] Mansouri, H.R., Pizzi, A., and Leban, J.M., Holz. Roh. Werkst. 64, 218–220 (2006).

[7] Park, B.D., Kim, Y.S., Singh, A.P., and Lim, K.P., J. Appl. Polym. Sci. 88, 2677–

2687 (2003).

15
 [8] Kim, S. J., Hazard. Mater. 176, 14–29 (2010).

[9] Wolkoff, P., Clausen, P.A., and Wilkins, C.K., Nielsen, G.D., Indoor Air. 10, 82–91

(2000).

[10] Abdullah, Z.A., and Park, B.D. J. Appl. Polym. Sci. 117, 3181-3186 (2010).

[11] Zhao, C., Pizzi, A., and Garnier, S. J. Appl. Polym. Sci. 74, 359–378(1999).

[12] Pizzi, A., and Mittal, K.L., Handbook of Adhesive Technology, (Marcel Dekker,

New York, 2003).

[13] Rozman, H.D., Tan, K.W., Kumr, R.N., Abubakr, A., Mohd, Z.A., and Ismail, H.,
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

Europ. Polym.J. 36,1483-1494 (2000).

[14] Torre, M.J.D.L., Moral, A., Hernandez, M.D, Cabeza, E., and Tijero, A., Ind. Crop.

Prod. 45, 58–63 (2013).

[15] Doherty, W., Mousaviouna, P., and Fellows, C., Ind. Crop. Prod. 33, 259-276

(2011).

[16] Mai, C., Milstein, O., and Huttermann, A., J. Biotechnol. 79, 173-83 (2000).

[17] Mansouri, N.E.E.l., and Salvado, J., Ind.Crop. Prod. 24, 8–16 (2006).

[18] Hu, L., Pan, H., Zhou, Y., Zhang, M., Bioresource. 6, 3515-3525 (2011).

[19] Alonso, M.V., Oliet, M., Rodriguez, F., Garcia, J., Gilarranz, M.A., and Rodriguez,

J., J. Technol. 96, 1013-1018 (2005).

[20] Mancera, C., Ferrando, F., Salvado, J., and Mansouri, N.E.E.l., Biomass. Convers.

Biorefin. 35, 2072-2079 (2011).

[21] Younesi- Kordkheili, H., Kazemi-Najafi, S., Behrooz, R., and Pizzi, A., Holz. Roh.

Werckst. 73, 77-85 (2015).

[22] Cetin, N.S., and Ozmen, N., Int. J. Adhes. Adhes. 22, 477-480 (2002).

16
 [23] Vazquez, G., Gonzalez, J., and Antorrena, F.G., Bioresource. Technol. 60, 191-198

(1997).

[24] Park, B.D., and Jeong, H.W. Int. J. Adhes. Adhes. 31, 524–529 (2011).

[25] Tejado, A., Kortaberria, G., Pena, C., Labidi, J., Echeverria, J.M., and Mondragon,

I., Ind. Crop. Prod. 27, 208–213 (2008).

[26] Khan, M.A., and Ashraf, S.M., Indian. J. Chem. Techn. 13, 347-52 (2006).

[27] Gavrilovic-Grmusa, I., Dunky, M., Miljkovic, J., and Djiporovic-Momcilovic, M. J.,

Adhes. Sci. Technol. 24, 1753-1768 (2012).

Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

[28] Christjanson, P., Suurpere, A., and Siimer, K., E-polymers. 4, 398- 407 (2004).

[29] Que, Z., and Furuno, T., Wood. Sci. Technol. 41, 267-79 (2007).

[30] Levendis, D., Pizzi, A., and Ferg, E., Holzforchung. 46, 263-69 (1992).

[31] Sevastyanova, Q., Qin, W., and Kadla, J.F. J. Appl. Polym. Sci. 117, 2877-2881

(2010).

17
 Table 1. FTIR assignment of lignin

Assignment Bond position(cm-1)

O-H stretching 3421

C-H stretching 2937

C-H stretching 2840

C=O stretching 1682

Aromatic skeletal vibration+ C=O stretching 1603

Aromatic skeletal vibration 1514

Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

C-H deformation 1462

C-H in-plane deformation with aromatic ring stretching 1425

C-O of the syringyl ring 1327

C-O of the guaiacyl ring 1269

C-C and C-H stretching 1215

Aromatic C-H in-plane deformation in the guaiacyl ring 1151

Aromatic C-H deformation in the syringyl ring 1116

Aromatic C-H in-plane deformation 1033

18
 Table 2 Physicochemical Properties of resins

Properties Resin Viscosity Content of Gel Density (kg/l)

(mPa*s) free time (s)

formaldehyde

(%)

UF (control) 278±13 0.40±0.01 55±2 1.238±0.031

LUF 10 244±10 0.34±0.02 74±4 1.220±0.03

LUF 15 231±11 0.31±0.01 76±3 1.217±0.011

Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

LUF 20 222±14 0.3±0.03 85±2 1.215±0.01

PLUF 10 269±7 0.26±0.009 60±4 1.231±0.0013

PLUF 15 260±10 0.24±0.02 63±3 1.228±0.012

PLUF 20 252±9 0.22±0.008 66±5 1.226±0.02

19
 Figure 1. FTIR spectra of unmodified and penolated Kraft lignins.
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

20
 Figure 2. Internal bond strength (IB) of the manufactured particleboard made from

synthesized resins.
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

21
 Figure 3. Formaldehyde emission from manufactured particleboards made from

synthesized resins.
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

22
 Figure 4. XRD analysis of UF and PLUF resins.
Downloaded by [Antonio Pizzi] at 10:51 07 June 2015

23

View publication stats