Composites Science and Technology 72 (2012) 667–674

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Composites Science and Technology

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Formulation optimization of unreinforced and lignin nanoparticle-reinforced

phenolic foams using an analysis of variance approach
B. Del Saz-Orozco ⇑, M. Oliet, M.V. Alonso, E. Rojo, F. Rodríguez
Dpto. de Ingeniería Química, Facultad de CC. Químicas, Universidad Complutense de Madrid, Avda. Complutense s/n, 28040 Madrid, Spain

a r t i c l e i n f o a b s t r a c t

Article history: Formulations of unreinforced and lignin nanoparticle-reinforced phenolic foams were optimized using an
Received 1 August 2011 analysis of variance approach. The variables studied in the formulation of phenolic foams were stirring
Received in revised form 11 January 2012 speed (650–850 rpm) and blowing agent amount (1.5–3.5 wt.%). For lignin nanoparticle-reinforced phe-
Accepted 15 January 2012
nolic foams, the variables were lignin nanoparticle weight fraction (1.5–8.5 wt.%) and blowing agent
Available online 25 January 2012
amount (1.5–3.5 wt.%). The responses measured for both foams were density, compressive modulus,
and compressive strength. In addition, the morphology of the foams was observed using scanning elec-
Keywords:
tron microscopy (SEM) to determine cell size distributions. The results showed that the variables studied
A. Particle–reinforced composites
A. Polymer–matrix composites (PMCs)
exhibited a strong influence on the responses and the cell size distribution of the foams. Statistical mod-
B. Mechanical properties els allowed for prediction of the properties of the foams and for comparison of the properties of unrein-
C. Modelling forced and lignin nanoparticle-reinforced phenolic foams. The incorporation of lignin nanoparticles in
D. Scanning electron microscopy (SEM) phenolic foams results in a compressive modulus and compressive strength that has up to 128% and
174%, respectively, of the values for unreinforced foams. The amount of blowing agent saved to produce
a reinforced foam was up to 31% of the amount necessary to produce an unreinforced foam of the same
density.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction polymeric materials. Some blends of lignin and thermoplastic

Phenolic foams exhibit low thermal conductivity, exceptional
fire-resistant properties, high thermal stability over a broad range
of temperatures, and low cost [1–3]. These advantageous features
make this type of foam suitable for structural and insulating appli-
cations where fire resistance is critical. In contrast, these materials
show relatively low mechanical performance and extreme friability
compared to other polymeric foams [4–6]. Due to these drawbacks,
much research has been focused on creating tougher phenolic foams
[4–10]. A first approach to increase the toughness of phenolic foams
involved the incorporation of modifiers and certain inert fillers, but
the success was limited [4–6]. The addition of synthetic fibers, such
as glass and aramid, has been found to increase the strength and
toughness of phenolic foams [4–10]. In recent years, the emphasis
on creating low-environmental-impact products has led many
researchers to study the improvement of polymeric material perfor-
mance using bio-based reinforcements or fillers, such as wood flour,
pulp fibers, flax, sugarcane bagasse, and lignin [11–17]. Lignin is an
amorphous phenolic heteropolymer and is one of the main
components of wood. This natural polymer has a low density, low
cost, and high availability [18]. The most promising alternative for
the revalorization of lignin is its use in the synthesis of new
⇑ Corresponding author. Tel.: +34 91 394 42 49; fax: +34 91 394 42 43.
E-mail address: bsazorozco@quim.ucm.es (B. Del Saz-Orozco).
polymers were found to show high mechanical and thermal perfor-
mance [19,20]. With respect to phenolic materials, researchers have
mainly focused on the use of lignin as a phenol substitute in the syn-
thesis of lignin–phenol–formaldehyde resins because of the similar
chemical structures [21–24]. The use of lignin as a reinforcing agent
or filler in phenolic composites has not been widely reported.
Several studies have developed predictive models to estimate
the behavior of composite foams [10,25–27]. One of the most
successful approaches uses analysis of variance (ANOVA), which
reduces the number of experimental interactions and yields the
maximum amount of information about the variables affecting
the system. Some work demonstrates the utility of the ANOVA
method by describing the behavior of reinforced plastic foams
[10,25]. For example, Alonso et al. [25] studied the influence of
the density of foams, length, and loading of glass fibers on the
mechanical properties of glass fiber-reinforced epoxy foams. Desai
et al. [10] predicted the mechanical properties and density of
reinforced phenolic foams as a function of blowing agent amount,
loading, and length of glass fiber using ANOVA.
The aim of the present work is to apply the ANOVA method to
determine the influence of the formulation variables of phenolic
foams (PFs) and lignin nanoparticle-reinforced phenolic foams
(LRPFs), such as stirring speed, blowing agent amount, and lignin
nanoparticle weight fraction, on the mechanical properties and
density of the product foam.

0266-3538/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2012.01.013
668 B. Del Saz-Orozco et al. / Composites Science and Technology 72 (2012) 667–674

Table 1
Experimental conditions and results of the experiments for PFs and LRPFs.

Run Design I Design II

3
S (rpm) B (wt.%) q (kg/m ) E (MPa) rc (MPa) L (wt.%) B (wt.%) q (kg/m3) E (MPa) rc (MPa)
1 750 2.5 142.9 25.32 1.021 5 2.5 100.5 9.57 0.466
2 650 3.5 193.5 46.59 1.691 8.5 3.5 91.6 8.24 0.392
3 850 1.5 173.9 39.93 2.113 8.5 1.5 158.0 37.20 1.639
4 750 3.91 137.2 20.09 0.650 9.95 2.5 100.9 10.69 0.548
5 891 2.5 130.2 17.79 0.877 5 3.91 80.3 4.30 0.270
6 850 3.5 122.7 23.19 0.816 1.5 3.5 126.9 15.58 0.738
7 650 1.5 255.0 74.17 3.972 0.05 2.5 130.2 18.66 0.878
8 750 2.5 149.4 24.06 1.078 5 2.5 108.8 10.03 0.500
9 750 2.5 159.5 30.56 1.253 1.5 1.5 206.2 42.19 2.394
10 750 1.09 239.8 69.93 3.551 5 2.5 98.6 9.85 0.428
11 609 2.5 255.1 74.77 3.492 5 1.09 211.5 41.34 2.145

2. Materials and methods

a
2.1. Materials and synthesis of the foams

The phenolic resol resin and hardener (ACE 1035) used for foam
preparation were supplied by Momentive Specialty Chemicals. The
Ò
surfactant, catalyst, and blowing agent employed were Tween 40
(Sigma Aldrich), phenol-4-sulfonic acid (Sigma Aldrich), and n-
pentane (Panreac). Lignin nanoparticles were calcium softwood
lignosulfonates with an average diameter of 1.6 lm (Lignotech Ibé-
rica). The foams were synthesized with a phenolic:surfactant:cata-
lyst:blowing agent:hardener ratio of 100:2:4:1.1–3.9:20 (by
weight). A previous mixing step for resol resin and lignin nanopar-
ticles was performed for the formulation of LRPFs. After mixing the
components, the sample was poured into a mold and held for 1 h at
80 °C. Finally, the material was post-cured for 24 h at 105 °C.
b
2.2. Experimental set-up and procedure

Experimental design is a statistical tool that allows for reduc-

tion of the total number of runs necessary to study a system. In
addition, experimental design enables one to simultaneously ana-
lyze the influence of all variables (factors) that affect the system
[28–30]. The first step in developing a statistical design is to know
the variables that influence the system and to determine which are
independent and dependent. Then, it is necessary to decide the fac-
tors (independent variables) and their ranges and to determine the
responses (dependent variables) to be measured [30]. The next
step is to choose the type of experimental design. In the present
work, two central composite experimental designs were chosen
to study the formulation of PFs and LRPFs, designated by 22. This
designation signifies that experimental designs have two factors
c
and two levels. The experimental designs were employed to obtain
statistical models that explain the relationship between the factors
and responses considered. ANOVA and multiple regression meth-
ods were performed using statistical software. ANOVA allows one
to determine which effects show significance at a given level. Each
effect has a probability (P-value) and an F distribution (F-test),
which indicate the significance of that effect. The fit of the model
is given by the scatter and R2 (correlation coefficient), which must
be near 100%. Finally, the responses can be plotted as a response
surface or as a contour map to graphically study the influence of
the factors within the ranges considered.

2.3. Plan of experiments

2 2
Two 2 central composite experimental designs (11 runs: 2 + 3
center points + 4 star points) were employed to study the formula-
tion of PF (Design I) and LRPF (Design II). The variables studied in
Design I were stirring speed (S) and blowing agent amount (B),
Fig. 1. Contour map for (a) density (kg/m3), (b) compressive modulus (MPa), and (c)
compressive strength (MPa) of PF.
and their ranges were 650–850 rpm and 1.5–3.5 wt.% (relative to
the mass of the resin), respectively. In Design II, the variables stud-
 B. Del Saz-Orozco et al. / Composites Science and Technology 72 (2012) 667–674
a e
b f
c g
d h
Fig. 2. SEM images for PFs formulated at (a) 609, (b) 750, (c) 891 rpm and 2.5 wt.% blowing agent and (d) their respective cell size distributions; (e) 1.09, (f) 2.5, (g) 3.91 wt.%
blowing agent and 750 rpm and (h) their respective cell size distributions.
ied were the lignin nanoparticle weight fraction (L) and the blow-
ing agent amount (B), and the respective ranges were 1.5–8.5 wt.%
and 1.5–3.5 wt.% (both relative to the mass of the resin). The re-
sponses measured for model development in both designs were
density (q), compressive modulus (E), and compressive strength
(rc). Stirring speed was kept constant at 820 rpm for the formula-
tion of the foams of Design II. The experimental conditions and re-
sults from the study of the formulation of PFs and LRPFs are
summarized in Table 1.
Data processing was performed using Statgraphics Centurion XV.
Quadratic models were obtained using the least squares method,
and model equations for the responses can be represented by Eq.
(1).
669
Z ¼ a0 þ a1 X 1 þ a2 X 2 þ a12 X 1 X 2 þ a11 X 21 þ a22 X 22 ð1Þ
where Z is the response (q, E, and rc), a0 is a constant, a1 and a2 are
linear coefficients, a12 is a cross-product coefficient, a11 and a22 are
quadratic coefficients and X1 and X2 are the factors studied. Using
ANOVA, non-significant effects were rejected from the model
regression, and the suitability of the model was checked. Contour
maps of the responses were plotted to show the most appropriate
operating conditions in the formulation of the foams.
In addition, scanning electron microscopy (SEM) was used to
study the morphology and cell size distributions of the foams to
establish how these are affected by the formulation variables
studied.
670 B. Del Saz-Orozco et al. / Composites Science and Technology 72 (2012) 667–674

2.4. Apparent density E ðMPaÞ ¼ 806:759  1:65747  S  60:6653  B

Apparent density was calculated in accordance with ASTM
D1622 [31]. Cubic specimens were cut with a keyhole saw (Bosh
Ò
PST 900 PEL) and polished with a Buehler MetaServ 3000 polisher
to a size of 2.54 cm. A minimum of five replicates of each sample
were measured.
2.5. Compression tests
Compression tests were performed using a universal testing
machine (Zwick/Roell Z030) in accordance with ASTM D1621
[32]. The same specimens employed for apparent density measure-
ments were placed between stainless steel plates, and a load was
applied uniformly with a crosshead rate of 2.5 mm/min. Compres-
sive strength was obtained from the maximum value of stress–
strain curve (strain <10%), and compressive modulus was deter-
mined from the slope of the curve. A minimum of five replicates
of each sample were tested.
þ 0:000989794  S2 þ 9:26294  B2 ð3Þ
rc ðMPaÞ ¼ 42:7202  0:0882842  S  3:42488  B
þ 0:000053496  S2 þ 0:49296  B2 ð4Þ
The contour maps for compressive modulus and strength are
shown in Fig 1. Compressive modulus and strength decreased
when stirring speed and blowing agent amount were increased.
This is because of a drop in the density of the foams [10,27].
The morphology of the PFs was observed using SEM to establish
the effect of stirring speed and blowing agent content on the cellu-
lar structure. SEM images of the foams formulated at 609, 750, and
891 rpm with 2.5 wt.% blowing agent, as well as the corresponding
cell size distributions, are shown in Fig. 2. Altering the stirring
speed changes the cell size distribution in the PFs. For example,
the mean cell size (D) in the PF formulated at 609 rpm was
0.103 mm, whereas the mean cell size in the PFs formulated at stir-

2.6. Scanning electron microscopy

a
A scanning electron microscope (JEOL JM-6400) was used to ob-
serve the cellular structure of the foams. Specimens were cut with
a keyhole saw to obtain square bars with a 10 mm2 cross-section
and 30 mm in length. The samples were fractured after being cryo-
genically frozen to avoid structural deformation of the foams. The
fractured surface was gold coated to create a conductive interroga-
tion surface. The operation voltage of the SEM was 40 kV.

3. Results and discussion

3.1. Unreinforced phenolic foams

The influence of stirring speed (S) and blowing agent amount

(B) on density (q), compressive modulus (E), and compressive b
strength (rc) were studied using statistical tools. The average den-
sity values of the PFs were in the range of 122.7–255.0 kg/m3 (Ta-
ble 1). The ANOVA for the density (q) of the PFs used a significance
level of 95%, as shown in Table A1. The factors with F <18.51 and P-
values >0.05 exhibit a statistical significance level lower than 95%
for density, and they must be rejected based on the ANOVA, as is
the case for effect SB. The model for the density (q) of PFs with
all significant effects is given by Eq. (2):

q ðkg=m3 Þ ¼ 1773:07  3:40318  S  121:6  B

þ 0:001995  S2 þ 17:875  B2 ð2Þ
The contour map for the density of PFs is shown in Fig. 1. Den-
sity decreased when the stirring speed and blowing agent amount
were increased. As stirring speed increased, the surface tension of c
the formulation mixture decreased; therefore, the energy required
to nucleate a bubble became lower [33]. Thus, the amount of gas
phase formed was higher, and the foam density was lower. When
the amount of blowing agent was increased, the gas content in the
mixture rose [34]. Hence, the gas/solid phase ratio in the foams be-
came higher, and their density decreased.
The average values of compressive modulus (E) and strength
(rc) for the PFs were in the ranges of 17.79–74.77 MPa and
0.650–3.972 MPa, respectively, and are summarized in Table 1.
The ANOVA results for compressive modulus and strength are
shown in Tables A2 and A3, respectively. For both responses, the
SB effects were rejected because they exhibited significance lower
than 95%. The models obtained for compressive modulus (E) and
strength (rc) are given by:
Fig. 3. Contour map for (a) density (kg/m3), (b) compressive modulus (MPa), and (c)
compressive strength (MPa) of LRPFs.
 B. Del Saz-Orozco et al. / Composites Science and Technology 72 (2012) 667–674 671

ring speeds greater than or equal to 750 rpm was approximately
0.07 mm. When stirring speed is increased, the surface tension of
the formulation mixture decreases. The decrease in surface tension
favors the nucleation of bubbles in the foaming process, resulting
in finer cells in the foam structure [33].
SEM images for the PFs formulated at 750 rpm and blow-
ing agent amounts of 1.09, 2.5, and 3.91 wt.% are also shown in
Fig 2. The influence of the blowing agent amount on the
morphology of the foams is less pronounced than the stirring
speed. However, when the blowing agent amount was increased,
the mean cell size (D) of the foams increased. When the blowing
agent amount increases, the gas supply into the formulation mix-
ture is higher. Therefore, the coalescence of nearby gas bubbles
was favored and resulted in an increase in the cell size of the foams
[34].
The selection of stirring speed during the formulation of pheno-
lic foams was based on a compromise between achieving the best
insulating features, the lowest density, and the greatest mechani-
cal performance of the material. The coefficient of thermal conduc-
tivity of polymeric foams decreases as the cell size become smaller
because of fewer paths for heat transfer by radiation and convec-
tion [1,27]. The mean cell size (D) obtained for the PFs formulated
at stirring speeds greater than or equal to 750 rpm was much lower
than that obtained for foams formulated at stirring speeds lower
than 750 rpm (Fig. 2). Thus, a stirring speed greater than or equal
to 750 rpm seems suitable. The contour maps for density, compres-

a e

b f

c g

d h

Fig. 4. SEM images for LRPFs formulated at (a) 0.05, (b) 5, (c) 9.95 wt.% lignin nanoparticles and 2.5 wt.% blowing agent and (d) their respective cell size distributions; (e) 1.09,
(f) 2.5, (g) 3.91 wt.% blowing agent and 5 wt.% lignin nanoparticles and (h) their respective cell size distributions.
672 B. Del Saz-Orozco et al. / Composites Science and Technology 72 (2012) 667–674
sive modulus, and compressive strength of the foams are approxi-
mately unchanged for a particular blowing agent amount at stir-
ring speeds faster than 820 rpm. Thus, the stirring speed for the
formulation of LRPFs was set at 820 rpm.
3.2. Lignin nanoparticle-reinforced phenolic foams
The influence of lignin nanoparticle weight fraction (L) and
blowing agent amount (B) on density (q), compressive modulus
(E), and compressive strength (rc) was studied using statistical
methods. The average values of density of the LRPFs studied were
in the range of 80.33–211.5 kg/m3, as exhibited in Table 1. The AN-
OVA for the density (q) of LRPFs using a statistical significance le-
vel of 95% is shown in Table A4. The factor LB was rejected because
it was not significance. The model for the density of LRPFs with all
significant effects is shown below:
q ðkg=m3 Þ ¼ 407:92  12:7937  L  168:344  B
þ 0:833433  L2 þ 25:3897  B2
The contour map obtained for the density of LRPFs is shown in
Fig 3. As the lignin nanoparticle weight fraction and blowing agent
amount increased, the density of LRPFs decreased. Lignosulfonates
exhibit surfactant properties [35], which decreases the surface ten-
sion of the formulation mixture, improves the compatibility be-
tween the reagents and favors the nucleation of bubbles [2,33].
Therefore, bubble formation in the system is greater, and the
amount of gas in the foam increases, decreasing its density.
The average values of the compressive modulus (E) and strength
(rc) of the LRPFs studied were in the range of 4.30–42.12 MPa and
0.270–2.394 MPa, respectively, and are summarized in Table 1. The
ANOVA using a significance level of 95% for compressive modulus
and strength are shown in Tables A5 and A6. The models for the
compressive modulus (E) and strength (rc) of LRPFs are given by
Eqs. (6) and (7).
EðMPaÞ ¼ 105:884  3:84604  L  53:9821  B
þ 0:342278  L2  0:167857  LB þ 8:26546  B2
rc ðMPaÞ ¼ 6:10491  0:297781  L  3:1106  B
þ 0:0168889  L2 þ 0:0291786  LB þ 0:454092  B2
The contour maps obtained for compressive modulus and
strength of LRPFs are shown in Fig. 3. Compressive modulus and
strength decreased when the lignin nanoparticle weight fraction
and blowing agent amount were increased. This is because of a de-
crease in foam density, as was discussed for PFs in Section 3.1.
The morphology of the LRPFs was observed using SEM to estab-
lish how the foam is affected by the lignin nanoparticle weight
fraction (L) and blowing agent amount (B). SEM images of foams
formulated with 0.05, 5, and 9.95 wt.% lignin nanoparticles and
2.5 wt.% blowing agent, as well as the cell size distributions of
these foams are shown in Fig 4. As the lignin nanoparticle weight
fraction increased, the mean cell size decreased. For example, the
mean cell size for foams formulated with 9.95 wt.% lignin
nanoparticles was 0.066 mm, whereas the mean cell size of foams
formulated with 0.05 wt.% lignin nanoparticles was 0.086 mm.
Lignosulfonates exhibit surfactant properties and decrease the sur-
face tension of the formulation mixture. This reduction in surface
tension favors the nucleation of bubbles in the system and results
in finer cells in foam structure [2,33].
SEM images of the foams formulated with 5 wt.% lignin nano-
particles and 1.09, 2.5, and 3.91 wt.% blowing agent, as well as
the cell size distributions of these foams are shown in Fig. 4. As
the blowing agent amount increased, the mean cell size also in-
creased. The observed trend is consistent with that obtained for
PFs, as mentioned in Section 3.1.
3.3. Comparison between unreinforced and lignin nanoparticle-
reinforced phenolic foams
Combining the contour maps for density and mechanical prop-
erties of LRPFs (Fig. 3) indicates that the most favorable mechanical
properties of LRPFs occur with 8.5 wt.% lignin nanoparticles in
the material. The predictive models obtained in Sections 3.1 and
3.2 allow for determination of density, modulus, and strength of
PFs and LRPFs (Eqs. (2)–(7)). The mechanical properties of PFs (for-
mulated at 820 rpm) and LRPFs (formulated with 8.5 wt.% lignin
nanoparticles) in the density range of 120–160 kg/m3 are shown in
Fig 5. This range of density is chosen due to the applications con-
sidered, e.g., insulating and structural applications. In addition,
the corresponding amounts of blowing agent employed in the for-
mulation of these foams are also given.
ð5Þ The compressive moduli of LRPFs are greater than those of PFs
at studied densities that were lower than 155 kg/m3. For example,
the compressive moduli for the PF and LRPF with a density of
120 kg/m3 were 14.70 and 18.86 MPa, respectively; thus, the com-
pressive modulus of the LRPF was 128% of the compressive modu-
lus of the PF. The compressive strengths of LRPFs are greater than
those of PFs at the studied densities that were lower than 145 kg/
m3. For example, the compressive strengths for the PF and LRPF
with a density of 120 kg/m3 were 0.474 and 0.824 MPa, respec-
tively; thus, the compressive strength of the LRPF was 174% of
the compressive strength of the PF.
The improvement in mechanical properties obtained with the
addition of lignin nanoparticles as a reinforcing agent in phenolic
foams is similar or superior to the improvement shown in other re-
search, in which phenolic foams were reinforced with non-biode-
gradable reinforcements, such as aramid and glass fibers [6,9,10].
For example, the compressive modulus and strength of phenolic
foams reinforced with 5 wt.% aramid fibers, reported by Shen and
ð6Þ
ð7Þ
Fig. 5. Compressive modulus and strength predicted by statistical models and
blowing agent amount employed in the formulation for PFs (820 rpm) and LRPFs
(8.5 wt.% lignin nanoparticle) with several densities.
 B. Del Saz-Orozco et al. / Composites Science and Technology 72 (2012) 667–674 673

Nutt [6], were 92% and 118%, respectively, of the reference foam Table A2
used in that study. The compressive modulus and strength of Analysis of variance for the compressive modulus of PFs.

10 wt.% glass fiber-reinforced phenolic foams were 197% and Source SDQ Mean square d.f.a F-test P-values
145%, respectively, of the reference foam used in that study. S 2388.16 2388.16 1 200.98 0.0049
Note that the use of lignin nanoparticles as a reinforcing agent B 1647.51 1647.51 1 138.65 0.0071
reduces the amount of blowing agent needed to formulate phenolic SB 29.3764 29.3764 1 2.47 0.2565
foams, as shown in Fig. 5. The ratio between the blowing agent em- S2 553.235 553.235 1 46.56 0.0208
B2 484.526 484.526 1 40.78 0.0237
ployed in the formulation of LRPFs and PFs varied between 69% Lack of fit 151.576 50.5255 3 4.25 0.1962
(density 120 kg/m3) and 83% (density 160 kg/m3). Therefore, blow- (180.953) (45.2382) (4) (3.81) (0.2187)
ing agent saved with the incorporation of lignin nanoparticles is up Pure error 23.7651 11.8825 2 – –
to 31%. The reduction in blowing agent is potentially interesting Total 5043.02 – 10 – –
because lignin nanoparticle-reinforced phenolic foams can be pro- (): New lack of fit values after analysis of variance with all the significance effects.
duced that are competitive with glass and aramid fiber-reinforced R2 = 95.94%.
a
phenolic foams while reducing the use of chemicals and the d.f.: degrees of freedom.
associated costs.

4. Conclusions Table A3
Analysis of variance for the compressive strength of PFs.
The formulation of PFs and LRPFs was studied using statistical Source SDQ Mean square d.f.a F-test P-values
models derived using ANOVA and cell size distributions obtained
S 5.1716 5.1716 1 353.82 0.0028
using SEM. The most appropriate stirring speed for the formulation B 7.37402 7.37402 1 504.51 0.0020
of the foams is 820 rpm. The greatest mechanical performance of SB 0.242064 0.242064 1 16.56 0.0554
LRPFs (q = 120–160 kg/m3) is obtained when the amount of lignin S2 1.61608 1.61608 1 110.57 0.0089
nanoparticles in the foam is 8.5 wt.%. With the addition of lignin B2 1.37228 1.37228 1 93.89 0.0105
Lack of fit 0.150671 0.0502238 3 3.44 0.2335
nanoparticles to the phenolic foam, the modulus and strength were (0.392735) (0.0981838) (4) (6.72) (0.1338)
up to 128% and 174%, respectively, of the values for the Pure error 0.0292327 0.0146163 2 – –
unreinforced foams. Total 15.28 – 10 – –
Moreover, the amount of blowing agent saved in the formula-
(): New lack of fit values after analysis of variance with all the significance effects.
tion of a LRPF is up to 31% of the amount employed in the formu- R2 = 97.24%.
lation a PF of the same density. The incorporation of lignin a
d.f.: degrees of freedom.
nanoparticles allows for the following: LRPFs to be competitive
in mechanical performance with synthetic fiber-reinforced pheno-
lic foams, a reduction of the amount of blowing agent employed in
the formulation of the foams, the use of a industrial byproduct, and
the manufacture of more environmentally friendly foams. Table A4
Analysis of variance for the density of LRPFs.

Source SDQ Mean square d.f.a F-test P-values

Acknowledgement L 1948.83 1948.83 1 65.78 0.0149
B 13708.6 13708.6 1 462.69 0.0022
The authors are grateful to the ‘‘Ministerio de Educación y LB 41.8609 41.8609 1 1.41 0.3566
Ciencia’’ (Project CTQ2007-64071) and the ‘‘Ministerio de Ciencia L2 588.622 588.622 1 19.87 0.0468
B2 3640.28 3640.28 1 122.87 0.0080
e Innovación’’ (Project CTQ2010-15742) for financial support. Lack of fit 866.413 288.804 3 9.75 0.0945
(908.274) (227.069) (4) (7.66) (0.1187)
Pure error 59.2555 29.6277 2 – –
Appendix A Total 20311.7 – 10 – –

(): New lack of fit values after analysis of variance with all the significance effects.
Tables A1–A6. R2 = 95.24%.
a
d.f.: degrees of freedom.

Table A1
Analysis of variance for the density of PFs.
Table A5
Source SDQ Mean square d.f.a F-test P-values Analysis of variance for the compressive modulus of LRPFs.
S 13491.9 13491.9 1 192.82 0.0051 Source SDQ Mean square d.f.a F-test P-values
B 8307.49 8307.49 1 118.73 0.0083
SB 26.5225 26.5225 1 0.38 0.6008 L 69.6276 69.6276 1 1295.80 0.0008
S2 2247.54 2247.54 1 32.12 0.0297 B 1456.72 1456.72 1 27110.12 0.0000
B2 1804.32 1804.32 1 25.79 0.0367 LB 1.38062 1.38062 1 25.69 0.0368
Lack of fit 244.674 81.558 3 1.17 0.4926 L2 99.2781 99.2781 1 1847.61 0.0005
(271.197) (67.7991) (4) (0.97) (0.5649) B2 385.792 385.792 1 7179.75 0.0001
Pure error 139.94 69.97 2 – – Lack of fit 100.955 33.6517 3 626.27 0.0016
Total 25349.4 – 10 – – Pure error 0.107467 0.0537333 2 – –
Total 2033.77 – 10 – –
(): New lack of fit values after analysis of variance with all the significance effects.
R2 = 98.38%. R2 = 95.03%.
a
a
d.f.: degrees of freedom. d.f.: degrees of freedom.
674 B. Del Saz-Orozco et al. / Composites Science and Technology 72 (2012) 667–674

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