Journal of Thermal Analysis and Calorimetry (2021) 146:1049–1062

https://doi.org/10.1007/s10973-020-10096-0

Effect of quantitative characteristic structure of resole phenolic

prepolymer resin on thermal stability, pyrolysis behaviors,
and ablation properties
Honglin Hu1 · Ying Zhang1 · Liang Liu1 · Yunhua Yang1 · Ruilian Yu1 · Jinming Wang1

Received: 28 December 2019 / Accepted: 17 July 2020 / Published online: 4 August 2020
© Akadémiai Kiadó, Budapest, Hungary 2020

Abstract
The chemical structure of resole phenolic prepolymer resin is difficult to be accurately described because it is a mixture
composed of different polymerization degree structures. Limited by the knowledge of prepolymer resin structure, the cross-
linking degree (CLD) of cured resin and the effects of structure on the ablation properties remain unclear. The objective of
this work is to understand the relationship between prepolymer resin structure, CLD of cured resin, and performance. The
quantitative characteristic structure of resole prepolymer and CLD of curing resin was proposed in this work based on the
full understanding of the chemical structure. A fast and accurate identification method was provided for the quality conform-
ity identification of mass production of resole prepolymer phenolic resin. A novel CLD characterization method for high
cross-linking resole phenolic resin was proposed. The results showed that the ablation properties of resole phenolic resin are
optimum when formaldehyde/phenol value of prepolymer is in the range of 1.20–1.46. This study may provide meaningful
information to the understanding of the ablation mechanism of resole phenolic resin, which is a benefit for developing novel
anti-ablation resin.

Keywords Chemical structure · Ablation properties · Cross-link degree · Pyrolysis behavior · Thermal stability

Introduction being quantified. As is known that resole phenolic prepoly-

Resole phenolic resin-based composites are widely applied
in aerospace [1–3], military industry [4], and so on [5, 6],
due to their excellent heat resistance, anti-ablation, mechani-
cal performance, reliability, and low cost. With the rapid
advancement of high-technologies, requirement of resin
matrix used in rigorous environments including high speed,
high temperature, high pressure, high corrosion, is ever
increasing. However, the lack of a full understanding of the
relationship between structure and ablation for resole phe-
nolic resin may be one of the biggest obstacles for develop-
ing novel anti-ablation composites.
For the purpose of comprehension of the relationship, the
chemical structure of prepolymer resin should be prior to
* Yunhua Yang
nanofibre@sina.com
1
Science and Technology on Advanced Functional
Composites Laboratory, Aerospace Research Institute
of Materials & Processing Technology, Beijing 100076,
China
mer resin is a mixture composed of different polymeriza-
tion degree structures. It is difficult to describe the chemical
structure exactly. Compared with novolac phenolic resin,
the cross-linking reaction of resole phenolic resin occurs to
form three-dimensional network structures without adding
any hardener. Lots of excellent work had been reported in
the literature [7]. King and his co-workers [8] had focused
on the analysis of the chemical structure of resole resin by
the method of nuclear magnetic resonance (NMR) and gel
permeation chromatography (GPC). Infrared (IR) spectros-
copy was used to quantitatively characterize the structure
of phenol-formaldehyde resole resin [9]. Nuclear magnetic
resonance (13C-NMR) characterization was employed to
identify the characteristic structure of resole prepolymer
phenolic resin [10]. All these studies pointed to the fact
that important influencing factors on the properties of cured
resin determined quantitatively for resole prepolymer res-
ins were the formaldehyde/phenol (F/P) ratio after synthesis
reaction and the average molecular weight. Therefore, the
F/P and average molecular weight can be as the quantitative
characteristic structure of resole phenolic prepolymer resin.

13
Vol.:(0123456789)
1050
Specifically, the F/P has a significant effect on the perfor-
mance of cured resin including thermal stability, pyrolysis
behaviors, and ablation. Average molecular weight has an
influence on the performance of the composite molding
process such as the resin transfer molded (RTM) process-
ing. However, these analytical ways can not provide a fast
and accurate identification method. For example, in order to
obtain a high-resolution 13C-NMR spectrogram, it is neces-
sary to increase the number of scanning, which will inevi-
tably increase the test time and reduce test efficiency. It is
unfavorable for the quality conformity identification of mass
production of resole phenolic resin. Another example, the
replacement of a chromatographic column with the old one
would bring great results fluctuation of average molecular
weight by GPC, which would influence the quality evalua-
tion of resin.
Subsequently, the quantitative characteristic structure
for cured resole phenolic resin should be defined so as to
build the relationship of prepolymer before and after curing
reaction. Cross-link density is a wide consensus for describ-
ing the cured resin structure [11]. But the measurement of
cross-link density is still a challenge. Several methods are
available for testing the cross-link density of resole phenolic
resin, including the dynamical mechanical analysis (DMA),
swelling, and glass transition temperature (Tg) measure-
ments. DMA method is widely recognized as a more accu-
rate one for evaluating cross-link density. The elastic modu-
lus of resin in the rubbery regime (i.e., T > Tg) is measured
by using a thermal-mechanical testing instrument [12]. The
rubber elasticity theory is applied to calculate the cross-link
density. However, it is difficult to prepare DMA samples
without inner bubbles. Because the curing process of resole
phenolic resin will always release small molecular gas such
as water. Besides, rubber elasticity theory becomes invalid
due to the failure of the Gaussian chain assumption when
the cross-link density is too high. In most cases, the cross-
link density of the fully cured resole phenolic resin used in
ablative materials is high. Therefore, the DMA method is
not entirely applicable in that case.
Pyrolysis mechanism of the phenolic resin has been
reported. Typically, Trick [13] proposed a mechanism of
pyrolysis consisting of three stages. First, the functional
groups of the cured phenolic resin react with each other to
form additional cross-links. Then, the cross-link is destroyed,
leading to the formation of methane, hydrogen, and carbon
monoxide. Finally, the hydrogen atom is stripped from the
phenol ring structure and hydrogen is released. Phenolic
resin is converted into amorphous carbon, accompanied by
the release of a large number of gas products. Each of the
three stages does not represent an elementary reaction but
rather a relatively complicated set of reactions. On the base
of this, Pyrolysis kinetics of phenolic resin was investigated
by non-isothermal thermogravimetry. These results showed
13
H. Hu et al.
that the apparent activation energy of the pyrolysis of phe-
nolic resin was in the range of 150–300 kJ mol−1 [14–16].
The relationship between the structure and thermal prop-
erties of phenolic resin had been investigated [17–20]. Chen
et al. [21] studied the influence of feed F/P on pyrolysis
temperature and char yield of phenolic resin. A maximum
in the benzene ring substitutions, methylene bridge, and the
result of the thermal properties showed that the resin with
F/P molar ratio 1.2 has the highest cross-link density and
highest char yield, over 73%. Hu et al. [22] reported that the
effects of feed F/P ratios on physicochemical characteristics
and foaming properties of the resulting resins were analyzed
based on viscosity, solids content, hydroxymethyl index,
residual monomer content, and molecular structure. Wang
et al. [23] focused on the influence of different cross-link
density on the heat resistance of novolac resin by adjusting
the amount of hardener hexamethylenetetramine (HMTA).
The results reveal that the cross-link of novolac phenolic
resin can improve the thermal stability and char yield of
cured PR simultaneously. However, the relationship between
the structure of resole prepolymer resin, cross-link density
of cured resin, and performance including thermal stability
and ablation remains unclear.
To address the problems mentioned previously, quantita-
tive characteristic structure of resole prepolymer and cross-
link degree (CLD) of curing resin was proposed in this work
based on the full understanding of the chemical structure.
A fast and accurate identification method of the chemical
structure of prepolymer was provided for the quality con-
formity identification of mass production of resole prepoly-
mer phenolic resin. A novel CLD characterization method
for high cross-linking resole phenolic resin was proposed.
The relationship between the structure of resole prepolymer
resin, CLD of cured resin, and performance was studied. The
investigation focused on the effect of prepolymer structure
on the CLD and properties that may provide meaningful
information to the understanding of the ablation mechanism
of resole phenolic resin. It may be a benefit for developing
novel anti-ablation resin.
Experimental
Raw materials
Phenol (P) and formaldehyde (F) were purchased from Sin-
opharm Chemical Reagent Co. Ltd. Ba(OH)2·8H2O used as
a catalyst was purchased from Sinopharm Chemical Reagent
Co., Ltd. Phosphoric acid was obtained from Tianjin Chemi-
cal Plant, China.
Effect of quantitative characteristic structure of resole phenolic prepolymer resin on thermal…
Synthesis of phenolic prepolymer resin
F and P were mixed in a 3000 mL three-neck round-bot-
tomed flask with mechanical stirring at 40 °C. The mole
ratio between F and P was 1.0:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1.
Then, Ba(OH)2·8H2O was added in the mixture under the
agitation. Subsequently, the system temperature was raised
to 60 °C and kept for 2 h, to 90 °C kept for 1 h. 10 mass%
phosphoric acid solution was added into the mixture for
neutralizing the Ba(OH)2·8H2O. The phenolic resin was
obtained after vacuum dewatering and filter.
Samples preparation
20 g resin was put in a closed steel mold. The curing process
was as follows: rising temperature to 80 °C kept for 1 h,
100 °C kept for 2 h, 120 °C kept for 2 h, 140 °C kept for 2 h,
160 °C kept for 2 h, 180 °C kept for 2 h.
The cured samples were ground to ensure its uniform
particle size. Before the thermogravimetric analysis, the
samples were put into an oven at 110 °C for 1 h and then
put into a dryer.
T300 carbon fiber-reinforced phenolic resin composites
were fabricated via RTM, the curing process was the same
with resin.
Characterization
Characteristic structures of resole phenolic prepolymer resin
were characterized by Agilent DD2 600 MHz nuclear mag-
netic resonance (NMR) instrument. The phenolic resin was
dissolved in 99.8% DMSO of the CIL company, and the con-
centration was 20 mg mL−1. The number of scans was used
as 16. Tetramethylsilane was used as an internal standard.
The resonance signal peak at the chemical displacement of
3.5–4.0 ppm corresponds to the methylene proton signal,
and the integral area is defined as ­S1; the resonance signal
peak at 4.2–4.75 ppm is hydroxymethyl proton signal, and
the integral area is defined as S
­ 2; the resonance signal peak
at 6.5–7.5 ppm corresponds to the proton signal of phenol
ring, and the integral area is defined as S ­ 3; the resonance
signal peak at 2.0–2.4 ppm corresponds to the proton signal
of methyl, and the integral area is defined as ­S4. Because the
natural abundance of the hydrogen atom is nearly 100%, the
number of NMR signal peaks is equivalent to the number
of hydrogen atom chemical environment, and the ratio of
sum of dimethylphenol and trimethylphenol
CLD =
sum of benzene and its homologues, phenol and its homologues
1051
the area of the resonance signal peaks is equivalent to the
simplest integer ratio of the number of hydrogen atoms. The
1
H-NMR spectrum has a very high resolution and accuracy
for describing the characteristic functional groups of phe-
nolic resin. Therefore, the characteristic structure of phe-
nolic resin is described by the calculated methylene index
(MI), hydroxymethyl index (HI), and F/P value.
MI can be calculated according to formula (1) as follows:
5S1
MI = (1)
S4
S1 + S3 + 0.5S2 + 3
HI can be calculated according to formula (2) as follows:
5S2
HI = (
S4
)
(2)
2 S1 + S3 + 0.5S2 + 3
F/P value can be calculated according to formula (3) as
follows:
( )
5 S1 + S2
F∕P = ( (3)
)
S
2 S1 + S3 + 0.5S2 + 34
Pyrolysis gas-chromatography–mass-spectrometry (PY-
GC/MS) system was employed to separate and identify the
pyrolysis volatiles. A PY-2020S (Frontier, Japan) pyro-
lyzer joining with GCMS-QP2010 (Shimadzu Co., Japan)
mass spectrometer was used. The pyrolysis temperatures
of 400 °C and 550 °C were used. The temperature of the
pyrolysis chamber before heating and during the separation
of the volatiles was maintained at 200 °C. The separation
of the volatile products was performed in a 30 m capillary
quartz column. Before the chromatography separation, the
temperature of the chromatographic column was progres-
sively increased as follows: (a) 40 °C for 3 min; (b) from 40
to 260 °C at a rate of 10 °C min−1; (c) the capillary column
was maintained at 260 °C for 10 min. Helium gas was used
as the carrier gas. The mass range used for the mass selective
detector was 19–500 m/z. The decomposition products were
identified using the comparison between the experimental
mass spectrum and the mass spectrum library attached to
the PY-GC/MS apparatus. The identification of each vola-
tile product can be confirmed if the qualification percentage
reaches 85% and even higher. In this paper, a quantitative
description of cross-link density is firstly suggested in for-
mula (4), i.e., cross-link degree (CLD), which was obtained
from the result of Py-GC/MS at 550 °C.
× 100% (4)
13
1052
The char residue of pure PF resins was measured by using
TGA (Netzsch STA409PC), which was carried out under
the protection of nitrogen gas in a range of 120–900 °C at
a constant heating velocity of 5 °C min−1, 10 °C min−1,
15 °C min−1, 20 °C min−1. A scanning electron microscope
(SEM) with the type of APOLLO 300 was employed to
investigate the surface morphologies of the specimens after
ablation. The average molecule weight was measured by Gel
Permeation Chromatography(GPC) (DAWN 8+, WYATT).
The temperature of the environment fluctuation is less than
2 °C. The temperature inside and outside of the detector is
35 °C. The flow rate is 1 mL min−1 with 5–8 mg mL−1 for
sample concentration and the injection volume is 20 L. The
sample solution is injected into the chromatographic col-
umn through the injection system. Then, the spectrogram
is recorded. The ablation performance of the composite is
investigated by the arc heating ablation. The sample with a
size of 8.5 cm × 5.0 cm is inlaid on the sample table. During
the test, the high-temperature airflow heated by the lami-
nated heater flows through the supersonic nozzle, forming
the required flow field in the test section, and conducting
the ablation test on the sample. The surface of the sample is
heated for t = 10 s. Mass ablation rate and linear ablation rate
can be calculated according to formula (4) and (5) as follows:
m0 − mf
Mass ablation rate = (5)
8.5 × 5 × t
where m0 and mf are the sample mass at initial and final,
respectively.
h0 − hf
Linear ablation rate = (6)
t
where h0 and hf are the sample thickness at initial and final,
respectively.
Theoretical method
The equation of activation energy E calculated by Kissinger
[24] method is as follows :
( )
dln 𝛽TP−2 E and molecular weight, GPC analysis was carried out to evaluate
( −1 ) = − (7)
d TP R molecular weight in Table 2. It can be obvious observed that
where β and Tp are the heating rate and peak temperature,
respectively.
The reaction frequency factor A calculated by Kissinger
method is as follows:
𝛽Ee(E∕RTP )
A≈ (8)
RTP2
The kinetic analysis from the TGA was carried out using
the conversion rate α according to the formula:
13
H. Hu et al.
m0 − mi
𝛼=
m0 − mf (9)
where m0, mf and ­mi are the mass at initial, final, and
moments, respectively.
The equation of activation energy E calculated by Ozawa
[25] method is as follows:
AE E
lg𝛽 = lg ( ) − 2.315 − 0.4567 (10)
Rg 𝛼T RT
At the same conversion rate αT, lgβ is linearly correlated
with T−1. The activation energy E is calculated according to
the slope of the linear regression equation.
Results and discussion
Characteristic structure of resole phenolic
prepolymer resin
Figure 1 shows the NMR spectrum of phenolic prepolymer
resin synthesized under different F/P ratios and fixed other
synthesis conditions. According to Fig. 1, the characteris-
tic structure including MI, HI, and F/P value was listed in
Table 2. It indicates that the feed ratio of F/P is close to
the F/P value of 1H-NMR. This proves that describing the
characteristic structure of phenolic resin by 1H-NMR is fea-
sible. In addition, it should be noted that the F/P value of
1
H-NMR is slightly higher than the feed ratio of F/P, which
may be caused by the volatilization of free phenol during
the vacuum dehydration stage, resulting in F/P value of 1H-
NMR slightly higher than the feed ratio of F/P.
The MI value increases with the increase in the content of
–CH2-according to the formula (1), which means that the MI
has a directly proportional relation with molecular weight. The
bigger the MI value is, the higher the molecular weight is. It is
worth noted that the MI value of sample No. 3 is lower than
that of sample No. 2 in Table 1, which infers that the molecular
weight of sample No. 2 should be higher than that of sample No.
3. In order to further prove the relationship between MI value
the weight average molecular weight (Mw) of sample No. 2 is
higher than that of sample No. 3. As a result, 1H-NMR has a
good resolution for the evaluation of the characteristic structure
of resole phenolic prepolymer resin. MI value mainly influences
on weight average molecular weight of the resin.
Much of the works had been focused on the effect of
feed ratio F/P on the properties of resin [20, 21]. F/P value
obtained by 1H-NMR finally decides the ratio of alkyl bridge
to phenol ring of resin after curing processing, which is
important for heat resistance, pyrolysis behaviors, and
Effect of quantitative characteristic structure of resole phenolic prepolymer resin on thermal… 1053

(a)
1.88
(b)

0.55

9.61

0.80

0.90

4.26

1.00
0.52

0.48

6.49

0.61

0.60
0.48
1.27

0.65

3.41
0.20

1.00
9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0
10 9 8 7 6 5 4 3 2
f1/ppm
f1/ppm

(c) (d)

4.59

0.80

1.00
0.94
0.80

0.60

0.55

4.13
1.41

0.72

7.83

1.07

1.02

5.86

1.00
0.61

9.5 9.0 8.5 8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 10 9 8 7 6 5 4 3 2
f1/ppm f1/ppm

(e)
0.66

0.19

0.55

0.54
0.66

0.87

4.42

1.00
4.22

10 9 8 7 6 5 4 3 2
f1/ppm

Fig. 1  1H-NMR spectrum of different feed ratios of F/P with a 1.0:1; b 1.2:1; c 1.4:1; d 1.6:1; e 1.8:1

ablation properties. Therefore, the influence of F/P value on kinetic via TG/DTG analysis. Figure 2 shows the TG curves
the performance is systematically investigated as follows. and DTG curves of phenolic resin at the different heating
rates with different F/P values. The peak temperatures in
Influence of F/P value on thermal stability every DTG curves are listed in Table(3.
According to formula (7), the dln 𝛽TP−2 is used to plot
)

The thermal stability of resins with different F/P values TP−1. The linear regression equations of phenolic resin with
was investigated by the method of non-isothermal pyrolysis the different structures are obtained. According to the slope

13
1054 H. Hu et al.

Table 1  Analysis of characteristic structure of phenolic resin by 1H-
NMR
No. Feed ratio of F/P MI HI F/P value of
1
H-NMR
1 1.0:1 0.392 0.836 1.03
2 1.2:1 0.544 0.927 1.20
3 1.4:1 0.425 1.246 1.46
4 1.6:1 0.653 1.349 1.68
5 1.8:1 0.673 1.487 1.82
of the equation, the apparent activation energy of the thermal
decomposition of resin is calculated. The pre-exponential
factor A is calculated according to formula (8). The results
are listed in Table 4. The correlation coefficient R2 is above
0.95, which shows that the linear relationship is significant.
As the increase in F/P value, the apparent activation
energy of thermal decomposition in the range of 723–873 K
tends to decrease from Table 5. It can be seen that the appar-
ent activation energy in this temperature range is the highest
when the F/P value is 1.03, but it does not mean that the
thermal stability of resin is the best. It is worth noting that
there is an obvious pyrolysis rate peak at 673 K from the
DTG curve (Fig. 3a) when the F/P value is 1.03, correspond-
ing apparent activation energy of 174.12 kJ mol−1. For the
reason, the cross-linking density of resin with F/P = 1.03
may be lower than the others, which results from methyl-
ene formed by formaldehyde is not enough to make bridges
between the phenols. Partial end group phenols as pyroly-
sis product may release, which leads to the mass loss in
this temperature range of 600–700 K (DTG curves of resin
with F/P = 1.03 in Fig. 2a). Residual resin carbon becomes
compact under the slowly heating rate of 5–20 K min−1,
which may result in the highest apparent activation energy
of thermal decomposition in the range of 723–873 K. Com-
pared with other resins (Fig. 2b–e), only the resin with
F/P = 1.03 has a large weight loss in the temperature range
of 600–700 K. When the F/P value is 1.20 and 1.46, the
corresponding apparent activation energy of thermal decom-
position is 239.37 kJ mol−1, 213.60 kJ mol−1, respectively.
It infers that the thermal stability of the resin with the F/P
value in the range of 1.20–1.46 may be optimum. For the
cases of F/P value with 1.68 and 1.82, the cross-linking den-
sity of resin may be higher than the others due to the excess
formaldehyde to phenol. However, excessive formaldehyde
forms more alkyl chains or bridges between phenols. Exces-
sive alkyl structure may lead to the decrease in activation
energy of thermal decomposition in the range of 723–873 K.
Table 5 shows the char yield of phenolic resin with dif-
ferent F/P at 1073 K. It indicates that the char yield of resin
at 1073 K from high to low in turn is F/P = 1.20, 1.46, 1.68,
1.82. The results further prove the fact that the thermal sta-
bility of resole phenolic resin may be optimal when the F/P
value is in the range of 1.20–1.46.
The apparent activation energy of phenolic resin at dif-
ferent F/P values was also calculated by the Ozawa method.
Table 6 shows the temperature corresponding to the conver-
sion ratio αT at different heating rates. According to formula
(10), for the same conversion αT, lgβ is linearly correlated
with T−1. The linear regression curves of phenolic resin at
different F/P values are shown in Fig. 3. According to the
slope of the equation, the apparent activation energy of the
thermal decomposition of resin is calculated and showed in
Fig. 4. The value of the average activation energy obtained
by the Ozawa method is slightly smaller than the activation
energy obtained by the Kissinger method, which is con-
sistent with other research [26]. It infers that the results of
apparent activation energy are reliable.
As a result, thermal stabilization of resin may be optimum
when F/P value in the range of 1.20–1.46. In order to further
prove the results discussed above, the Py-GC/MS experi-
ments and were carried out, and CLD of resin at different
F/P values were evaluated as follows.
Influence of F/P value on pyrolysis behaviors
and CLD
The ideal cross-linked structure of resole phenolic resin is
that: all the three activated points of phenol ring are involved
in the formation of body structure. However, because of the
synthesis, curing, and other reasons, the actual curing struc-
ture contains different proportions of terminal groups of sin-
gle bridge biphenyl, a certain proportion of double bridge
biphenyl (Fig. 5), which results in the decrease in cross-
link density of the cured resin. Methylene bridges between

Table 2  The molecular weight No. Feed ratio of F/P Number average molecular Weight average molecular Mw/Mn
of the different characteristic weight/Mn weight/Mw
structure
1 1.0:1 326.2 571.1 1.75
2 1.2:1 357.5 701.2 1.96
3 1.4:1 384.1 637.5 1.66
4 1.6:1 478.8 883.3 1.84
5 1.8:1 512.6 940.8 1.84

13
Effect of quantitative characteristic structure of resole phenolic prepolymer resin on thermal… 1055

0.05
(a) (b)
100 20 K min–1 100
0.00 20 K min–1 0.00
15 K min–1 15 K min–1
10 K min–1
10 K min–1 90 5 K min–1 – 0.05

DTG/% min–1
5 K min–1

DTG/% min–1
20 K min–1 – 0.05
Mass/%

Mass/%
15 K min–1
80 80 20 K min–1 – 0.10
10 K min–1 – 0.10 15 K min–1
5 K min–1 10 K min–1
5 K min–1 – 0.15
70
– 0.15
– 0.20
60 60
– 0.20
– 0.25
600 800 1000 600 800 1000
Temperature/K Temperature/K

0.05 110 0.05

(c) (d)
100
20 K min–1 0.00 100
0.00
15 K min–1 20 K min–1
10 K min–1 15 K min–1

DTG/% min–1
DTG/% min–1
90 90
5 K min–1 – 0.05 10 K min–1
– 0.05

Mass/%
5 K min–1
Mass/%

– 0.10 80
80 20 K min–1
15 K min–1 – 0.10
10 K min–1 20 K min–1
– 0.15 70 15 K min–1
70 5 K min–1
10 K min–1
5 K min–1 – 0.15
– 0.20 60
60
– 0.25 50 – 0.20
600 800 1000
600 800 1000
Temperature/K
Temperature/K
(e)

0.05
100
(e)
20 K min–1 0.00
90 15 K min–1
10 K min–1
DTG/% min–1

5 K min–1 – 0.05
80
Mass/%

20 K min–1
15 K min–1
10 K min–1 – 0.10
70 5 K min–1

60 – 0.15

50 – 0.20
600 800 1000
Temperature/K

Fig. 2  The TG and DTG curves of phenolic resin at the different heating rates with F/P value a 1.03; b 1.20; c 1.46; d 1.68; e 1.82

phenol rings are well-known formed by polycondensation of
formaldehyde [27]. Under the condition of the resin cured
in an airtight container such as RTM processing, the ratio of
methylene bridge to phenol ring should equal to F/P value
obtained by 1H-NMR. It means that CLD value increases
with the enhance of F/P value. The phenolic resin could be
compared to the brick wall. The phenol ring is compared to
brick. The methylenes and little other bridging structures are
compared to cement. The proportion of cement and brick
should directly determine the performance of a brick wall.
Therefore, cross-link density can be defined as the ratio of
alkyl bridge to the phenol ring.
Figure 6 shows the total ion chromatograms of phenolic
resin pyrolysis at 400 °C with different F/P value, the peak
identification of pyrolysis are listed in Table 7. It indicates
that mass loss of F/P value with 1.03 at 400 °C is mainly

13
1056 H. Hu et al.

Table 3  Peak temperature in DTG curves under different F/P ratios Table 5  Char yield of phenolic resin with different F/P at 1073 K
F/P value/ Peaks in DTG curves, Tp/K F/P value Char yield/%
temperature −1 −1 −1 −1
range/K 5/K min 10/K min 15/K min 20/K min 5/K min−1 10/K min−1 15/K min−1 20/K min−1

1.03/653–703 661.50 673.75 684.67 688.81 1.03 60.906 63.895 62.170 60.455
1.03/723–873 793.07 810.16 816.15 822.46 1.20 63.486 65.550 65.031 64.598
1.20/723–873 785.73 802.52 809.93 814.27 1.46 62.309 62.776 63.325 62.503
1.46/723–873 782.46 798.47 807.16 815.22 1.68 57.140 59.781 57.724 58.398
1.68/723–873 761.59 776.31 791.48 801.11 1.82 59.139 58.475 55.541 57.625
1.82/723–873 750.42 762.96 776.68 787.45

composite is investigated by the arc heating ablation under

owing to releasing end group phenol. As the increase in F/P
value, the content of pyrolysis product phenol decreases
obviously. Therefore, the content of single bridge biphenyl
increases with the decrease in F/P, leading to a decrease in
thermal stability of the resin.
Pyrolysis gases of resole phenolic mainly include CO,
­CH4, ­CO2, ­H2O, benzene and its homologs, phenol and its
homologs, which has been reported in the literature [20,
28, 29]. Figure 7 shows the total ion chromatograms of the
pyrolysis gas of phenolic resin with different characteristic
structure at 550 °C. The peak identifications of pyrolysis
gas are listed in Table 8. It should be noted that the sum
of the ion intensity of small molecules increases with the
increase in F/P value. The sum of the ion intensity of small
molecules was calculated by the ion intensity of CO, C ­ H4,
­CO2, ­H2O. The CLD of resin also raises with the increase in
F/P value (Fig. 8). Methanol is the polymerization inhibitor
contained in formalin, which is unnecessary to count in. It
infers that the excess formaldehyde may form more alkyl
structures, which leads to an increase in CLD and release
more small-molecule pyrolysis products such as ­CH4, CO,
­H2O, and ­CO2.
Influence of F/P value on ablation properties
In order to verify that the thermal stability of the resin is
optimal when the F/P value is in the range of 1.20–1.46,
carbon fiber-reinforced composites with different F/P values
of resin were fabricated. The ablation performance of the
the same ablation state. The results are shown in Table 9 and
Fig. 9. It can be seen that the linear ablation rate and mass
ablation rate of the composite from low to high in turn is
F/P = 1.20, 1.46, 1.68, 1.82, 1.03. It infers that the thermal
stability of the resin is optimum when the F/P value is in the
range of 1.20–1.46.
Figure 10 shows the surface morphology of compos-
ites after ablation. When the F/P value is 1.03, due to the
low CLD of the cured resin (10.9%), the mass loss of resin
increases during the ablation process, which leads to less
residual resin carbon between the carbon fibers (Fig. 10a).
Heat penetration of composites quickly occurs due to the
lack of resin carbon connection between the fibers, which
results in the increase in the ablation rate of composites.
When the F/P value increases to 1.20, the CLD of the
resin increases to 15.7%. The compact resin carbon can be
observed between the fibers (Fig. 10b). When the F/P value
increases to 1.46, the CLD of the resin increases to 22.3%.
The resin carbon can be obviously observed between the fib-
ers. It is worth noting that the pore morphology of the resin
carbon area appears (Fig. 10c), which should be caused by
the release of small molecular pyrolysis gases such as C ­ H4,
CO, ­H2O, and C ­ O2. With the increase in F/P value to 1.68,
the CLD of the cured resin increases to 35.4%. The ratio of
small molecular pyrolysis gases increases. The inner pres-
sure caused by small molecular gases leads to micro-erosion
of composite (Fig. 10d), which results in an increase in the
ablation rate. When the F/P value increases to 1.82, the CLD
of the cured resin increases to 40.1%. A large number of
small molecular pyrolysis gases were released, resulting

Table 4  Activation energy F/P value/tempera- Slope Ea/KJ mol−1 Average of A value Correlation coefficient
and A value obtained by the ture range/K of linear regression R2
Kissinger method of phenolic
resin with different F/P ratios 1.03/653–703 − 20,943 174.12 1.37817 × 1013 0.98624
1.03/723–873 − 29,190 242.69 5.99079 × 1010 0.98624
1.20/723–873 − 28,790 239.37 1.84695 × 1015 0.98071
1.46/723–873 − 25,691 213.60 3.82531 × 1013 0.99807
1.68/723–873 − 19,412 161.40 2.10130 × 1010 0.97261
1.82/723–873 − 20,181 167.79 9.42428 × 1010 0.95279

13
Effect of quantitative characteristic structure of resole phenolic prepolymer resin on thermal… 1057

1.4 (a) 1.4 (b)

1.3 1.3

1.2 1.2

1.1 1.1
Igβ

Igβ
1.0 1.0

0.9 0.9

0.8 0.8

0.7 0.7

0.6
α :90% α :5% 0.6 α :90% α :5%

0.0010 0.0015 0.0020 0.0010 0.0012 0.0014 0.0016 0.0018 0.0020

T – 1/K–1 T – 1/K–1

1.4 (c) 1.4 (d)

1.3 1.3

1.2 1.2

1.1 1.1

1.0 1.0
Igβ

Igβ

0.9 0.9

0.8 0.8

0.7 0.7

0.6 α :90% α :5% 0.6 α :90% α :5%

0.0010 0.0015 0.0020 0.0010 0.0015 0.0020

T – 1/K–1 T – 1/K–1

1.4 (e)
1.3

1.2

1.1

1.0
Igβ

0.9

0.8

0.7
α :90% α :5%
0.6

0.0010 0.0012 0.0014 0.0016 0.0018 0.0020 0.0022

T – 1/K–1

Fig. 3  Curves of lgβ versus T−1 with F/P value a 1.03; b 1.20; c 1.46; d 1.68; e 1.82

13
1058 H. Hu et al.

Table 6  Temperature (K) αT/% 5 10 15 20 25 30 35 40 45

corresponding to the conversion
ratio αT at different heating rates F/P = 1.03
5/K min−1 513.43 577.08 622.14 648.01 668.78 689.88 710.48 729.25 746.33
10/K min−1 524.57 588.30 628.23 658.67 682.43 699.10 718.92 737.75 756.70
15/K min−1 527.49 593.42 635.40 668.32 693.79 707.56 726.73 746.25 765.81
20/K min−1 533.22 601.65 643.05 676.99 704.50 716.47 734.80 754.76 774.22
αT/% 50 55 60 65 70 75 80 85 90
5/K min−1 762.10 776.62 790.10 803.20 816.74 832.03 851.27 877.96 913.81
10/K min−1 773.75 786.14 802.41 815.54 828.91 845.44 863.59 890.09 926.66
15/K min−1 784.42 795.56 813.88 826.71 839.92 857.08 875.15 901.67 938.70
20/K min−1 793.59 805.03 824.59 835.82 850.70 867.42 885.76 913.78 950.27
F/P = 1.20
αT/% 5 10 15 20 25 30 35 40 45
5/K min−1 524.22 633.36 669.66 694.86 715.99 732.89 747.35 760.53 773.01
10/K min−1 530.43 641.48 676.77 702.74 724.36 741.85 756.23 770.75 782.88
15/K min−1 536.70 649.45 684.68 711.31 733.58 751.51 764.89 779.91 792.54
20/K min−1 542.92 657.22 692.56 720.27 741.64 759.72 774.11 788.57 801.42
αT/% 50 55 60 65 70 75 80 85 90
5/K min−1 784.86 796.56 808.37 821.06 835.54 853.17 875.50 902.89 935.05
10/K min−1 794.22 806.22 820.05 832.84 849.22 865.50 887.16 916.12 950.73
15/K min−1 804.90 816.90 829.71 842.50 860.88 876.86 899.82 928.24 964.46
20/K min−1 814.76 825.50 841.39 853.73 869.99 887.08 909.51 941.45 976.44
F/P = 1.46
5/K min−1 503.45 570.23 650.78 681.32 704.90 725.05 740.30 752.96 764.50
10/K min−1 510.12 578.85 659.64 692.28 715.56 735.71 749.57 763.64 773.22
15/K min−1 517.38 585.04 666.62 702.22 724.21 743.84 760.83 773.13 784.45
20/K min−1 522.26 592.81 676.48 705.51 733.76 752.95 771.05 784.49 794.16
αT/% 50 55 60 65 70 75 80 85 90
5/K min−1 775.43 786.28 797.20 808.78 821.87 837.59 858.30 885.97 921.22
10/K min−1 784.40 794.97 808.56 818.44 832.23 850.25 870.65 897.31 930.10
15/K min−1 795.63 807.33 819.42 830.04 839.09 858.81 880.31 913.85 944.46
20/K min−1 805.74 818.90 831.75 842.61 854.46 874.17 894.85 924.19 961.01
F/P = 1.68
αT/% 5 10 15 20 25 30 35 40 45
5/K min−1 503.31 546.85 615.43 663.99 692.50 714.76 730.72 743.50 755.49
10/K min−1 515.11 559.08 623.09 676.66 708.38 728.33 744.94 754.75 768.71
15/K min−1 521.23 567.63 633.41 686.40 717.07 741.00 755.29 768.32 781.26
20/K min−1 527.48 576.78 641.63 694.91 726.94 749.70 767.84 781.73 795.47
αT/% 50 55 60 65 70 75 80 85 90
5/K min−1 767.57 779.68 792.11 805.20 819.92 837.56 860.33 883.88 915.36
10/K min−1 780.69 794.89 806.33 820.87 834.06 853.33 878.01 901.10 931.52
15/K min−1 794.35 806.36 820.58 835.08 846.91 869.67 893.23 916.64 949.50
20/K min−1 806.94 820.59 835.03 848.32 863.22 882.65 909.60 933.87 966.05
F/P = 1.82
αT/% 5 10 15 20 25 30 35 40 45
5/K min−1 494.64 531.17 582.83 651.70 685.09 709.79 727.97 741.25 753.22
10/K min−1 502.99 539.76 591.06 662.58 697.85 721.44 741.08 755.57 766.77
15/K min−1 511.65 547.31 600.60 671.89 708.46 733.68 752.35 766.80 779.54
20/K min−1 519.54 554.52 609.71 679.44 718.13 742.67 762.82 779.39 790.87
αT/% 50 55 60 65 70 75 80 85 90
5/K min−1 765.17 777.22 789.35 802.05 815.86 831.63 851.69 878.88 914.34
10/K min−1 777.52 793.51 805.03 816.74 831.43 848.30 866.92 895.61 931.90

13
Effect of quantitative characteristic structure of resole phenolic prepolymer resin on thermal… 1059

Table 6  (continued) αT/% 5 10 15 20 25 30 35 40 45

−1
15/K min 791.17 805.68 816.62 830.11 845.55 862.62 881.01 913.42 948.51
20/K min−1 802.08 819.13 829.63 843.66 859.28 877.84 897.74 928.55 964.05

5
300
a 12 3
4 e
b
c
200 d
e
E/KJ mol–1

Ion intensity
100
Average value of E:
a: 210.7 KJ mol–1 c
0
b: 226.7 KJ mol–1
c: 207.5 KJ mol–1
– 100 b
d: 164.8 KJ mol–1
e: 166.9 KJ mol–1 6
– 200 a
0 20 40 60 80 100
α T/% 0 10 20 30 40 50 60 70 80
Time/min
Fig. 4  Activation energy obtained by the Ozawa method of phenolic
resin with F/P value a 1.03; b 1.20; c 1.46; d 1.68; e 1.82 Fig. 6  Total ion chromatograms of phenolic resin pyrolysis at 400 °C
with F/P value a 1.03; b 1.20; c 1.456; d 1.68; e 1.82

OH H2C in the higher inner pressure and a large number of micro-

H2 H2 erosion on the composite’s surface (Fig. 10e). The ablation
C C CH2 C OH
H2 rate further increases. Therefore, the decrease in residual
HO OH CH2 CH2 resin carbon will lead to losing the connection between fib-
CH2 H2C H2C
CH2 OH ers when the F/P value is low, which results in the decrease
in the ablative performance of the composite. The increase
OH
H2C
CH2
OH CH2
in inner pressure caused by pyrolysis gases will result in
OH CH2
micro-erosion when the F/P value is high, which leads to
the decrease in ablative properties of the composite. As a
OH consequence, the optimum F/P value of resin using in the
ablation composite is in the range of 1.20–1.46.
Fig. 5  Cross-linking structure of resole-typed resin

Table 7  Pyrolysis products of Peak no. Pyrolysis gases Peak area of ion intensity under different F/P values (× 10−8/mg)
Py-GC/MS at 400°C
1.03 1.20 1.46 1.68 1.82

1 CO 0.031 0.030 0.324 0.603 0.239

2 CO2 0.074 0.097 0.420 0.681 0.566
3 H2O 0.814 1.181 1.531 2.144 2.248
4 HCHO 0 0 0 0 0.205
5 Methanol 0.037 0.085 0.094 2.692 2.907
6 Phenol 1.249 0.074 0.032 0.037 0.034

13
1060 H. Hu et al.

11
10 40
5 121314
123 4 6 15 e
35

d 30
Ion intensity

CLD value/%
25
c
20

b
15

7 89 a 10
0 20 40 60
1.0 1.2 1.4 1.6 1.8
Time/min
F/P value of 1H-NMR
Fig. 7  Total ion chromatograms of phenolic resin pyrolysis at 550 °C
with F/P value a 1.03; b 1.20; c 1.456; d 1.68; e 1.82 Fig. 8  CLD of phenolic resin pyrolysis at 550 °C with different F/P
values

Conclusions Table 9  Ablation performance of carbon fiber-reinforced phenolic

resin composites
F/P and MI value obtained by 1H-NMR can be used for F/P value of 1H-NMR Mass ablation Linear ablation
quantitative characteristic structure of resole phenolic pre- rate/g cm−2 s−1 rate/mm s−1
polymer resin. The CLD is defined as the percentage of the
1.03 0.08871 0.44250
sum of dimethylphenol and trimethylphenol to sum of ben-
1.20 0.07026 0.28667
zene and its homologs, phenol and its homologs, which was
1.46 0.07763 0.35000
obtained from the result of Py-GC/MS at 550 °C. F/P value
1.68 0.08072 0.40833
has a directly proportional relation with CLD. The phenolic
1.82 0.08936 0.41667
skeleton structure such as phenol ring is easy to break and

Table 8  Analysis of pyrolysis Peak no. Pyrolysis gases Peak area of ion intensity under different F/P
products of Py-GC/MS at values (× 10−8/mg)
550 °C
1.03 1.20 1.46 1.68 1.82

1 CO 0.282 0.365 0.405 0.415 0.414

2 CH4 0.171 0.276 0.548 0.616 0.605
3 CO2 1.004 1.354 1.539 1.674 1.662
4 H2O 2.931 3.160 3.228 3.247 3.418
5 Methanol 0.050 0.306 0.288 2.810 2.680
6 pentadiene 0.054 0.119 0.068 0.113 0.246
7 benzene 0.249 0.100 0.083 0 0
8 toluene 0.532 0.198 0.271 0.089 0.126
9 xylene 0.335 0.087 0.193 0.074 0.113
10 Phenol 14.849 5.465 4.637 3.707 4.336
11 O-cresol 12.575 4.965 7.552 8.079 9.451
12 P-cresol 8.011 2.303 3.584 2.893 3.922
13 2,6-dimethylphenol 2.180 1.224 2.022 3.390 4.532
14 2,4-dimethylphenol 2.295 1.126 2.417 3.895 6.064
15 2,4,6-trimethylphenol 0 0.086 0.235 0.842 1.407
Sum of ion intensity of small molecules (× 10−8/mg) 4.388 5.155 5.72 5.952 6.099
CLD/% 10.9 15.7 22.3 35.4 40.1

13
Effect of quantitative characteristic structure of resole phenolic prepolymer resin on thermal… 1061

0.50 0.12 micro-erosion when the CLD is high, leading to a decrease

in ablative properties. As a consequence, heat resistance and

Mass ablation rate/g cm–2 s–1

Linear ablation rate/mm s–1

0.45
a ablation properties of resin are optimum when the F/P value
0.40
0.10 of resin is in the range of 1.20–1.46.
0.35
b Acknowledgements The authors would like to acknowledge Science
0.30 and Technology on Advanced Functional Composites Laboratory
0.08 for funding the research under the Grant No. HTKJ2019KL703002.
0.25
Thanks to Prof. Zhongping Li for his useful suggestions on the research
0.20 of the paper.

0.15
1.0 1.2 1.4 1.6
F/P value of 1H-NMR
Fig. 9  Analysis of ablation performance of carbon fiber-reinforced
phenolic resin composites. Curve a: Linear ablation rate; curve b:
Mass ablation rate
Fig. 10  Surface morphology of carbon fiber-reinforced composites
after ablation using different resins with F/P value a 1.03; b 1.20; c
1.46; d 1.68; e 1.82
release during the ablation when the F/P value is too low.
When the F/P value is too high, a lot of small-molecule
pyrolysis gases produced by excessive alkyl structure will
release. Both of the situations will reduce the heat resistance
and ablation properties of the resin. The decrease in resid-
ual resin carbon will lead to losing the connection between
fibers when the CLD is low, which results in a decrease
in the ablative performance of composites. The increase
in inner pressure caused by pyrolysis gases will result in
0.06 Author contributions Methodology: H.H., L.L. Formal analysis and
1.8
investigation: H.H., R.Y. Writing-original draft preparation: H.H.
Writing-review and editing: H.H., Y.Z. Data collection and analysis:
H.H., Y.Z. Funding acquisition: J.W. Supervision: Y.Y.
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