materials

Article
Study on the Design, Preparation, and Performance Evaluation
of Heat-Resistant Interlayer-Polyimide-Resin-Based
Neutron-Shielding Materials
Hu Xu 1,2 , Dan Liu 3 , Wei-Qiang Sun 1 , Rong-Jun Wu 3 , Wu Liao 3 , Xiao-Ling Li 3 , Guang Hu 1, * and Hua-Si Hu 1, *

1 College of Nuclear Science and Technology, Xi’an Jiaotong University, Xi’an 710049, China;
xuhu_xu@[Link] (H.X.); sunweiqiang@[Link] (W.-Q.S.)
2 Department of Radiation Protection and Detection, Sino Shaanxi Nuclear Industry Group, Xi’an 710054, China
3 The Sixth Research Laboratory, Wuhan Second Ship Design and Research Institute, Wuhan 430205, China;
liudan@[Link] (D.L.); wurongjun@[Link] (R.-J.W.); liaowu@[Link] (W.L.);
lixl005@[Link] (X.-L.L.)
* Correspondence: guanghu@[Link] (G.H.); huasi_hu@[Link] (H.-S.H.)

Abstract: Polymers have an excellent effect in terms of moderating fast neutrons with rich hydrogen
and carbon, which plays an indispensable role in shielding devices. As the shielding of neutrons is
typically accompanied by the generation of γ-rays, shielding materials are developed from monomers
to multi-component composites, multi-layer structures, and even complex structures. In this paper,
based on the typical multilayer structure, the integrated design of the shield component structure and
the preparation and performance evaluation of the materials is carried out based on the design sample
of the heat-resistant lightweight polymer-based interlayer. Through calculation, the component



structure of the polymer-based materials and the three-layer thickness of the shield are obtained. The


mass fraction of boron carbide accounts for 11% of the polymer-based material. Since the polymer-
Citation: Xu, H.; Liu, D.; Sun, W.-Q.;
based material is the weak link of heat resistance of the multilayer shield, in terms of material selection
Wu, R.-J.; Liao, W.; Li, X.-L.; Hu, G.;
and modification, the B4 C/TiO2 /polyimide molded plate was prepared by the hot-pressing method,
Hu, H.-S. Study on the Design,
Preparation, and Performance
and characterization analysis was conducted for its structure and properties. The results show that
Evaluation of Heat-Resistant the ball milling method can mix the materials well and realize the uniform dispersion of B4 C and
Interlayer-Polyimide-Resin-Based TiO2 in the polyimide matrices. Boron carbide particles are evenly distributed in the material. Except
Neutron-Shielding Materials. for Ti, the other elemental content of the selected areas for mapping is in good agreement with the
Materials 2022, 15, 2978. https:// theoretical values of the elemental content of the system. The prepared B4 C/TiO2 /polyimide molded
[Link]/10.3390/ma15092978 plate presents excellent thermal properties, and its glass transition temperature and initial thermal
Academic Editors: Philippe
decomposition temperature are as high as 363.6 ◦ C and 572.8 ◦ C, respectively. In addition, the molded
Colomban and Giovanni Bruno plate has good toughness performs well in compression resistance, shock resistance, and thermal
aging resistance, which allows it to be used for a long time under 300 ◦ C. Finally, the prepared
Received: 10 March 2022
materials are tested experimentally on an americium beryllium neutron source. The experimental
Accepted: 11 April 2022
results match the simulation results well.
Published: 19 April 2022

Publisher’s Note: MDPI stays neutral Keywords: neutron shielding; heat resistance performance; optimal design; lightweight interlayer
with regard to jurisdictional claims in
published maps and institutional affil-
iations.

1. Introduction
The material exerts its shielding effect through an interaction with neutrons and γ-rays
Copyright: © 2022 by the authors.
by its internal nuclei and extra-nuclear electrons, respectively. For neutrons, the smaller
Licensee MDPI, Basel, Switzerland. atomic number the nuclide, the better the moderating effect, which makes polymers indis-
This article is an open access article pensable in shielding devices. In the early days, shielding materials were often monomer
distributed under the terms and materials such as water, polyethylene, paraffin, and lead. As with the development of nu-
conditions of the Creative Commons clear technology application devices, the diversified functions, compactness, light weight,
Attribution (CC BY) license (https:// and high-power results constitute increasingly strict requirements for shielding materi-
[Link]/licenses/by/ als. Shielding materials were gradually developed into multi-component composites or
4.0/). multi-layer structures, or even more complex coating structures [1,2].

Materials 2022, 15, 2978. [Link] [Link]

Materials 2022, 15, 2978 2 of 15

The requirement for shielding materials varies based on different types of nuclear
radiation. Low-density materials such as PMMA, leaded glass, rubber products, fiber
fabrics, and concrete are more often used to shield low-energy X-rays [3]; heavy metals
such as iron, lead, and tungsten, as the reinforcing phase particles, are effective choices for
γ-rays [4,5], and lead may also be replaced with alternative materials due to its chemical
toxicity [6]; materials with high hydrogen content such as paraffin, polyethylene, and
polypropylene are more effective as fast neutron moderator materials to shield neutrons.
Materials containing boron or lithium elements such as elemental boron, boric acid, boron
carbide, lithium bromide, and lithium fluoride can be used as excellent slow neutron
absorbers. When the neutron energy is very high, a layer of heavy metal is often placed
at the very front to reduce the neutrons’ energy through inelastic scattering. A single
material cannot protect against the coupling of multiple kinds of nuclear radiation in reality.
Therefore, it is essential to develop a composite material that can shield multiple radiations.
In such a material, heavy substances would shield X-rays, γ-rays, etc., and have the effect of
moderating high-energy neutrons through inelastic scattering, while light elements would
be mainly used to further slowdown the neutrons.
Due to their unique molecular structure and high content of hydrogen for neutron mod-
eration, polymer materials are indispensable in shields. However, compared with metal and
ceramic materials, polymer-based materials are often the bottleneck to heat the resistance
performance of the entire shield. Therefore, the development of high-temperature-resistant
polymer-based nuclear radiation shielding materials has become the priority. In early
days, polyethylene was widely used since would not be activated due to its high hydrogen
content. However, it softens at 110 ◦ C with poor radiation resistance performance, which
means it must be replaced before becoming invalid because of decomposition by radiation-
mixed boron carbide and ultra-high-molecular-weight polyethylene if one seeks to develop
a new neutron composite shielding material and an added KH570 silane coupling agent
to improve the interface effect of the material. The neutron attenuation coefficient of the
material improves with the increase of boron carbide content, but excessive particles will
cause increased agglomeration and reduce the shock resistance of the material [7]. In
addition, NASA studied boron-containing multifunctional composites, and they chose
high-density polyethylene as the continuous phase and boron carbide and boron nitride
as reinforcing fibers. High-density polyethylene outperforms pure polyethylene in tensile
modulus, tensile strength, and shielding effect [8].
However, the weakness in heat resistance and radiation resistance of polyethylene-
based material have limited its use in many environments. Therefore, scholars have carried
out research on other composite materials with other bases, such as epoxy resin and hy-
drogel, and yielded a great deal of scientific research achievements. The Japan Institute of
Technology has designed a new type of neutron-shielding material that uses epoxy resin as
the base and colemanite as the reinforcing phase. Compared with concrete and polyethy-
lene boron carbide composite materials, it enhances mechanical properties, achieves heat
resistance temperatures as high as 133 ◦ C, and presents a better shielding effect [9]. JAEA
developed a series of epoxy resin and heat-resistant neutron composite materials with
different contents of boron. The developed material performs well in both shielding and
heat resistance and can be used in the external shield of vacuum containers and super-
conducting Tokomak device [10]. Seyhun Kipcak has studied epoxy-based composites
with different contents of boron fiber. Those materials are based on epoxy resin and are
configured according to different combinations of boron fiber and boron nano powder
B4 C, which perform excellently in terms of both their shielding effect and mechanical
properties [11]. Kyoto University developed a series of samples with thermosetting resin
as the base. It has been verified that among all the samples, the resin + 35% 6 LiF composite
material is the most effective and practical neutron-shielding material, and it can be applied
in medical and biological facilities such as boron neutron capture therapy [12]. Masoud
Sabzi and Morteza Shamanian developed a series of new metal matrix composite shielding
materials and achieved good results [13–15]. Guang Hu developed a high-temperature-
Materials 2022, 15, x FOR PEER REVIEW 3 of 15

Materials 2022, 15, 2978 can be applied in medical and biological facilities such as boron neutron capture therapy 3 of 15
[12]. Masoud Sabzi and Morteza Shamanian developed a series of new metal matrix com-
posite shielding materials and achieved good results [13–15]. Guang Hu developed a
high-temperature-resistant composite by adding boron carbide to epoxy resin [16].
resistant composite by adding boron carbide to epoxy resin [16]. PVA/PEO hydrogel
PVA/PEO hydrogel materials were successfully developed by physical cross-linking
materials were successfully developed by physical cross-linking method and based on
method and based on which new metal ion-containing hydrogel materials were devel-
which new metal ion-containing hydrogel materials were developed by adding compounds
oped by adding compounds containing heavy metal ions and rare earth elements [17,18].
containing heavy metal ions and rare earth elements [17,18]. Additionally, the micro and
Additionally, the micro and nanostructured composite materials for neutron-shielding
nanostructured composite materials for neutron-shielding applications was reviewed by
applications was reviewed materials
Sajith [19]. Polymer-based by Sajith [19].
havePolymer-based
great potentialmaterials have great potential
in high temperature resistance,in
high temperature resistance, and the improvement of their heat resistance is the
and the improvement of their heat resistance is the key to improving the service perfor- key to
improving the service
mance of multilayer performance
shields. of multilayer
This paper studies theshields.
design,This paper studies
preparation, the design,
and performance
preparation, and performance evaluation of polymer-based interlayer materials
evaluation of polymer-based interlayer materials based on the structural optimization based on of
the structural optimization of
typical multilayer structures. typical multilayer structures.

2. Material and Method

2.1. Optimal Design of the Materials
The composition
composition of ofthethematerials
materialsisisdesigned
designedasas Figure
Figure 1 prior to material
1 prior preparation.
to material prepara-
The
[Link] adopts
The source the fission
adopts neutron
the fission spectrum
neutron and fission
spectrum gammagamma
and fission ray spectrum, which
ray spectrum,
which are vertically incident to the shield from the left side. The shield has a total oflayers,
are vertically incident to the shield from the left side. The shield has a total of three three
which
layers, are 304 are
which stainless steel (SS),
304 stainless a polymer-based
steel composite
(SS), a polymer-based material,material,
composite and 304 stainless
and 304
steel (SS),steel
stainless with(SS),
the polymer-based material as
with the polymer-based the middle
material as theinterlayer. The polymer-based
middle interlayer. The poly-
mer-based material is composed of polyimide and boron carbide. In thismiddle
material is composed of polyimide and boron carbide. In this way, the interlayer
way, the middle
is lightweight
interlayer and easy to
is lightweight and prepare.
easy to The iron The
prepare. on both
iron sides
on bothis asides
traditional [Link]-
is a traditional The
block shied, with a total thickness, height, and width of 10 cm, can provide
rial. The block shied, with a total thickness, height, and width of 10 cm, can provide better better support.
At far right
support. At isfara right
detector
is a with a height
detector with and width
a height both
and of 10both
width [Link] The
10 multi-layer shield is
cm. The multi-layer
modeled and calculated by MCNP software, and the shield is optimized
shield is modeled and calculated by MCNP software, and the shield is optimized by com- by combining with
AI algorithms to obtain the composition of the polymer-based material
bining with AI algorithms to obtain the composition of the polymer-based material and and the thickness of
each layer of the three-layer shield.
the thickness of each layer of the three-layer shield.

Neutrons

Gamma rays

Polymer matrix Detector

SS SS
composites
Figure
Figure 1.
1. Multilayer
Multilayer structural
structural material containing aa polymer-based
material containing polymer-based interlayer.
interlayer.

The designed
designedmethod
methodisisestablished
established byby genetic
genetic algorithm
algorithm (GA)
(GA) combing
combing withwith
MCNP MCNP[20].
[20]. parameters,
The The parameters,suchsuch asthickness,
as the the thickness, density,
density, and and components
components of the
of the material,
material, are are
set
set in cell cards and material cards in the MCNP code. The data representative
in cell cards and material cards in the MCNP code. The data representative of the of the dose
equivalent of of neutrons
neutronsandandγγrays
raysininthe
theoutput
output file
file areare extracted.
extracted. TheThe extracted
extracted data
data are are
set
as the
set objective
as the function
objective of GA.
function In the
of GA. GAGA
In the program,
program, the the
optimal combination
optimal combination of structure,
of struc-
components,
ture, and density
components, is sought
and density out for
is sought outsatisfying
for satisfyinga preset objective.
a preset In the
objective. shielding
In the shield-
design,
ing the objective
design, commonly
the objective commonly is theislowest dosedose
the lowest equivalent of neutrons
equivalent and γ-rays
of neutrons after
and γ-rays
their penetration through the shield. Equation (1) is the objective function
after their penetration through the shield. Equation (1) is the objective function

MinH (L, A) = min [αHn (L, A) + βHγ (L, A)] (1)

Materials 2022, 15, x FOR PEER REVIEW 4 of 15

Materials 2022, 15, 2978 4 of 15

MinH (L, A) = min [αHn(L, A) + βHγ(L,A)] (1)

where
where H Hnn((L,LA
, A) )is is
thethe dose
dose equivalent
equivalent ofof the
the neutron
neutron andHγH
and  (A
( L, L), A
is)the
is dose
the dose equiv-
equivalent
of γ ray.α
alent of γ ray.  represents
represents the counting of neutrons,
the counting of neutrons, and  represents
and β represents counting of γ-rays in
counting ofthe
γ-
initial source. Equations (2)–(4) are the constraint conditions.
rays in the initial source. Equations (2)–(4) are the constraint conditions.
p p
Li
∑LallLi
L
= 11 (2)
(2)
i 1 all
i =1
p
p A A 1 2   Ai  1 (3)
∑ A1 + A2 + · · · A i = 1
i 1 (3)
i =1
x  eff   y (4)
ρ x ≤ ρe f f ≤ ρy (4)
where Li is the thickness of each layer, Lall is the total thickness of the shield, Ai is the
where Li is the thickness of each layer, L all is the total thickness of the shield, Ai is the mass
mass ratio
ratio of of component,
each each component, e f f is 
and ρand the is the equivalent
eff equivalent densitydensity of the shield.
of the shield.
Figure 2 is the flow chart of GA combing with
Figure 2 is the flow chart of GA combing with MCNP, which isMCNP, which is used
used to
to design
design the
the
structure and component of the shield. It contains
structure and component of the shield. It contains five [Link] steps.

Start

Calculate the thickness and

component of the material

Produce “Inpn”for Produce “Inpp”for

calculating neutrons calculating γ rays

Run MCNP, Produce “Inpno” Run MCNP, Produce “Inppo”

No Flux or dose of neutron h1 and

Flux or dose of primary γh3
secondary γh2

α(h1+h2)+βh3

Reaching the minimum

or the value preset

Yes

End

Figure 2. Flow chart of representing the structure and components of the shielding.
Materials 2022, 15, x FOR PEER REVIEW 5 of 15

Materials 2022, 15, 2978 5 of 15

Figure 2. Flow chart of representing the structure and components of the shielding.

(1) Input the parameters expressing the thickness of the shield and the components of
(1) the
Inputmaterials.
the parameters expressing the thickness of the shield and the components of
(2) Produce
the [Link] “inpn” file and “inpp” file for simulating the neutron and γ ray trans-
(2) Produceinthe
mission the“inpn” file and “inpp” file for simulating the neutron and γ ray transmis-
material.
(3) sion“inpn”
The in the material.
file and “inpp” file are calculated by MCNP, and the “outpn” file and
(3) The “inpn”
“outpp” file and “inpp” file are calculated by MCNP, and the “outpn” file and
are produced.
(4) “outpp” are produced.
Extract the data expressing the dose equivalent of neutron in the “outpn” file and the
(4) Extractinthe
γ-rays thedata expressing
“outpp” file. the dose equivalent of neutron in the “outpn” file and the
(5) γ-rays
The in the stops
program “outpp”when [Link] fitness value is not changed or the iteration times reach
(5) toThe N0program stops when
(the generation the fitness
number). value
If not, is not
a new changedand
thickness or the iteration times
component will bereach
pro-to
N0 (the
duced andgeneration
then the number). If not, awill
next calculation newstart.
thickness and component will be produced
and then the next calculation will start.
GA can seek out the optimal combination solutions of a question quickly from all
GA can seek
combinations. In ouroutestablished
the optimalmethod, combination solutions
the function of aisquestion
of GA seeking quickly from all
out the optimal
combinations.
combination of In our established
thickness method, thefrom
and the components function
all theofcombinations.
GA is seekingWith out the optimal
generation
combination
after generation’s of thickness and the
calculation components
of the GA method fromcombing
all the combinations.
with MCNP,With the generation
total dose
after generation’s
equivalent of neutrons calculation
and γ rays of the GA to
tends method
be smallcombing
on the with
whole. MCNP,
Figurethe total dose
2 shows the
equivalent of
relationship neutrons
between and γ rays tends to be small on the whole. Figure 2 shows the
them.
relationship
Throughbetween calculation,them. the component structure of the polymer-based material and the
three-layer thickness of thethe
Through calculation, component
shield structure
are obtained. The of the fraction
mass polymer-based
of boronmaterial
carbide and
ac-
the three-layer thickness of the shield are obtained. The
counts for 11% of the polymer-based material. The shielding effect comparison betweenmass fraction of boron carbide
accounts
the designed for 11%
materialof theand
polymer-based
several typical material.
combined The shields
shieldingareeffect comparison
as shown in Figurebetween
3, in
the designed
which the group material
(1) SS and
+ 43.5several
vol% typical
compositecombined
+ SS is shields are as sample,
the designed shown in theFigure 3, in
thickness
which the group (1) SS + 43.5 vol% composite + SS is the designed
of the first layer is SS, the second layer of the polymer-based material is 4.35 cm thick, and sample, the thickness of
the first layer is SS, the second layer of the polymer-based material
the third layer material is 0.42 cm thick; the group (2) SS + 43.5% sphere composite seeks is 4.35 cm thick, and the
third
to make layerthematerial
polymer-basedis 0.42 cm thick; into
material the group
a ball, (2)
theSS + 43.5%
radius sphereiscomposite
of which 0.153 cm, and seekstheto
make the polymer-based material into a ball, the radius of which
total thickness of the material is 10 cm; the group (3) SS + 50.6% sphere B4C seeks to make is 0.153 cm, and the total
Bthickness of the material is 10 cm; the group (3) SS + 50.6% sphere B4 C seeks to
4C into a ball, the radius of which is 0.153 cm, the total material thickness is make B4 C
0.153 cm,
into the
and a ball, the radius
thickness is 10ofcm;
whichgroup is 0.153 cm,isthe
(4) BSS total material thickness
boron-containing stainlessissteel
0.153with
cm, and the
a mass
thickness is 10 cm; group (4) BSS is boron-containing stainless steel
fraction of B4C of 1.7%; group (5) is a boron carbide material; and the group (6) composite with a mass fraction of
B4 C of 1.7%; group (5) is a boron carbide material; and the group (6) composite is a designed
is a designed polymer-based interlayer material. It can be seen from the results that the
polymer-based interlayer material. It can be seen from the results that the designed samples
designed samples are comparable to groups (5) and (3), which are better than the other
are comparable to groups (5) and (3), which are better than the other groups. Additionally,
groups. Additionally, the designed sample has the advantages of simple disassembly and
the designed sample has the advantages of simple disassembly and installation, and good
installation, and good support structure. Moreover, it just needs to prepare the middle
support structure. Moreover, it just needs to prepare the middle interlayer.
interlayer.

(a) (b)

Figure 3. Cont.
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15

(c) (d)
Figure
Figure 3.
3. The shielding performance
The shielding performanceofofsix
sixgroups
groupsofof materials.
materials. (a)(a)
TheThe dose
dose equivalent
equivalent of the
of the neu-
neutron.
tron. (b) The dose equivalent of the second gamma rays. (c) The dose equivalent of the primary
(b) The dose equivalent of the second gamma rays. (c) The dose equivalent of the primary gamma
gamma rays. (d) The dose equivalent of the total.
rays. (d) The dose equivalent of the total.
2.2.
2.2. Preparation
Preparation ofof Materials
Materials
The
The main
main raw
raw materials
materials used used inin this
this experiment
experiment are are asas follows:
follows: (1)(1) the
the thermosetting
thermosetting
polyimide
polyimide molding powder; (2) the boron carbide (B4 C) powder, 99.9%; the
molding powder; (2) the boron carbide (B 4 C) powder, 99.9%; (3) (3) nano tita-
the nano
nium dioxide (TiO ) powder, which is analytically pure. Here,
titanium dioxide (TiO2 ) powder, which is analytically pure. Here, thermosetting polyimide
2 thermosetting polyimide
molding powder is mainly used for fast neutron moderation; boron carbide (B44C) powder powder
is mainly used for thermal neutron absorption, absorption, and and for fast neutron moderation, but its
moderation ability is slightly
slightly inferior
inferior toto that
that of
ofthermosetting
thermosetting polyimide
polyimide molding
molding powder;
powder;
and nano titanium dioxide (TiO22)) is mainly employed employed for material modification. All All raw
raw
materials are dried at 200 °C ◦ C for 2 h before use.

The key factors influencing

influencingthe theperformance
performanceof ofthe
theBB4 4C/TiO
C/TiO22/polyimide
/polyimide molded
molded plate
plate
mainly include the raw material material properties,
properties, the uniformity
uniformity of component
component distribution,
distribution, and
Therefore, two aspects are focused on during the preparation of the
the molding process. Therefore,
molded plate: (a) even mixing of the molding powder; and (b) the hot pressing process.
(a) Blending of raw materials
In order to ensure the even dispersion of B4 C and TiO2 in in the polyimide matrix, B44C, C,
TiO2, and the polyimide molding
2, and the polyimide molding powder need topowder need to be thoroughly compounded before hot
pressing. Here, the MSK-SFM-1-1L planetary ball mill is selected to blend blend BB44C, TiO2,2, and
the polyimide
the polyimide molding
molding powder.
powder. The The details
details are
are as
as follows:
follows: firstly,
firstly, pretreat
pretreat polyimide
polyimide
molding powder
powder and and B B44CC and
and TiOTiO22 powders
powders at at 200
200 °C◦ C for 2 h; secondly, put polyimide
molding for 2 h; secondly, put polyimide
molding powder,
molding powder,BB44C C powder,
powder,TiO TiO 2 2powder,
powder,and andceramic
ceramic balls
balls into thethe
into ceramic
ceramic ballball
millmill
jar,
according to [Link] (mass ratio), and then place the jar into the
jar, according to [Link] (mass ratio), and then place the jar into the ball mill; thirdly,ball mill; thirdly, turn on
the ball mill and set the rotational speed to 380~500 r/min, then
turn on the ball mill and set the rotational speed to 380~500 r/min, then turn off the ball turn off the ball mill after
30~60
mill min30~60
after of ball milling;
min of balland finally,
milling; andusefinally,
a 100-mesh sieve to separate
use a 100-mesh sieve tothe ceramic
separate theballs
ce-
and obtain the well-mixed
ramic balls and obtain the well-mixed B 4 C/TiO /polyimide powder.
2 B4C/TiO2/polyimide powder.
In this
In this process,
process, not not only
only cancan B C, TiO
B44C, TiO2,2, and
and the
the polyimide
polyimide be be evenly
evenly mixed
mixed by by ball
ball
milling but the particle size and distribution of the mixed powder
milling but the particle size and distribution of the mixed powder can be controlled by can be controlled by
adjusting the diameter and proportion of the ceramic balls, which
adjusting the diameter and proportion of the ceramic balls, which lays a good foundation lays a good foundation
for the
for the preparation
preparation of of the
the B C/TiO2/polyimide
B44C/TiO 2 /polyimide moldedplate
molded platewith
withexcellent
excellentperformance.
performance.
(b) Hot-pressing process
(b) Hot-pressing process
The hot-pressing process of the polyimide profile is the key factor that affects the
The hot-pressing process of the polyimide profile is the key factor that affects the
performance of its products. During the experiment, after preliminary process exploration
performance of its products. During the experiment, after preliminary process exploration
and optimization, the hot-pressing process of the B4 C/TiO2 /polyimide molded plate is
and optimization, the hot-pressing process of the B4C/TiO 2/polyimide molded plate is de-
determined as follows.
termined as follows.
Weigh 140 g of the mixed molding powder and put it into the customized hot-pressing
Weigh 140 g of the mixed molding powder and put it into the customized hot-press-
mold, and then place it between the upper and lower platens of a hot press machine; after
ing mold, and then place it between the upper and lower platens of a hot press machine;
that, perform cold pressing on the mold at 30 MPa and then release the pressure, and set
after that, perform cold pressing on the mold at 30 MPa and then release the pressure, and
set the temperature of the upper and lower platens at the same time to 300 °C. Preserve
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Materials 2022, 15,
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x FOR PEER REVIEW 7 of 15

the temperature
the heat for 30 minof when
the upper and lower platens
the temperature reachesat300 the°C,
same
andtime
thento 300 ◦ C. Preserve
pressurize the moldthe
to
heat for 30 min when the temperature reaches 300 ◦ C, and then pressurize the mold to more
more than 20 MPa; afterwards, depressurize and repeatedly exhaust the air; after exhaust-
than 20 MPa; afterwards,
ing, pressurize the upper anddepressurize and repeatedly
lower platens to 20 MPa, exhaust the temperature
and set the air; after exhausting,
of them
pressurize the upper and lower platens to 20 MPa, and set the temperature
at the same time to 390 °C. When the temperature reaches 390 °C, preserve the of them at the
heat for 20
same time to 390 ◦ C. When the temperature reaches 390 ◦ C, preserve the heat for 20 min,
min, and then stop heating; when the temperature of the platens drops to 200 °C, take out
and then stop
the mold heating; the
and demold when the temperature
sample, and a B4C/TiO of the platens drops to 200 ◦ C, take out
2/polyimide molded plate with good
the mold and
toughness can demold the sample,
be obtained. Figure 4and
showsa Bthe
4 C/TiO 2 /polyimide
pressed molded plate
B4C/TiO2/polyimide with plate,
molded good
toughness can be obtained. Figure 4 shows
the size of which is 100 mm × 100 mm × 10 mm. the pressed B4 C/TiO 2 /polyimide molded plate,
the size of which is 100 mm × 100 mm × 10 mm.

Figure
Figure 4. The B
4. The B44C/TiO
C/TiO2/polyimide
2 /polyimide molded
molded plate.
plate.
3. Results and Discussion
3. Results and Discussion
3.1. Analysis of Chemical Structure and Composition
3.1. Analysis of Chemical Structure and Composition
FT-IR and XPS are used to characterize and analyze the chemical composition, struc-
ture, FT-IR and XPS
and element are used
valence of tothecharacterize and analyzemolded
B4 C/TiO2 /polyimide the chemical
plate. composition,
Figure 5 shows struc-
the
ture, and element valence of the B C/TiO /polyimide molded plate.
FT-IR spectra of the molding powder before hot pressing and the molded plate after hot-
4 2 Figure 5 shows the FT-
IR spectraAs
pressing. ofcan
thebe molding
seen, thepowder
spectrabefore hot pressing
show obvious and the molded
characteristic plate
absorption peaksafterofhot-
the
pressing. As can be seen, the spectra show obvious characteristic
imine ring, before and after the sample is hot pressed, at 1780 cm (γC = O , asymmetricabsorption
− 1 peaks of the
imine ring,vibration),
stretching before and after
1725 cmthe−1 (γsample is hot pressed, at 1780 cm−1 (γC1375
= O, cm −1 (γ
asymmetric
C = O , symmetric stretching vibration), C-N ,
stretching vibration), and 1725720 −1 −
cmcm(γC (γ 1 = O, symmetric
, bendingstretching
vibration), vibration),
indicating1375
that cm
the−1 (γC-N,
imine
C=O
stretching
ring vibration),
structure and 720 cm
of the polyimide (γC be
will−1 not , bending after
= Odestroyed vibration), indicating
hot pressing. Afterthat
hotthe imine
pressing,
ringC-N
the structure
bond of the polyimide
stretching vibrationwillcharacteristic
not be destroyed peakafter hot pressing.
of polyimide After
at 1375 cmhot−1 red-shifts
pressing,
the C-N
(i.e., bond
moves to stretching vibration characteristic
the low wavenumber direction), with peakanofoffset
polyimide 9 cm−
at 1375
of about cm1 . −1The
red-shifts
reason
(i.e., moves
might to the
be, after hot low wavenumber
pressing, the polyimide direction), with an
molecular offset
chains areofcrosslinked,
about 9 cmso. The
−1 reason
the rigidity
might
of the be, after hotchains
molecular pressing, the polyimide
is further increased; molecular chainsthe
additionally, areimine
crosslinked, so the rigid-
ring is twisted to a
ity of the
certain molecular
extent; chains
the C-N is further
bond energyincreased;
in the ring additionally, the imineand
is slightly reduced; ringthe
is twisted
polyimideto a
molecular stability
certain extent; the is decreased.
C-N bond energyThese in leadthetoring
the red-shift
is slightlyof reduced;
the corresponding stretching
and the polyimide
vibration
[Link] is decreased. These lead to the red-shift of the corresponding stretching
vibration peak.
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After hot-pressing

After hot-pressing
1780

Transmittance/%
Before hot-pressing 720

1725
1780
Transmittance/% Before hot-pressing 720

1725

1375

3500 3000 2500 2000 1500 1000 500

1375
-1
Wavenumber/cm
Figure 5. The FT-IR spectra of the molding powder before hot pressing and the molded plate after
3500
hot pressing.
3000 2500 2000 1500 1000 500
Wavenumber/cm-1
3.2. Microscopic
Figure
Figure 5. The
5. Morphology
The FT-IR
FT-IR spectra of
spectra Test
of the and Analysis
the molding
molding powder before
powder before hot
hot pressing
pressing and
and the
the molded
molded plate
plate after
after
hot pressing.
SEM was used to analyze the microstructure in the B4C/TiO2/polyimide molded plate
hot pressing.
and the distribution of B4C and TiO2. Before the test, the molded plate was ruptured by
3.2.
3.2. Microscopic
Microscopic
applying Morphology
an externalMorphology
force to Test
Test and
andAnalysis
expose Analysis
its internal microstructure. In order to show the dis-
SEM
SEM was used
used to
to analyze
analyze the
the microstructure
microstructure
tribution of B4C and TiO2 more clearly, we selected inin
thethe
two B4 C/TiO
B4different
C/TiO 2 /polyimide
2/polyimide
areas for moldedmolded
[Link]
Fig-
plate
and and
the the distribution
distribution of
ures 6 and 7 show the SEM photos B 4of
C Band
4 C and
TiO TiO
. .
BeforeBefore
the the
test,test,
the the molded
molded
of the2 cross-section of the molded plate.
2 plate
plate was was ruptured
ruptured by
by applying
applying an
an external
In Figures external
6 andforce force
7, the to expose
toBexpose its internal
its internal
4C particles microstructure.
are inmicrostructure.
red circles and In In order
theorder to show
TiO2toparticles
show the the
dis-
are in
distribution
tribution of B
green circles. of4ItCBcan
4 C be
and and
TiO TiO
seen 2 more
2 more
from theclearly,
clearly, we
thatselected
we selected
figures andtwo
B4C two TiO2different
different areasareas
are evenly for for analysis.
analysis.
dispersed inFig-
the
Figures
ures
polyimide 6 and
6 and 7 show
7matrix.
show B4Cthe
the is SEM
SEM photos
photos
irregularly of the
ofshaped,
the cross-section
cross-section
with poorof of
thethe molded
molded
uniformity plate. size.
of plate.
particle
In Figures 6 and 7, the B4C particles are in red circles and the TiO2 particles are in
green circles. It can be seen from the figures that B4C and TiO2 are evenly dispersed in the
polyimide matrix. B4C is irregularly shaped, with poor uniformity of particle size.

Figure6.6. SEM
Figure SEMphoto
photoof
ofthe
thecross-section
cross-sectionofofthe
theB4BC/TiO
4C/TiO2/polyimide
2 /polyimide molded
molded plate
plate (Area
(Area 1).
1). (a)
(a) BB44C,
C,
TiO 2 particle distribution (100 μm), (b) B4C, TiO2 particle distribution (20 μm), (c) B4C, TiO2 particle
TiO2 particle distribution (100 µm), (b) B4 C, TiO2 particle distribution (20 µm), (c) B4 C, TiO2 particle
distribution(10
distribution (10µm),
μm),(d)
(d)BB4C,
C, TiO
TiO2 particle
particle distribution
distribution (5
(5 µm).
μm).
4 2
Figure 6. SEM photo of the cross-section of the B4C/TiO2/polyimide molded plate (Area 1). (a) B4C,
TiO2 particle distribution (100 μm), (b) B4C, TiO2 particle distribution (20 μm), (c) B4C, TiO2 particle
distribution (10 μm), (d) B4C, TiO2 particle distribution (5 μm).
Materials 2022,15,
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[Link]
Figure SEMphoto
photoofofthe
thecross-section
cross-sectionofofthe
theB4BC/TiO
4C/TiO2/polyimide
2
/polyimide molded
molded plate
plate (Area
(Area2).
2).(a)
(a)BB44C,
C,
TiO 2 particle distribution (100 μm), (b) B4C, TiO2 particle distribution (50 μm), (c) B4C, TiO2 particle
TiO2 particle distribution (100 µm), (b) B4 C, TiO2 particle distribution (50 µm), (c) B4 C, TiO2 particle
distribution (20 μm), (d) B4C, TiO2 particle distribution (10 μm).
distribution (20 µm), (d) B4 C, TiO2 particle distribution (10 µm).

The
In large particle
Figures 6 and 7,size theisBaround 30–50 μm, and the small particle size is around 5 μm.
4 C particles are in red circles and the TiO2 particles are in
The TiO particles are small and
green circles. It can be seen from the figures
2 adhere to thethatpolyimide
B4 C and TiO matrix, which shows good com-
2 are evenly dispersed in the
patibility. matrix.
polyimide The polyimide matrix in the
B4 C is irregularly cross-section
shaped, with poor hasuniformity
a sheet-shaped porous
of particle structure,
size.
whichThe maylargebe particle
due to the sizeductile
is aroundfracture30–50of the
µm,polyimide resin and
and the small the “wire
particle size ispulling”-
around
5like
µ[Link] when it are
The TiO2 particles is damaged
small and by adhere
an external to theforce.
polyimide matrix, which shows
good The distribution
compatibility. Theof B 4C and TiO
polyimide 2 in the
matrix inBthe
4C/TiO 2/polyimide
cross-section molded
has plate wasporous
a sheet-shaped further
confirmed by an energy spectrometer, and the test results are
structure, which may be due to the ductile fracture of the polyimide resin and the “wire shown in Figure 8. Accord-
ing to the components
pulling”-like phenomenon and when
the elemental composition
it is damaged of the molded
by an external force. plate, the distribution
of the
TheB element is theofkey
distribution B4to
C confirming
and TiO2 inB4the C, and the Ti2element
B4 C/TiO /polyimideis themolded
key to confirming
plate was
TiO2 distribution.
further confirmed by Theandistribution of B element
energy spectrometer, andmatches
the test well with
results arethe
shownblackinmasses
Figure in8.
Figure 3c (the
According firstcomponents
to the figure), further andproving that thecomposition
the elemental black massesofare thethe added plate,
molded B4C parti-
the
distribution
cles. Figure of 8cthe
(theB fifth
element is the
figure) key tothe
shows confirming
distribution B4 C,
ofand
the the Ti element
Ti element, is the
and the key to
Ti ele-
confirming TiO distribution. The distribution of B element
ments are more2 evenly distributed but with a low content, which is mainly due to a lowmatches well with the black
masses in Figure
TiO2 addition, 3c (theparticles,
smaller first figure),
better further provingwith
compatibility that the
thepolyimide
black masses are the
matrix, andadded
heavy
Bembedding.
4 C [Link]
Figure 8c (the withfifth
the figure)
analysisshowsresultsthe indistribution
Figures 6–8,ofit the Ti element,
is strongly and that
proved the
Ti
B4elements
C and TiOare more
2 have evenly
been evenlydistributed
dispersed butinwith a low content,
the polyimide which
matrix. Tableis 1mainly
showsdue the to a
con-
low
tentTiO 2 addition,
of the elements smaller
in theparticles,
system and better
theircompatibility with the
theoretical values polyimide
obtained from matrix, and
the cross-
heavy embedding.
sectional mappingCombined withthat
test. It is clear the the
analysis results
elemental in Figures
content of the6–8, it is strongly
selected areas forproved
map-
that B
ping is C and TiO
4 in good agreement
2 have been evenly dispersed in the polyimide matrix.
with the theoretical values of the elemental content of the Table 1 shows
sys-
the
tem,content
exceptoffor [Link]
There are in two
the system and their
main reasons for theoretical values
the large error obtained
of the from the
Ti element: the
cross-sectional mapping
content of Ti element [Link],
is low; It is clear athat
smallthemeasurement
elemental content errorof thelead
will selected areaserror
to a large for
mapping is in good
in the Ti element agreement
content; and TiO with the theoretical values of the elemental content of the
2 is well embedded by the polyimide resin, which makes
system, except for Ti.
some Ti elements [Link] are two main reasons for the large error of the Ti element: the
content of Ti element is low; therefore, a small measurement error will lead to a large error
in the Ti element content; and TiO2 is well embedded by the polyimide resin, which makes
some Ti elements undetectable.
Materials 2022,15,
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Figure8.
Figure 8. (a)
(a) An
An SEM
SEM photo
photo ofof the
the material;
material; (b)
(b) the
the element
element distribution
distributionmap;
map;and
and(c)
(c)EDS
EDSelemental
elemental
mapping consisting of B, C, N, O, and
mapping consisting of B, C, N, O, and Ti. Ti.

Table 1. The elemental content of the B4C/TiO2/polyimide molded plate cross-section.

Table 1. The elemental content of the B4 C/TiO2 /polyimide molded plate cross-section.
Element B C N O Ti
Element B C N O Ti
Measured value (wt%) 7.38 62.21 10.90 18.48 1.03
Measured value (wt%) 7.38 62.21 10.90 18.48 1.03
Theoretical value (wt%) 7.82
Theoretical value (wt%)
62.30
7.82 62.30
9.54 9.54 16.84
16.84
1.80
1.80

3.3. Thermal Properties Analysis

3.3. Thermal Properties Analysis
The thermal properties of the B4C/TiO2/polyimide molded plate are characterized
The thermal properties of the B C/TiO2 /polyimide molded plate are characterized
and analyzed by adopting DMA and4 TGA. Figure 9 shows the process of the DMA test on
and analyzed by adopting DMA and TGA. Figure 9 shows the process of the DMA test on
the molded plate, and its results. According to the Figure, as the temperature rises, the
the molded plate, and its results. According to the Figure, as the temperature rises, the
storage modulus of the molded plate presents certain fluctuations under a slow rising
storage modulus of the molded plate presents certain fluctuations under a slow rising trend,
trend, while the degree of change is not significant. When the temperature reaches about
while the degree of change is not significant. When the temperature reaches about 240 ◦ C,
240 °C, the storage modulus decreases slowly, which might be caused by the secondary
the storage modulus decreases slowly, which might be caused by the secondary relaxation
relaxation phenomenon due to the “thawing” of small motion units of the polyimide mo-
phenomenon due to the “thawing” of small motion units of the polyimide molecular chains.
lecular chains. When the temperature reaches about 300 °C, an obvious turning point of
When the temperature reaches about 300 ◦ C, an obvious turning point of the storage
the storage modulus-temperature
modulus-temperature curve appearscurve appears
with with an accelerated
an accelerated decrease, decrease, illustrating
illustrating that the
that the polyimide molecular chains have gradually thawed
polyimide molecular chains have gradually thawed and have become “free”. When and have become “free”.
the
When the temperature reaches ◦ about 400 °C, the decrease of the storage
temperature reaches about 400 C, the decrease of the storage modulus becomes slow again, modulus becomes
slow again,
indicating indicating
that that the
the polyimide polyimide
molecular molecular
chains chains have
have completed completed
“thawing” and “thawing”
become
and become fully “free”. In consideration of the wide thawing temperature
fully “free”. In consideration of the wide thawing temperature range of the polyimide range of the
molecular chains, the peak of the Tanδ- temperature curve within this range is selectedis
polyimide molecular chains, the peak of the Tanδ- temperature curve within this range
selected
as the glassas the glass transition
transition temperature,
temperature, whichthe
which means means
glassthe glass transition
transition temperature
temperature of the
of the B 4 C/TiO 2 /polyimide molded
B4 C/TiO2 /polyimide molded plate is 363.6 [Link] is 363.6
◦ °C.
Figure 10 shows the TGA-DTG curve. To effectively reduce the influence of the
thermal hysteresis on the TAG test, we grind the plate into powder for the test. The TAG
curve proves the outstanding thermal stability of the prepared molded plate. When the
temperature is below 550 ◦ C, no significant weight loss occurs. With the initial pyrolysis
temperature as high as 572.8 ◦ C, the molded plate’s Td , 5% (temperature corresponding to
5% weight loss) and Td , 10% (temperature corresponding to 10% weight loss) are 582.7 ◦ C
and 607.8 ◦ C, respectively. At 800 ◦ C, the char formation rate is 23.24 wt%. It can be seen
from the DTG curve that the temperature for the maximum pyrolysis rate is 617.2 ◦ C,
meaning the plate reaches the maximum pyrolysis rate at 617.2 ◦ C.
 5.0

Storage Modulus/GPa
4.5

4.0

Tanδ
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15
3.5

3.0
5.5
2.5
363.6 ℃
5.0
2.0

Storage Modulus/GPa
4.5
100 150 200 250 300 350 400
4.0
Temperature/℃

Tanδ
Figure
3.59. The storage modulus-temperature curve (blue) and the Tanδ-temperature curve (red) of
the B4C/TiO2/polyimide molded plate.
3.0
Figure 10 shows the TGA-DTG curve. To effectively reduce the influence of the ther-
mal hysteresis
2.5 on the TAG test, we grind the plate into powder for the test. The TAG curve
proves the outstanding thermal stability of the prepared molded plate. When the temper-
ature2.0is below 550 °C, no significant weight loss occurs. With the initial pyrolysis temper-
ature as high as 572.8 °C, the molded plate’s Td, 5% (temperature corresponding to 5%
100 150 200 250 300 350 400
weight loss) and Td, 10% (temperature corresponding to 10% weight loss) are 582.7 °C and
Temperature/℃
607.8 °C, respectively. At 800 °C, the char formation rate is 23.24 wt%. It can be seen from
the DTG
Figure
Figure curve
[Link]
The thatmodulus-temperature
storage
storage the temperature forcurve
modulus-temperature the maximum
curve (blue)
(blue) andandpyrolysis
thethe rate is 617.2
Tanδ-temperature
Tanδ-temperature °C, meaning
curve
curve (red)
(red) of
of the
the B C/TiO
plate /polyimide
reaches the molded
maximum
B4 C/TiO2 /polyimide molded plate.
4 2 plate.
pyrolysis rate at 617.2 °C.

Figure 10 shows the TGA-DTG curve. To effectively reduce the influence of the ther-
TGA 572.8 ℃
mal100
hysteresis on the TAG test, we grind the plate into powder for the test. The TAG curve
proves the outstanding thermal stability of the prepared molded plate. When the temper-
90
ature is below 550
DTG°C, no significant weight
582.7 ℃ loss occurs. With the initial pyrolysis temper-
Residual weight/%

ature
80 as high as 572.8 °C, the molded plate’s Td, 5% (temperature corresponding to 5%
607.8 ℃
weight loss) and Td, 10% (temperature corresponding to 10% weight loss) are 582.7 °C and
70
607.8 °C, respectively. At 800 °C, the char formation rate is 23.24 wt%. It can be seen from DTG
the DTG
60 curve that the temperature for the maximum pyrolysis rate is 617.2 °C, meaning
the plate reaches the maximum pyrolysis rate at 617.2 °C.
50

40 TGA 572.8 ℃
100
30
90
DTG 582.7 ℃ 617.2 ℃
20
Residual weight/%

80 607.8 ℃
100 200 300 400 500 600 700 800
70 Temperature/℃
DTG

Figure
Figure 10. The
6010. The TGA-DTG
TGA-DTG curve
curveof
ofthe
themolded
moldedplate.
plate.

3.4.
3.4. Mechanical
50
Mechanical Properties
Properties Analysis
Analysis
Adding
Adding additives to a polymer
40 additives to a polymer is is an
an important
important method
method toto improve
improve aa polymer’s
polymer’s prop-
prop-
erties
erties and endow it with special characteristics. In this process, the addictive type,
and endow it with special characteristics. In this process, the addictive type, volume
volume
of 30
of addition,
addition, andand scattering
scattering status
status influence
influence the the mechanical
mechanical properties
properties of
of the
the compound
compound
materials in a significant way. Considering the 617.2
B ℃
4B4C/TiO22/polyimide molded plate
C/TiO /polyimide molded will
materials
20 in a significant way. Considering the plate will be
be
used for a long time under a high temperature of 300 ◦ C, the molded plate is aged for 100 h
100 200 300 400 500 600 700 800
at 300 ◦ C, and its compression and impact resistance before and after aging are tested. To
ensure the accuracy of testTemperature/℃
results, the compression and impact resistance are tested three
times
[Link] the mechanical
The TGA-DTG curve ofproperties
the molded [Link]-aging properties of the molded plate
accordingly.
Figure 11 shows
3.4. Mechanical the compression
Properties Analysis test process and stress-strain curve of the B4 C/TiO2 /
polyimide molded plate. The
Adding additives to a polymer compression rate of the
is an important experiment
method is 1 mm/min.,
to improve a polymer’s and the
prop-
environment temperature is 10 ◦ C. According to the stress-strain curve in the Figure 11a),
erties and endow it with special characteristics. In this process, the addictive type, volume
at
ofthe initial compression
addition, and scatteringofstatus
three influence
tests (deformation lower than
the mechanical 4%), the
properties linear
of the change
compound
presented by the stress-strain curve indicates the plate is in the elastic deformation process
materials in a significant way. Considering the B4C/TiO2/polyimide molded plate will be
 three times to assess the mechanical properties and anti-aging properties of the mold
plate accordingly.
Figure 11 shows the compression test process and stress-strain curve of
B4C/TiO2/polyimide molded plate. The compression rate of the experiment is 1 mm/m
Materials 2022, 15, 2978 and the environment temperature is 10 °C. According to the stress-strain12curve of 15 in the F
ure 11a), at the initial compression of three tests (deformation lower than 4%), the lin
change presented by the stress-strain curve indicates the plate is in the elastic deformat
process of
of the compression. Thethecalculated
compression.
Young’sThe modulus
calculatedinYoung’s
three tests modulus in three
is 2.65 GPa, 2.61tests
GPa,is 2.65 G
2.61 GPa, and 2.38 GPa, respectively, with an average value
and 2.38 GPa, respectively, with an average value of 2.55 ± 0.12 GPa. Later, the increase of 2.55 ± 0.12 GPa. Later,
of stress gradually slows and basically remains unchanged after the deformation exceedsdeformat
increase of stress gradually slows and basically remains unchanged after the
exceeds 10%.
10%. The maximum The maximum
compression compression
strength strength
for the three tests isfor125.39
the three
MPa, tests is 125.39
121.95 MPa,MPa, 121
MPa, and 128.68 MPa, with an average value of 125.34
and 128.68 MPa, with an average value of 125.34 ± 2.75 MPa. When the deformation ± 2.75 MPa. When theisdeformat
less than 8%,is no
lessobvious
than 8%, no obvious
change occurs change occurs on
on the surface thesample.
of the surface However,
of the [Link],
the wh
the deformation exceeds 8%, cracks gradually appear on
deformation exceeds 8%, cracks gradually appear on the molded plate’s surface. Therethe molded plate’s surface. Th
is nobrittle
is no significant significant brittle fragmentation
fragmentation phenomenon phenomenon in the compression
in the compression process, which process,
is which
further proof of the soundness and toughness of the B C/TiO
further proof of the soundness and toughness of the B4 C/TiO2 /polyimide molded plate.
4 2 /polyimide molded pla
Therefore, itTherefore,
follows thatit follows
the B4that
C/TiO the2B/polyimide
4C/TiO2/polyimide
moldedmolded plate presents
plate presents outstanding co
outstanding
compressionpression resistance
resistance properties.
properties.

Figure
Figure 11. The 11. The curve
strain-stress strain-stress curve ofplate:
of the molded the molded plate:
(a) before (a) before
aging and (b)aging and (b) after aging.
after aging.

For the stress-strain curve after curve

For the stress-strain aging,after
thereaging,
is no significant
there is no trend of weakening
significant in
trend of weakening
terms of change and peak. In initial compression, the curve also presents
terms of change and peak. In initial compression, the curve also presents linear chan linear change,
and the Young’s
and themodulus
Young’s is 2.32 GPa, 2.36
modulus GPa,
is 2.32 and2.36
GPa, 2.30GPa,
GPa,andrespectively,
2.30 GPa,making for an making
respectively,
average value of 2.33 ±value
an average 0.03 ofGPa.2.33It±is0.03
revealed
GPa. Itthat after thethat
is revealed thermal aging,
after the the Young’s
thermal aging, the Youn
modulus of modulus
the molded plate
of the decreases
molded plateslightly,
decreasesmeaning themeaning
slightly, aging treatment
the agingreduces
treatmentthe reduces
rigidity of the molded
rigidity plate.
of the The maximum
molded plate. Thecompression strength forstrength
maximum compression three compressions
for three compressio
after aging is 124.68
after MPa,
aging is 127.19
124.68MPa,MPa,and 132.30
127.19 MPa,MPa, andrespectively,
132.30 MPa, with an average value
respectively, with an avera
of 128.06 ±value
3.17 MPa.
of 128.06 ± 3.17 MPa. The results, which demonstrate that compression
The results, which demonstrate that the maximum the maximum compr
strength after aging
sion is even
strength slightly
after aging higher
is eventhan that before
slightly higher thethan
treatment, indicate
that before the that the
treatment, indic
thermal agingthattreatment
the thermalwill aging
not produce
treatmentadverse influences
will not produce onadverse
the compression
influencesresistance
on the compress
properties of the molded
resistance plate. of
properties Table 2 showsplate.
the molded the test results
Table of the
2 shows theimpact resistance
test results of the impact
properties of the molded plate before and after aging. According to the results,
sistance properties of the molded plate before and after aging. According to the result a good
impact resistance properties
good impact is presented
resistance properties by is
the average by
presented impact resistance
the average impactstrength of stren
resistance
11.77 ± 0.59ofkJ/m 2 before the aging; after the test, the average impact resistance strength
11.77 ±2 0.59 kJ/m before the aging; after the test, the average impact resistance stren
2
is 11.57 ± 0.58 kJ/m± ,0.58
is 11.57 a slight
kJ/mdecrease
2, a slight ofdecrease
1.3% compared
of 1.3% with that before
compared the aging.
with that beforeThe the aging. T
raw materialrawpolyimide is thermosetting. The molecular bond breaks at high
material polyimide is thermosetting. The molecular bond breaks at high temperatu temperature,
which gradually
whichreduces
graduallyits mechanical properties. The
reduces its mechanical results show
properties. that the
The results showmaterial canmaterial c
that the
be used long-term under 300 ◦ C.
be used long-term under 300 °C.
Materials 2022, 15, x FOR PEER REVIEW 13 of 15
Materials 2022, 15, 2978 13 of 15

Table 2. The impact resistance properties of the B4C/TiO2/polyimide molded plate.

Table 2. The impact resistance properties of the B4 C/TiO2 /polyimide molded plate.
Section Width Section Thickness Impact Resistance Strength
Test Section Width Section ThicknessAbsorption
Absorption Work
Work(J) Impact Resistance
Test (mm) (mm) (kJ/m2) Strength
(mm) (mm) (J) (kJ/m2)
1 10.25 3.57 0.42 11.48 ± 0.57
1 10.25 3.57 0.42 11.48 ± 0.57
2 10.24 3.34 0.41 11.99 ± 0.60
Before 2 10.24 3.34 0.41 11.99 ± 0.60
Before Aging
Aging 33 10.22 3.64 0.44 11.83 ± 0.59
0.59
10.22 3.64 0.44 11.83 ±
Average
Average - - - - -- 11.77 ± 0.59
11.77 ± 0.59
11 10.16
10.16 3.373.37 0.40
0.40 11.68 ± 0.58
11.68 ± 0.58
22 10.22
10.22 3.593.59 0.42
0.42 11.45 ±
11.45 ± 0.57
0.57
After Aging
After Aging
33 10.15
10.15 3.493.49 0.41
0.41 11.57 ±
11.57 ± 0.58
0.58
Average - - - 11.57 ± 0.58
Average - - - 11.57 ± 0.58

3.5.
3.5. Shielding Performance
Performance Test
Test
The
The shielding
shieldingexperiment
experimentofofthe
thepolymer-based
polymer-based interlayer material
interlayer was
material carried
was outout
carried on
the americium
on the americiumberyllium neutron
beryllium source.
neutron TheThe
source. experimental layout
experimental is shown
layout is shownin Figure 12.
in Figure
During the actual measurement, a neutron dose equivalent meter was used to measure
12. During the actual measurement, a neutron dose equivalent meter was used to measure the
dose equivalent
the dose behind
equivalent the shielding
behind material.
the shielding material.

Figure 12.
Figure 12. The
The neutron-shielding
neutron-shielding experimental
experimentallayout
layout(1:
(1:the
theneutron
neutronsource;
source;[Link]the shadow
the shadowcone; 3:
cone;
thethe
3: polyethylene moderator
polyethylene moderatorlayer;
layer;[Link]the
thepolyethylene
polyethyleneshield
shieldlayer
layer(to
(toshield
shield incident
incident neutron); and
neutron); and
5: the
5: the neutron
neutron dose
dose equivalent
equivalent meter).
meter).

The shadow
The shadow cone cone can
can completely
completely block
block normal-incident
normal-incident neutrons
neutrons andand is
is mainly
mainly used
used
to measure
to measure the thedose
doseofofscattered
scatteredneutrons.
neutrons. TheThe
polyethylene
polyethylenemoderator
moderatorlayerlayer
mainly mod-
mainly
erates the americium
moderates the americiumberyllium neutron
beryllium source
neutron to measure
source to measurethe shielding
the shieldingeffect under
effect the
under
two neutron energy spectra. Figure 13 shows the experimental and
the two neutron energy spectra. Figure 13 shows the experimental and simulation resultssimulation results of
thethe
of polymer-based
polymer-based materials,
materials,and
andexperiments
experimentsand andsimulations
simulationsare arecarried
carried out
out on
on boron-
boron-
containing steel
containing steelwith
withaaboron
boroncontent
content ofof 1.7%.
1.7%. It can
It can be be seen
seen fromfrom
the the results
results in Table
in Table 3 that3
thatexperimental
the the experimentalresultsresults
are in are
goodinagreement
good agreement
with the with the simulation
simulation results,verifies
results, which which
verifies
the the accuracy
accuracy of theand
of the design design and preparation.
preparation. The neutron-shielding
The neutron-shielding effect
effect of the of the
polymer-
polymer-based
based interlayer interlayer
material ismaterial is that
inferior to inferior to boron-containing
of the that of the boron-containing
steel becausesteel because
the average
energy of theenergy
the average americium-beryllium neutron source
of the americium-beryllium is 4.5 MeV,
neutron andisthe
source 4.5 moderating
MeV, and the effect of
mod-
the iron effect
erating is dominant in this
of the iron energy range.
is dominant The
in this polymer-based
energy range. Theinterlayer material
polymer-based is more
interlayer
effective
material with
is moretheeffective
help of the outer
with the layer
help ofsteel.
the outer layer steel.
MaterialsMaterials
2022, 15,2022,
x FOR15,PEER
2978 REVIEW 14 of 15 14 of 15

Figure Figure 13. A comparison

13. A comparison of the experimental
of the experimental and simulation
and simulation results results
of two of two materials.
materials.

Table 3. The simulation and experimental results of two materials at 10 cm.

Table 3. The simulation and experimental results of two materials at 10 cm.

MaterialMaterial Composite Composite

(10 cm) (10 cm) BSS (10 cm)
BSS (10 cm)
- - Experiment
Experiment SimulationSimulation Experiment
Experiment Simulation
Simulation
Transmission (%) 34.88 35.87 28.18
Transmission (%) 34.88 35.87 28.18 28.56 28.56

4. Conclusions
4. Conclusions
The component
The component structure
structure of theofpolymer-based
the polymer-based materials
materials andand
the the three-layer
three-layer thickness
thick-
of the shield are obtained by the design of GA combined with MCNP.
ness of the shield are obtained by the design of GA combined with MCNP. The mass frac- The mass fraction of
boron carbide accounts for 11% of the polymer-based materials. The
tion of boron carbide accounts for 11% of the polymer-based materials. The B4C, TiO2, and B 4 C, TiO 2, and poly-
imidemolding
polyimide moldingpowder
powderareareblended
blendedvia viaball
ballmilling
millingandandmade
madeinto
into aa BB44C/TiO
C/TiO2/polyi-
2 /polyimide
mide molded plate through hot pressing. The density and composition of the materials were
molded plate through hot pressing. The density and composition of the materials
[Link]
were tested. The elemental
elemental content
content of the
of the selected
selected areasareas for mapping
for mapping is in agreement
is in good good agreement
with thewith the theoretical
theoretical content.
content. Then, Then, the characterizations
the characterizations and analysis
and analysis of its structure
of its structure and and
properties are performed. The results show that B 4 C and TiO 2 are
properties are performed. The results show that B4C and TiO2 are evenly dispersed in the evenly dispersed in
the polyimide matrix, proving that the materials are well-blended by ball milling. The
polyimide matrix, proving that the materials are well-blended by ball milling. The pre-
prepared B4 C/TiO2 /polyimide molded plate presents outstanding thermal properties,
pared B4C/TiO2/polyimide molded plate presents outstanding thermal properties, with its
with its glass transition temperature and initial pyrolysis temperature up to 363.6 ◦ C and
glass transition temperature and initial pyrolysis temperature up to 363.6 °C and 572.8 °C,
572.8 ◦ C, respectively. The test results of the impact resistance properties of the molded
respectively. The test results of the impact resistance properties of the molded plate before
plate before and after aging. According to the results, a good impact resistance property
and after aging. According to the results, a good impact resistance property is presented
is presented by the average impact resistance strength of 11.77 ± 0.59 kJ/m2 before the
by the average impact resistance strength of 11.77 ± 0.59 kJ/m2 before the aging; after 2the
aging; after the test, the average impact resistance strength is 11.57 ± 0.58 kJ/m , a slight
test, the average impact resistance strength is 11.57 ± 0.58 kJ/m2, a slight decrease of 1.3%
decrease of 1.3% compared with that before the aging. In addition, the plate demonstrates
compared with that before the aging. In addition, the plate demonstrates sound tough-
sound toughness, and excellent performance on compression resistance, impact resistance,
ness, and excellent performance on compression resistance, impact resistance, and ther-
and thermal aging resistance, which allow for its long-time use under 300 ◦ C. Finally, the
mal aging resistance, which allow for its long-time use under 300 °C. Finally, the prepared
prepared materials are tested experimentally on an americium beryllium neutron source.
materials
Theare tested experimentally
experimental results matchonthe ansimulation
americiumresults
beryllium
[Link] source. The ex-
perimental results match the simulation results well.
Author Contributions: Data curation, H.X., D.L., W.-Q.S. and X.-L.L.; Formal analysis, X.-L.L.;
AuthorInvestigation,
Contributions: Data
G.H.; curation, H.X.,
Methodology, W.L.;D.L., W.-Q.S.
Software, and X.-L.L.;
W.-Q.S. Formal
and R.-J.W.; analysis, X.-L.L.;
Supervision, G.H. and In-H.-S.H.;
vestigation, G.H.; Methodology, W.L.; Software, W.-Q.S. and R.-J.W.; Supervision, G.H. and H.-S.H.;
Writing—original draft, H.X.; Writing—review & editing, G.H. and H.-S.H. All authors have read
Writing—original
and agreed draft,
to the H.X.; Writing—review
published version of the&manuscript.
editing, G.H. and H.-S.H. All authors have read
and agreed to the published version of the manuscript.
Funding: This research is supported by the National Natural Science Foundation of China (11975182),
Funding: This research
the Foundation is supported
of Key Laboratoryby the National
of Science Natural Science
and Technology Foundation
on Reactor of China
System Design Technology
(11975182),
Laboratory, the Chinese Academy of Nuclear Power, the general projects of the Shaanxi Design
the Foundation of Key Laboratory of Science and Technology on Reactor System Provincial Na-
Technology Laboratory, the Chinese Academy of Nuclear Power, the general projects of the Shaanxi
ture Fund (2020JM-030), and the NSAF Joint Fund set up by the National Natural Science Foundation
Provincial Nature Fund (2020JM-030), and the NSAF Joint Fund set up by the National Natural
of China and the Chinese Academy of Engineering Physics (U1830128).
Science Foundation of China and the Chinese Academy of Engineering Physics (U1830128).
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
Materials 2022, 15, 2978 15 of 15

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