polymers

Review
Recent Advances and Challenges in Polymer-Based Materials for
Space Radiation Shielding
Elisa Toto 1 , Lucia Lambertini 1 , Susanna Laurenzi 1 and Maria Gabriella Santonicola 2, *

1 Department of Astronautical, Electrical and Energy Engineering, Sapienza University of Rome,

Via Salaria 851-881, 00138 Rome, Italy; [email protected] (E.T.); [email protected] (L.L.);
[email protected] (S.L.)
2 Department of Chemical Engineering Materials Environment, Sapienza University of Rome,
Via del Castro Laurenziano 7, 00161 Rome, Italy
* Correspondence: [email protected]

Abstract: Space exploration requires the use of suitable materials to protect astronauts and structures
from the hazardous effects of radiation, in particular, ionizing radiation, which is ubiquitous in the
hostile space environment. In this scenario, polymer-based materials and composites play a crucial
role in achieving effective radiation shielding while providing low-weight and tailored mechanical
properties to spacecraft components. This work provides an overview of the latest developments and
challenges in polymer-based materials designed for radiation-shielding applications in space. Recent
advances in terms of both experimental and numerical studies are discussed. Different approaches
to enhancing the radiation-shielding performance are reported, such as integrating various types of
nanofillers within polymer matrices and optimizing the materials design. Furthermore, this review
explores the challenges in developing multifunctional materials that are able to provide radiation
protection. By summarizing the state-of-the-art research and identifying emerging trends, this review
aims to contribute to the ongoing efforts to identify polymer materials and composites that are most
useful to protect human health and spacecraft performance in the harsh radiation conditions that are
typically found during missions in space.

Keywords: space radiation shielding; polymer-based materials; space exploration; irradiation tests;
Citation: Toto, E.; Lambertini, L.;
radiation transport codes
Laurenzi, S.; Santonicola, M.G. Recent
Advances and Challenges in
Polymer-Based Materials for Space
Radiation Shielding. Polymers 2024, 16, 1. Introduction
382. https://doi.org/10.3390/ The growing interest in outer space exploration draws attention to the importance of
polym16030382 protecting astronauts and facilities from exposure to hazardous radiation. Space radiation,
Academic Editor: Subhadip Mondal comprised of high-energy particles, possesses the potential to cause ionization of atoms
and molecular damage, affecting both biological tissues and spacecraft components [1,2].
Received: 22 December 2023 In this context, the use of effective shielding materials is essential to prevent and mitigate
Revised: 25 January 2024
deleterious effects on human health and on the systems that ensure a successful outcome
Accepted: 27 January 2024
of the mission [3].
Published: 30 January 2024
Ionizing space radiation includes solar particle events (SPEs) and galactic cosmic
radiation (GCR) [4]. GCR comprises highly energetic protons, alpha particles, electrons,
and high atomic number (Z > 2) particles. In particular, the GCR spectrum consists of
Copyright: © 2024 by the authors.
approximately 87% hydrogen ions (protons) and 12% helium ions (alpha particles), with
Licensee MDPI, Basel, Switzerland. the remaining 1–2% of high Z and energy (HZE) nuclei with charges from Z = 3 (lithium)
This article is an open access article to Z = 28 (nickel) [5]. Transition metals such as iron (Z = 26) are particularly difficult to
distributed under the terms and shield after ionization, thus posing a risk from a biological point of view. Electrons and
conditions of the Creative Commons positrons from GCR are considered a minor biological risk during space missions since they
Attribution (CC BY) license (https:// can be shielded more easily. GCR ions pose a significant health threat to astronauts during
creativecommons.org/licenses/by/ interplanetary travels, as their energies can penetrate several centimeters of biological tissue
4.0/). and spacecraft materials. SPEs are produced by impulsive flares or by coronal mass ejections

Polymers 2024, 16, 382. https://doi.org/10.3390/polym16030382 https://www.mdpi.com/journal/polymers

Polymers 2024, 16, 382 2 of 35

(CMEs). These fluxes involve electrons, protons, and other heavy-charged particles such as
iron. The nature of SPEs is sporadic and unpredictable, typically associated with intense
solar activity. SPEs generate energetic protons with fluences exceeding 109 protons/cm2 [5].
Primarily composed of low linear energy transfer (LET) protons with energies up to
1 GeV/n, these can be adequately shielded by the protective structures of spacecraft. SPE
dose rates vary during an event, ranging from 0 to 100 mGy/h inside a space vehicle and
from zero to 500 mGy/h for astronauts during extravehicular activities (EVAs) outside
of LEO. The frequency of SPEs is linked to sunspot activity, with the highest number of
events occurring during periods of strong equatorial sunspot activity. Exploration missions
beyond low earth orbit (LEO) that involve interplanetary travel may expose crew members
to multiple SPEs, as demonstrated by the five events that occurred during the recent transit
of the Mars Science Laboratory (MSL) spacecraft from Earth to Mars [6]. Moreover, the
interaction of high-energy SPE protons and heavy-charged GCR particles with spacecraft
structures causes onboard radiation hazards. In addition to the primary particles that can
affect spacecraft, secondary particles are generated through nuclear fission reactions. This
secondary radiation, including protons, alpha particles, beta particles, gamma rays, X-rays,
neutrons, and heavy-charged particles, can penetrate spacecraft shielding and contribute
significantly to the overall mission dose and has the potential to critically damage human
tissues [5]. NASA has categorized the human health risks from space radiation into four
groups: carcinogenesis, degenerative tissue risk (such as cardiovascular disease), acute
and late risks to the central nervous system (CNS), and acute radiation syndromes [7].
Concerning adverse effects on spacecraft materials, they can involve the development
of defects in the structure and chemical and mechanical degradation, including surface
erosion and embrittlement [8]. Therefore, the engineering of suitable, high-performance
radiation-shielding materials is crucial to preserve the integrity of spacecraft and the health
of astronauts.
Typically, radiation shielding exploits elements with the highest charge-to-mass ratio,
which are shown to be effective against HZE particles [9]. Although aluminum is commonly
used in spacecraft, its exposure to GCR can lead to the production of highly penetrating
secondary radiation, including neutrons and ions, which can cause electronic failures and
adverse biological effects. Hydrogen, with a high charge-to-mass ratio and the absence of
neutrons in its nucleus, proves effective in slowing down GCR through direct ionization [10].
Additional considerations could be taken into account. According to Bethe’s classical
theory, it can be demonstrated that, for minimizing the mass of the shielding material,
elements with low atomic numbers (low Z) are the most effective on a per-unit-mass basis.
Conversely, if the goal is to reduce the thickness of the shielding material, elements with
high atomic numbers (high Z) are most effective on a per-unit-thickness basis. A material
characterized by high Z acts as a better absorber of electrons and bremsstrahlung compared
to a low Z material, even if the production of bremsstrahlung is higher in materials with
high atomic numbers. Nevertheless, a high Z material is less effective in proton shielding.
Considering these effects, structures that incorporate both low Z and high Z materials
could be promising to achieve effective radiation shielding [11].
Polymer-based materials (PBMs) have emerged as effective candidates for achieving
protection against radiation while providing low-weight and tailored mechanical, ther-
mal, and electrical properties to spacecraft components. The incorporation of suitable
fillers into the polymers enables improved radiation-shielding properties. The addition
of hydrogen-containing nanoparticles, as well as the incorporation of light metals, can
enhance protection from GCR and SPEs [9]. Neutrons are produced as secondary par-
ticles through the interactions of GCR and SPEs with matter. Chemical elements with
significant thermal neutron absorptions, such as boron, lithium, and gadolinium, can be
exploited as radiation-shielding fillers [12]. Gadolinium nanoparticles, possessing the
highest neutron absorption cross-section among all elements, and boron, with a substantial
neutron absorption cross-section, emerge as excellent candidates for neutron shielding.
Nevertheless, the use of low-Z boron compounds should be preferred to those based on
Polymers 2024, 16, 382 3 of 35

gadolinium in order to avoid the generation of undesired secondary radiation, which has
detrimental effects on structural materials and parasitic effects on electronic components.
The neutron absorption cross-section for the isotope 10 B is 3835 barns, and enriching boron
compounds with 10 B could enhance protection against neutrons [9]. Compounds like boron
carbide (B4 C) and hexagonal boron nitride (hBN) in nanomaterial form, particularly nano-
B4 C and nano-hBN dispersed in polymer matrix, have demonstrated enhanced thermal
neutron attenuation [12]. The positive effect of using nanosized fillers can be related to
their surface-to-volume ratio, which increases the interactions with radiation, enhancing
the shielding effectiveness [13–16]. Boron and its low-Z compounds, like B4 C and hBN,
prove suitable for space neutron-shielding applications, while heavier elements are less
convenient due to their high atomic weight, leading to fragmentation and the generation of
secondary radiation.
This work provides an overview of the current developments in PBMs having radiation-
shielding properties suitable for application in outer space. In the first sections, recent
advances in terms of experimental and numerical investigations are discussed. In partic-
ular, the latest experimental studies on PBMs made of polyethylene (PE), polyimide (PI),
polydimethylsiloxane (PDMS), and other functional matrices are described, examining
the role of different fillers. The optimization of the PBM design, as well as the suitable
dispersion of the reinforcement, were considered for evaluating the overall performance of
the PBMs. The discussion includes the ability of PBMs to absorb incoming radiation and its
effects on their properties. Numerical studies on PBMs were argued after describing the
main radiation transport codes that are currently used. These codes are fundamental for
evaluating the material shielding effectiveness before missions and in the selection of the
most suitable radiation countermeasures. In this perspective, the strengths and weaknesses
of the different codes were highlighted. Then, numerical analyses performed in GCR, SPEs,
and low earth orbit (LEO) environments on different PBMs were discussed. Finally, before
the concluding remarks, a section on the summary and challenges regarding the design of
effective radiation-shielding PBMs was provided.
In summary, this review explores the challenges in developing multifunctional ma-
terials that are able to provide radiation protection in the harsh space environment. By
identifying emerging trends in the field, this review aims to contribute to the ongoing
efforts to define the PBMs that are most useful to protect humans’ health and spacecraft
performance in the radiation conditions that are typically found during space exploration.

2. Experimental Studies
2.1. Polyethylene-Based Materials
Polyethylene (PE) is a versatile material successfully employed in different fields
due to its ease of processing, chemical inertness, and low moisture absorption [17]. The
mechanical and physical behavior of PE is strictly dependent on its crystal structure and
molecular weight [18,19]. The PE properties are particularly valued for industrial storage,
electronics, and in the aerospace sector due to its ability to shield against radiation [20].
PE, composed of ethylene monomers, offers effective radiation shielding due to its high
hydrogen content, and this aptitude can be enhanced by embedding suitable fillers into
the polymer.
PE lacks the necessary strength and thermal stability for structural use. In this regard,
multifunctional fillers, such as carbon nanoparticles, have been employed to enhance the
mechanical and functional properties of PE and, at the same time, improve protection from
space radiation [21,22].
Zhang et al. proposed the use of a composite material made of ultrahigh-molecular-
weight polyethylene fiber (UPEF), boron nitride (BN), and polyurethane (PU) for effective
neutron radiation shielding [23]. Neutron radiation, composed of uncharged particles,
has harmful effects on human tissues, leading to diseases like cancer and cardiovascular
issues [24]. Traditional neutron-shielding materials like concrete and metal have limitations,
especially in aerospace applications, needing the development of new materials. In this
Polymers 2024, 16, 382 4 of 35

work, UPEF, known for its mechanical properties, is combined with boron, which absorbs
thermal neutrons effectively. The composite, made of UPEF, boron modified with tannic
acid (TA), and PU, showed promising neutron-shielding effectiveness. In particular, the
dispersion of fillers in the matrix is crucial for efficient shielding, and the modification of
boron with TA improved the dispersion. The results from mechanical testing indicated high
tensile strength, suggesting the potential use of the UPEF/BN/PU composite as a structural
material. Figure 1a schematically represents the irradiation test. The neutron wavelength
was 0.53 nm, and the sample-to-detector distance was 10.45 m. The neutron transmission
factor, denoted as I/I0 , was calculated to assess the neutron-shielding effectiveness of
the UPEF/BN/PU composites at different BN loadings. I and I0 represent the quantities
of transmitted neutron fluxes with and without the presence of the shielding composite,
respectively (Figure 1a). Following the Beer–Lambert law, the attenuation of neutrons
passing through the material is determined by the equation:

I
= e−µχ (1)
I0

where χ is the thickness of the UPEF/BN/PU composite and µ is the linear attenuation
coefficient that can be expressed as follows:

1 I0
µ= ln (2)
χ I

the mass attenuation coefficient (µ/ρ) was calculated as follows:

µ 1
= ln(I0 /I) (3)
ρ ρχ

where ρ is the density of the sample. The results unveiled that the neutron radiation inten-
sity decreases by approximately 25%, 63%, and 85% when passing through UPEF/BN/PU-0
with thicknesses of 0.8, 1.6, and 3.2 mm, respectively (Figure 1b). Considering samples
without BN, the neutron attenuation results from the high hydrogen content in UPEF. The
findings align with theoretical predictions that emphasize the effective neutron-shielding
properties of materials rich in hydrogen. For the UPEF/BN/PU samples loaded with BN
at 7 wt%, the neutron-shielding capability improves, as indicated by the decreasing of
the I/I0 value. This improvement is attributed to the ability of boron to absorb neutrons
through nuclear reactions with the boron nucleus in BN. Neutrons are sequentially mod-
erated by hydrogen and absorbed by boron. However, above 7 wt% of BN loadings, the
efficiency of neutron shielding decreases. This suggests that continuously adding BN fillers
may not enhance neutron-shielding efficiency and could potentially affect the mechanical
properties of the composites. Moreover, the thickness of the UPEF/BN/PU composite
significantly influences neutron-shielding performance. For BN content below 7 wt%, I/I0
for UPEF/BN/PU with a thickness of 1.6 mm is approximately 25–30% lower than that
of UPEF/BN/PU with a thickness of 0.8 mm. With increasing BN content, the difference
in the I/I0 value between UPEF/BN/PU composites with different thicknesses decreases.
Figure 1c indicates that both µ and µ/ρ increase as the BN content rises. Definitively,
an optimal BN content of 7 wt% is identified, balancing neutron-shielding efficiency and
mechanical properties. Hence, the UPEF/BN/PU composite can be considered a suitable
candidate for radiation shielding in aerospace structures.
Polymers
Polymers2024,
2024,16,
16,x382
FOR PEER REVIEW 5 5ofof38
35

Figure (a) Schematic

Figure1.1. (a) representationofofthe
Schematic representation theirradiation
irradiation test
test using
using a thermal
a thermal neutron
neutron source;
source; (b)
(b) Neu-
Neutron transmission factor (I/I0) as a function of BN loading for UPEF/BN/PU composites with
tron transmission factor (I/I0 ) as a function of BN loading for UPEF/BN/PU composites with
thickness of 0.8 mm, 1.6 mm, and 3.2 mm; (c) linear a enuation coefficient (µ), and mass a enuation
thickness of 0.8 mm, 1.6 mm, and 3.2 mm; (c) linear attenuation coefficient (µ), and mass attenuation
coefficient (µ/ρ) as a function of BN loading for UPEF/BN/PU composites with thickness of 1.6 mm.
coefficient (µ/ρ) as a function of BN loading for UPEF/BN/PU composites with thickness of 1.6 mm.
Adapted with permission from Ref. [23].
Adapted with permission from Ref. [23].

Neutronexposure
Neutron exposureexperiments
experimentswere wereconducted
conductedby byHerrman
Herrmanetetal. al.on
onhigh-density
high-density
polyethylene
polyethylene(HDPE)-based
(HDPE)-basedcomposites
composites[25]. [25].Boron
Boroncarbide
carbide(BC)(BC)and andboron
boronnitride
nitride(BN)
(BN)
with particle sizes less than 10 µm were chosen as fillers and added
with particle sizes less than 10 µm were chosen as fillers and added to injection-molding- to injection-molding-
grade
gradeHDPE.
HDPE.Irradiation
Irradiation tests were
tests were performed
performed using a 1-Curie
using Americium-Beryllium
a 1-Curie Americium-Beryllium neu-
tron source. A dose rate of 0.6 mSv/h/GBq at a distance of 1 m
neutron source. A dose rate of 0.6 mSv/h/GBq at a distance of 1 m was applied for 15 min, was applied for 15 min,
with
withthe thesource
sourcepositioned
positioned5050 cm cm away
away from
fromthethe detector, andand
detector, counts
counts were recorded
were recordedat 10at
s10intervals.
s intervals.TheThe neutron
neutron exposure
exposure tests were
tests were conducted
conducted using
using bare
bareindium
indiumfoilfoiland
andbare
bare
indium
indiumfoil/sample
foil/sample pairings.
pairings. BareBareindium
indium foil foil
waswas usedused
as a reference
as a reference due to its to
due highitsneu-
high
tron absorption
neutron absorption cross-section. The indium
cross-section. The indiumfoil/sample
foil/samplepairings included
pairings bare indium
included foils
bare indium
with
foils with 1%, 5%, and 30% BN samples. The neutron exposure tests aimed to determinethe
1%, 5%, and 30% BN samples. The neutron exposure tests aimed to determine the
mass
massabsorption
absorption cross-section (µ/ρ) for thermal neutrons
cross-section (µ/ρ) neutronsand andthetheeffectiveness
effectivenessofofshielding.
shield-
ing.
TheThe results
results suggested
suggested thatthat higher
higher BN BN content
content leads leads to lower
to lower initial
initial radiation
radiation detected,
detected, and
and
mass mass absorption
absorption (shield
(shield effectiveness)
effectiveness) increased
increased withwith
lower lower
initialinitial activity.
activity. Atomic Atomic
force
force microscopy
microscopy (AFM) (AFM)
studiesstudies revealed
revealed that HDPE-BN
that HDPE-BN blends blends
were were reasonably
reasonably uniform uniform
at low
atBNlow BN concentrations,
concentrations, while while
higherhigher percentages
percentages reduced reduced uniformity,
uniformity, potentially
potentially due toduethe
tolubricating
the lubricating effect of BN. Compressive strength was observed
effect of BN. Compressive strength was observed to decrease initially with BN to decrease initially
with BN addition,
addition, but higher butamounts
higher amounts
of BN induced of BNan induced
increaseaninincrease in theThe
the strength. strength.
presence Theof
boron nitride
presence of boronin the sample
nitride wassample
in the found to was influence
found tomass absorption,
influence confirming confirm-
mass absorption, its role in
shaping
ing its roletheinshielding
shaping the properties
shielding of the material.
properties ofBased on theseBased
the material. findings, the HDPE/BN
on these findings,
composites
the HDPE/BN can be considered
composites can beforconsidered
potential use for in aerospace
potential use due to their advantageous
in aerospace due to their
mechanical and
advantageous radiation-shielding
mechanical properties. properties.
and radiation-shielding
Zaccardi et al. fabricated multifunctional
Zaccardi et al. fabricated multifunctional nanocomposites nanocompositesusing using medium-density
medium-density
polyethylene(MDPE)
polyethylene (MDPE)loaded loadedwithwithmultiwalled
multiwalledcarbon carbonnanotubes
nanotubes(MWCNTs),
(MWCNTs),graphene graphene
nanoplatelets(GNPs),
nanoplatelets (GNPs), and hybrid MWCNT/GNP MWCNT/GNP fillers fillers [22].
[22]. Electrical
Electricalproperties,
properties,chemical
chemi-
structure,
cal structure, thermal
thermal behavior,
behavior,wettability,
we ability,and andmorphology
morphology were investigated before
were investigated beforeandand
after proton irradiation. In particular, the samples were irradiated for 294 s, with an
Polymers 2024, 16, 382 6 of 35

energy of 64 MeV and a current of 1 nA, resulting in a total dose of 50 Gy. According
to the U.S. Center for Disease Control and Prevention’s information on acute radiation
syndrome, a dose of 50 Gy is known to induce the fatal collapse of the human cardiovascular
and central nervous systems. This dosage exceeds the acceptable exposure limits for
astronauts [26]. The experiments were conducted at the Crocker Nuclear Laboratory
of the University of California (Davis, CA, USA). FTIR analyses revealed a decrease in
crystallinity (Xc) after irradiation, more pronounced in the GNP-filled nanocomposites.
Thermal analysis using differential scanning calorimetry (DSC) confirmed the decrease in
crystallinity and unveiled thermal stability after irradiation. Contact angle measurements
indicated a decrease in hydrophobicity after proton exposure, whereas morphological
analysis by SEM highlighted surface erosions after irradiation. The results indicated that
the MDPE/MWCNT 5 wt% nanocomposite maintains thermal stability, a hydrophobic
behavior, and negligible changes in crystallinity, making it a promising shielding material
in high-ionizing-radiation environments, such as space.
A multilayer composite material was developed by alternately stacking layers of high-
density polyethylene/hexagonal boron nitride (HDPE/hBN) and low-density polyethylene
(LDPE) [27]. The neutron-shielding ability of these PE/hBN composites was evaluated
after irradiation experiments using neutrons with a wavelength (λ) of 0.53 nm and a spread
∆λ/λ = 16%. The composites were fabricated by a two-step hot-pressing process, where
HDPE/hBN and LDPE layers were individually hot-pressed into slices and then stacked
alternately and hot-pressed to form multilayer composite films. This strategy aimed to
align hBN along the in-plane direction for improved performance. The neutron-shielding
effectiveness was evaluated using neutron transmission factor (I/I0 ), linear attenuation
coefficient (µ), and mass attenuation coefficient (µ/ρ). The results indicate that the neutron
radiation intensity decreases by ~50% when passing through PE films (Figure 2a), and this
can be justified by the high hydrogen content in PE. The incorporation of hBN into the PE
matrix enhances the neutron-shielding performance, as proven by a decrease in the I/I0
value at increasing hBN loadings. This result can be ascribed to the synergistic attenuation
effect of hydrogen and boron atoms. The optimal I/I0 value is achieved at 4.16% for the
multilayer composite with a 30 wt% hBN content, indicating that ~95.84% of neutron
radiation is shielded when passing through the composite. Comparatively, at filler loadings
below 15 wt%, multilayer composites exhibit similar shielding ability to random composites,
possibly due to incomplete coverage of hBN. Considering filler loadings above 20 wt%, the
multilayer composites showed superior shielding ability compared to random composites.
At 30 wt% filler content, the I/I0 for multilayer PE/hBN decreases to 4.16%, much lower
than the random PE/hBN value of 14.95%. Figure 2b,c reveal that both µ (linear attenuation
coefficient) and µ/ρ (mass attenuation coefficient) increase with higher hBN content, and
the multilayer PE/hBN values exceed those of random PE/hBN at the same hBN content.
Figure 2d shows the µ/ρ enhancement calculated by ∆µ/ρ = (µ/ρm − µ/ρr )/(µ/ρr ), where
µ/ρm and µ/ρr are referred to multilayer PE/hBN and random PE/hBN, respectively. At
low filler content, ∆µ/ρ is small, indicating that the multilayer structure has a minimal
impact on neutron-shielding enhancement. However, with a 30 wt% hBN content in the
multilayer composite, ∆µ/ρ reaches 41.37%, demonstrating the effective improvement of
neutron-shielding performance with a high filler content. A critical hBN content (30 wt%)
was detected for the noticeable enhancement of the multilayer structure compared to the
random composite. Overall, the performance of the PE/hBN multilayer sample suggests
its potential application in neutron shielding and thermal management in fields such
as aerospace.
Polymers 2024, 16, x FOR PEER REVIEW 7 of 38
Polymers 2024, 16, 382 7 of 35

Figure 2.
Figure (a) Neutron transmission
2. (a) transmission factor (I/I0),
(I/I0),(b)
(b)linear
linear aattenuation coefficient(µ),
enuation coefficient (µ), and
and (c)
(c) mass
mass
aattenuation coefficient (µ/ρ)
enuation coefficient as aa function
(µ/ρ) as function of hBN content
content for
for PE/hBN films. (d) µ/ρ
PE/hBN films. enhancement of
µ/ρenhancement of
multilayer
multilayer and
and random
random PE/hBN
PE/hBNfilms.films.Adapted
Adaptedwith
withpermission
permissionfrom Ref.[27]
fromRef. [27]..

Composite materials
Composite materials made
made ofof high-density
high-density polyethylene (HDPE) filled
polyethylene (HDPE) filled with
with Al O33,,
Al22O
Fe O , and PbO were fabricated and tested under γ-radiation [28]. A 60 KBq
Fe22O33, and PbO were fabricated and tested under γ-radiation [28]. A 60 KBq source of Ra source
226 of
226 Ra was used to obtain the γ-rays beam at different energies: 0.295, 0.352, 0.609, 1.12,
was used to obtain the γ-rays beam at different energies: 0.295, 0.352, 0.609, 1.12, and 1.747
and 1.747
MeV. TheMeV. The following
following parameters
parameters were were
usedused
to to comparethe
compare the radiation-shielding
radiation-shielding
effectiveness of the composites: linear attenuation coefficient (µ), transmission
effectiveness of the composites: linear a enuation coefficient (µ), transmission factor factor(TF),
(TF),
mean free path (MFP), half-value layer (HVL), and radiation protection efficiency
mean free path (MFP), half-value layer (HVL), and radiation protection efficiency (RPE). (RPE).
These parameters
These parameters are
are expressed
expressed asas follows:
follows:
II
==
TFTF (4)
(4)
I0I

I
MFP
MFP== I (5)
(5)
µµ
ln 2
HVL = ln 2 (6)
HVL = µ (6)
μ

RPE = 1 − e−µt × 100 (7)
The following materials wereRPE = (1 −and
prepared ) × 100
e tested: pure HDPE, HDPE + 30% Al2 O (7)3 ,
HDPE
The + 30% Fe
following 2 O3 , HDPE
materials were+prepared
10% PbO,
andHDPE + pure
tested: 30% PbO,
HDPE,and HDPE
HDPE + 50%
+ 30% Al2OPbO. The
3, HDPE

+ 30% Fe2O3, HDPE + 10% PbO, HDPE + 30% PbO, and HDPE + 50% PbO. The values ofob-
values of µ decrease at increasing radiation energies. A noticeable decrease in µ was µ
served foratradiation
decrease increasingenergies below
radiation 0.609 MeV,
energies. and this can
A noticeable be ascribed
decrease to the
in µ was dominance
observed for
of the photoelectric
radiation effects0.609
energies below in theMeV,
material. Above
and this can0.609 MeV, thetodominance
be ascribed of Compton
the dominance of the
scattering takes place. The results showed that the samples containing PbO have supe-
photoelectric effects in the material. Above 0.609 MeV, the dominance of Compton
rior attenuation capacity and efficiency compared to those loaded with Al O3 and Fe2 O3 .
sca ering takes place. The results showed that the samples containing PbO2 have superior
Among the composites, the one loaded with 50% PbO achieved the best results, demonstrat-
a enuation capacity and efficiency compared to those loaded with Al2O3 and Fe2O3.
Polymers 2024, 16, 382 8 of 35

ing the highest value of µ and the smallest values of MFP, HVL, and TF for all the tested
radiation energies. Hence, these composites can be considered effective radiation-shielding
materials to be potentially applied in fields requiring high γ-ray attenuation, such as space.

2.2. Polyimide-Based Materials

Polyimides (Pis) are a class of high-performing polymers showing outstanding ther-
mal stability, chemical and radiation resistance, and suitable mechanical and dielectric
properties [29–32]. Pis can be considered neutron moderators since their structure includes
carbon, hydrogen, nitrogen, and oxygen, which mitigate the generation of secondary par-
ticles after collision with neutrons. The radiation-shielding effectiveness of Pis has been
successfully enhanced by the incorporation of nanomaterials, such as bismuth oxide and
boron nitride.
Pavlenko et al. fabricated polyimide-based composites filled with bismuth oxide
(Bi2 O3 ) and tested their radiation-shielding behavior under γ-ray exposure [33]. The Bi2 O3
particles were modified with polymethylphenylsiloxane (PMPS) to achieve a uniform dis-
tribution in the composites. The irradiation tests were performed at 400 keV and 662 keV,
using radionuclides 192 Ir (400 keV) and 137 Cs (662 keV) as sources. The results demon-
strated that the incorporation of Bi2 O3 significantly improved the thermal stability of the
composites. Moreover, the modified Bi2 O3 particles showed hydrophobic behavior, enhanc-
ing their distribution in the non-polar PI matrix. Composites produced by hot-pressing
exhibited higher density and microhardness compared to those produced by cold-pressing,
indicating a more uniform distribution of fillers. The radiation-shielding properties of the
composites were assessed experimentally and theoretically, unveiling a high-radiation-
protective behavior. In particular, the results showed that the mass attenuation coefficient
(µm ) increases linearly with the Bi2 O3 loading (0–60 wt%). Overall, the incorporation of
PMPS-modified Bi2 O3 into the PI matrix and the hot-pressing method proved effective for
fabricating attractive materials for space technology and radiation protection.
Baykara et al. developed composite materials with shielding properties against both
neutrons and γ-rays. A thermoplastic polyimide was used as a matrix and filled with
gadolinium oxide (Gd2 O3 ) and hexagonal boron nitride (hBN) nanoparticles [34]. The
neutron-shielding properties of hBN/Gd2 O3 /PI samples with different filler loadings were
assessed after irradiation with a 239 Pu-Be neutron source. Neutron transmission factors
were determined experimentally by measuring the ratio of incident (I0 ) and transmitted (I)
neutron fluxes. The macroscopic cross-section (Σ) and mass attenuation coefficient (µ/ρ)
were computed based on the count rate (cps) for neutrons and the gamma dose rate (µR/h)
for gamma radiation measured during the experiments. The source used for experiments
generates both neutron and gamma radiation, and suitable measurements were conducted
to distinguish and evaluate the shielding efficiencies of the nanocomposites against each
type of radiation. The results unveiled that samples exhibited an exponential decrease in
neutron flux attenuation, with fluctuations observed as the thickness increased. The fluctu-
ations were attributed to the interaction of neutrons with nanoparticles within the shielding
materials. The nanocomposite with 11 wt% hBN showed the highest neutron-shielding
performance. Considering samples at high loadings of Gd2 O3 , the neutron transmissions
exhibited fluctuations dependent on the thickness of the shield material. To validate the
results, neutron permeability experiments for the nanocomposite with 11 wt% hBN/3 wt%
Gd2 O3 /PI were repeated at different thicknesses. In this case, results demonstrated con-
sistency in neutron-shielding efficiency between the initial and repeated experiments.
The gamma shielding ability of the nanocomposites was also thoroughly investigated.
The experiments involved measuring gamma dose rates resulting from the interaction
between the neutron source and the neutron-shielding material. The nanocomposites
showed an exponentially decreasing behavior in gamma transmission, with transmission
percentages superior to that of neat polyimide. Further analysis involved the calculation of
macroscopic cross-section and mass attenuation coefficient values for both neutron and
gamma rays. The macroscopic cross-section values for nanocomposites ranged between
Polymers 2024, 16, 382 9 of 35

0.1898 and 0.4052 cm−1 , exhibiting a significant improvement compared to neat polyimide
(0.1316 cm−1 ). In summary, the findings of this experimental study demonstrated the
multifunctional properties of the nanocomposites, with high efficacy in attenuating both
neutron and gamma radiation due to the interplay between hBN and Gd2 O3 . The results
indicate that these nanocomposites are promising materials for applications requiring
effective protection against radiation sources in fields such as aerospace.
Polyimide-hexagonal boron nitride (PI-hBN) nanocomposites were fabricated us-
ing direct forming technology (DF) to enhance their tribological and radiation-shielding
properties [35]. The process involved the incorporation of hexagonal boron nitride (hBN)
nanoparticles at concentrations of 2 wt% and 5 wt% into a polyimide matrix. The ball
milling technique was employed to minimize nanoparticle agglomeration and ensure the
uniform distribution of hBN within the PI matrix. The neutron-shielding effectiveness of
the samples was examined using an americium (241 Am)-beryllium (9 Be) neutron source.
The assessment of neutron shielding involved the examination of the linear absorption
coefficient (µ) and mass absorption coefficient (µ/ρ). In particular, µ was used to quantify
the extent of incident radiation attenuation, normalized by thickness, whereas µ/ρ ex-
presses the attenuated radiation normalized by both density and thickness, as indicated by
Equation (3). Quantitative measurements of neutron transmission through the nanocom-
posites were performed, and the results highlighted a significant decrease in neutron flux as
a function of the hBN content. The 2 wt% and 5 wt% hBN-loaded PI nanocomposites exhib-
ited significantly lower neutron transmission compared to the neat PI matrix. In particular,
the linear and mass absorption coefficients exhibited substantial improvement, increasing
by 1.9 and 2.2 times for 2 wt% and 5 wt% hBN-loaded PI, respectively, in comparison to
the neat PI. Figure 3a shows that the percentage of radiation shielded by 2 wt% and 5 wt%
hBN-loaded PI increased by 26.7% and 29.1%, respectively, in comparison to the unloaded
PI. These results confirm the efficacy of hBN as a neutron-absorbing component within the
composite. As schematically represented in Figure 3b, the presence of hydrogen-rich atoms
in PI facilitates the deceleration of neutron beams during collisions and contributes to
neutron absorption within the matrix. The shielding effectiveness of the PI matrix is further
heightened by hBN, where boron atoms play a role in thermal neutron capture. Neutron
absorption occurs when low-energy thermal neutrons irradiate the stable 10 B isotope in
hBN. As a result, reactions such as nuclear capture and fission take place, leading to the
formation of alpha particles (4 He) and (7 Li) nuclei, accompanied by the generation of heat.
Subsequently, the generated heat is dissipated through hBN within the PI matrix. Overall,
the nanocomposites demonstrated superior neutron-shielding properties, unveiling
Polymers 2024, 16, x FOR PEER REVIEW 10 of 38 their
potential suitability for applications in space missions where exposure to neutron radiation
is a critical concern.

Figure 3. Cont.
Polymers 2024, 16, 382 10 of 35

Figure
Figure3.3. (a)
(a) Percentage of
of radiation
radiationshielded
shieldedbybyneat
neat
PI,PI, 2 wt%
2 wt% hBN/PI,
hBN/PI, andand 5 wt%
5 wt% hBN/PI
hBN/PI nanocom-
nanocomposites; (b) schematic representation of the neutron-shielding mechanism of hBN/PI
posites; (b) schematic representation of the neutron-shielding mechanism of hBN/PI nanocomposites.
nanocomposites. Adapted with
Adapted with permission Ref. [35]. from Ref. [35].
permission
from

Cherkashina
Cherkashina et et
al. al.
focused on the
focused onimpact of electron
the impact irradiation
of electron on the structural
irradiation and
on the structural
property changes in polyimide materials [36]. Composite samples
and property changes in polyimide materials [36]. Composite samples based on PI track based on PI track
membranes
membranesand andnanodispersed
nanodispersed lead (70(70
lead wt%)
wt%)were fabricated.
were The The
fabricated. impact of fast
impact ofelectrons
fast electrons
with energies ranging from 1 to 5 MeV was evaluated on
with energies ranging from 1 to 5 MeV was evaluated on the neat PI and on the the neat PI and onPIthe PI
composite.
composite. The irradiation employed a one-sided mode, preceded
The irradiation employed a one-sided mode, preceded by thermal treatment of the samplesby thermal treatment
ofinthe samples oven
a vacuum in a vacuum
at 180 ◦oven
C forat3180
h. To°C assess
for 3 h.the
To assess
absorbedthe absorbed dose distribution
dose distribution and effective
and effective electron range, tests were conducted by incrementally increasing sample
electron range, tests were conducted by incrementally increasing sample thickness. Samples
thickness. Samples of 25 µm thickness were tightly stacked, and a detector was placed
of 25 µm thickness were tightly stacked, and a detector was placed behind them. The
behind them. The effective electron range was determined by the total film thickness at
effective electron range was determined by the total film thickness at which the detector
which the detector ceased detecting radiation. All samples received a total dose of 10 MGy.
ceased detecting radiation. All samples received a total dose of 10 MGy. The effective range
The effective range of electrons detected in PI and PI composite is directly proportional to
of electrons detected in PI and PI composite is directly proportional to initial electron energy
initial electron energy and increases with energy. Enhanced radiation-shielding
and increases with energy. Enhanced radiation-shielding characteristics of the composite,
characteristics of the composite, compared to PI, are attributed to the structure of
compared to PI, are attributed to the structure of composites. Contact between the track
composites. Contact between the track membrane and metallic lead results in a contact
membrane
potential and metallic
difference, leadanresults
creating electricinfield
a contact potential
preventing difference,
electron creating
transition. The an electric
near-
contact layer of the composite enriches with electrons, increasing conductivity. For high- with
field preventing electron transition. The near-contact layer of the composite enriches
electrons,
energy increasing
electrons, conductivity.
the increased Fordensity
electron high-energy
in the electrons,
near-contact thelayer
increased
leads electron
to a higherdensity
in the near-contact layer leads to a higher probability of scattering
probability of scattering at larger angles, causing ionization and radiation losses. This at larger angles, causing
ionization
results in a and radiation
significant losses. in
reduction This resultsflux
electron in ainsignificant reduction
the PI composite. in electron
Overall, resultsflux in
showed that the penetration depth of electrons into PI is greater than in the composite. PI is
the PI composite. Overall, results showed that the penetration depth of electrons into
greater
The than
tensile in the of
strength composite. The tensile
both materials decreasesstrength
slightlyof after
bothirradiation,
materials decreases slightly after
and the electrical
properties of the composite remain largely unaffected. The findings of this experimental The
irradiation, and the electrical properties of the composite remain largely unaffected.
findings of this experimental study suggested the potential use of the PI/lead composite in
space, offering protection against cosmic radiation.
Ultraviolet (UV)-shielding materials based on a highly fluorinated polyimide (FPI)
filled with allomelanin nanoparticles (AMNPs) were developed by Li et al. [37]. The pres-
ence of fluorinated groups in FPI increases porosity and decreases density, expanding the
propagation path of UV and enhancing UV-shielding performance. The results demonstrate
improved mechanical and UV-shielding properties with the synergistic absorption of UV
by FPI and AMNPs. In this study, curcumin was used to evaluate the UV-shielding per-
formance of the composites through UV-vis measurements, as schematically represented
in Figure 4a. Figure 4b schematically represents the UV interaction with the FPI/ANMPs
composite. Curcumin was chosen due to its high instability under UV irradiation, leading
to the decomposition of the α-carbon in its structure into aldehydes, further oxidizing into
acids [38]. In the blank control group (Figure 4c), the absorbance of curcumin dropped to
zero after 50 min of irradiation. This correlated with a color change from dark yellow to
 the propagation path of UV and enhancing UV-shielding performance. The results
demonstrate improved mechanical and UV-shielding properties with the synergistic
absorption of UV by FPI and AMNPs. In this study, curcumin was used to evaluate the
UV-shielding performance of the composites through UV-vis measurements, as
schematically represented in Figure 4a. Figure 4b schematically represents the UV
Polymers 2024, 16, 382 interaction with the FPI/ANMPs composite. Curcumin was chosen due to its high 11 of 35
instability under UV irradiation, leading to the decomposition of the α-carbon in its
structure into aldehydes, further oxidizing into acids [38]. In the blank control group
(Figure 4c), the absorbance of curcumin dropped to zero after 50 min of irradiation. This
colorless,with
correlated confirming complete
a color change from degradation.
dark yellow to In contrast,
colorless, curcumin
confirming covered by a pure FPI
complete
film only experienced
degradation. partialcovered
In contrast, curcumin degradation,
by a purewith a residual
FPI film rate reaching
only experienced partial 72.2% (Figure 4d),
degradation,
accompanied withbya residual
a slightrate reaching
solution 72.2%
fade. (Figure
When 4d), accompanied
curcumin by a slight
was shielded by FPI + 0.1% AMNPs,
solution fade. When
FPI + 0.3% AMNPs, curcumin
FPI +was shielded
0.5% by FPIFPI
AMNPs, + 0.1% AMNPs,
+ 0.7% FPI + 0.3%
AMNPs, andAMNPs,
FPI + 1% AMNPs films,
FPI + 0.5% AMNPs, FPI + 0.7% AMNPs, and FPI + 1% AMNPs films, the concentration of
the concentration of the curcumin solution decreased less with an increase in AMNPs
the curcumin solution decreased less with an increase in AMNPs content (Figure 4e–i).
content (Figure
Simultaneously, the 4e–i). Simultaneously,
color change thesolution
in the curcumin color change in the curcumin
was not gradually evident, solution was not
gradually evident, consistent with the initial solution.
consistent with the initial solution.

Figure
Figure 4. Schematic
4. Schematic representation
representation of (a) experiment
of (a) experiment and of (b) UVand of (b)with
interaction UV the
interaction
FPI/ANMPwith the FPI/ANMP
composites.
composites. (c) UV-vis spectra
(c) UV-vis of curcumin
spectra without shielding.
of curcumin withoutUV-vis spectraUV-vis
shielding. of curcumin covered
spectra of curcumin covered by
by (d) FPI, (e) FPI/AMNPs-0.1%, (f) FPI/AMNPs-0.3%, (g) FPI/AMNPs-0.5%, (h) FPI/AMNPs-0.7%,
(d) FPI, (e) FPI/AMNPs-0.1%, (f) FPI/AMNPs-0.3%, (g) FPI/AMNPs-0.5%,
and (i) FPI/AMNPs-1%. The inserted images show the corresponding shade of curcumin solution
(h) FPI/AMNPs-0.7%,
and (i) FPI/AMNPs-1%. The inserted images
from 0 to 50 min. Adapted with permission from Ref. [37]. show the corresponding shade of curcumin solution
from 0 to 50 min. Adapted with permission from Ref. [37].

To quantify the UV-shielding efficiency of FPI/AMNP films, decay and dynamic reac-
tion rate curves for curcumin decomposition were plotted (Figure 5a,b). Figure 5a shows
that curcumin decays most rapidly in the blank group, while the decay rate was signifi-
cantly reduced when shielded by pure FPI, indicating effective UV shielding. Moreover, the
attenuation degree of curcumin decreased with increasing AMNP content, demonstrating
enhanced UV shielding favored by AMNPs. The relationship between ln (At /A0 ) and time
(t) confirmed first-order linear reaction kinetics for curcumin decomposition (Figure 5b).
The largest kapp belonged to the blank group, and others corresponded to curcumin cov-
ered by pure FPI, FPI + 0.1% AMNPs, FPI + 0.3% AMNPs, FPI + 0.5% AMNPs, FPI + 0.7%
AMNPs, and FPI + 1% AMNPs, respectively. The results indicated that the UV-shielding
effect of FPI/AMNP films was proportional to the accumulation of AMNPs, highlighting
the synergistic effect of FPI and AMNPs in enhancing UV shielding. A considerable amount
of charge transfer complexes (CTCs) between molecular chains of FPI and excellent UV
absorption by AMNPs contribute to the enhanced UV-shielding properties of the composite
films. The R2 value, consistently above 0.87, indicates a well-fitted linear relationship for
this reaction (Figure 5c). Material reusability is crucial in practical use, with UV-shielding
efficiency increasing with higher AMNP content (Figure 5d). After 10 recycling tests,
FPI/AMNPs-1% exhibited a 13% amplification in UV-shielding efficiency compared to
pure FPI. Furthermore, pure FPI showed a 12% reduction in UV-shielding efficiency, while
FPI/AMNPs-1% showed only a 4% reduction. These results highlight the effective pro-
longation of UV-shielding life with the addition of AMNPs. In summary, FPI/AMNP
 the enhanced UV-shielding properties of the composite films. The R2 value, consistently
above 0.87, indicates a well-fi ed linear relationship for this reaction (Figure 5c). Material
reusability is crucial in practical use, with UV-shielding efficiency increasing with higher
AMNP content (Figure 5d). After 10 recycling tests, FPI/AMNPs-1% exhibited a 13%
Polymers 2024, 16, 382 amplification in UV-shielding efficiency compared to pure FPI. Furthermore, pure FPI 12 of 35
showed a 12% reduction in UV-shielding efficiency, while FPI/AMNPs-1% showed only
a 4% reduction. These results highlight the effective prolongation of UV-shielding life with
the addition of AMNPs. In summary, FPI/AMNP films demonstrated excellent UV-
films demonstrated
shielding properties and excellent UV-shielding
reusability, indicating properties and reusability,
them as potential indicating
candidates for them as
potentialshielding
ultraviolet candidates for ultraviolet shielding in space.
in space.

Figure
Figure5. (a)
5. Decay curvescurves
(a) Decay of the absorption intensity ofintensity
of the absorption the curcumin solution
of the at 425 nm
curcumin with and
solution at 425 nm with
without shielding by FPI/AMNPs composites; (b) dynamic reaction rate curve of curcumin
and without shielding by FPI/AMNPs composites; (b) dynamic reaction rate curve of curcumin
decomposition; (c) kinetic reaction rate constant and linear correlation coefficient curves; (d)
decomposition;
shielding efficiency(c) kinetic
after reaction
0–10 cycles rate
of UV constant
exposure. and linear
Adapted with correlation coefficient
permission from curves;
Ref. [37] . (d) shielding
efficiency after 0–10 cycles of UV exposure. Adapted with permission from Ref. [37].
2.3. Polydimethylsiloxane-Based Materials
2.3. Polydimethylsiloxane-Based Materials
PDMS shows advantageous properties such as flexibility, suitable thermal stability,
chemical inertness, and low cost [39–42]. These properties have been extensively exploited for
the development of membranes, enclosures, microfluidic structures, and sensors [43–47]. Low-
Z fillers have been successfully embedded in PDMS-based matrices, obtaining promising
radiation-shielding materials that can be potentially exploited in the space environment.
PDMS nanocomposites filled with tungsten oxide (WO3 ) and barium oxide (BaO) were
exposed to 137 Cs, 241 Am, and 60 Co with energies ranging from 0.059 to 1.333 MeV [48]. The
following samples were fabricated: 100 wt% PDMS (S-1), 60 wt% PDMS + 40 wt% WO3
(S-2), 60 wt% PDMS + 40 wt% BaO (S-3), double layers of S-2 and S-3 (S-4), and double
layers of S-3 and S-2 (S-5). The results showed that at the lowest energy level (0.059 MeV),
the sample S-3 exhibited the highest µ (5.66 cm−1 ), followed by S-4 (4.07 cm−1 ), while S-1
(neat PDMS) had the smallest µ (0.29 cm−1 ). The addition of WO3 and BaO consistently
improved the µ values, indicating enhanced radiation attenuation for the composites. The
transmission factor (TF) values obtained for the samples confirmed that the addition of
WO3 and BaO contributed to increased radiation attenuation, particularly at lower energies.
However, as energy increases, the differences in TF between samples decrease. The double-
layered samples (S-5 and S-6) showed better TF, especially at low energies, compared to
single-layered samples. The half-value layer (HVL), representing the material thickness
required to reduce radiation intensity by 50%, was calculated. The results showed that S-1
(neat PDMS) had the highest HVL, confirming poorer shielding performance compared to
samples containing WO3 and BaO. Sample S-2, loaded with 40 wt% WO3 , demonstrated
better radiation attenuation efficiency. Samples containing higher percentages of WO3 and
BaO showed lower MFP values, indicating improved shielding efficiency. In summary,
these flexible composites exhibited suitable performance against γ-ray radiation that could
be potentially exploited in different fields, such as aerospace.
Polymers 2024, 16, 382 13 of 35

Cheraghi et al. fabricated PDMS-matrix nanocomposites filled with bismuth oxide

(Bi2 O3 ) and multiwalled carbon nanotubes (MWCNTs) and tested their shielding properties
against high-energy electron beam for potential application in space [49]. Samples of pure
PDMS and nanocomposites filled with 30 wt% of Bi2 O3 and 3 wt% of MWCNTs were
prepared and tested under electron beam energies of 9, 12, 16, and 20 MeV in attenuation
mode. These values were selected according to the electron beam energies reported for
outer space. The shielding behavior of the samples was compared with that of aluminum,
which was considered as the reference material. During the irradiation tests, each sample
received a 100 cGy dose at a rate of 1000 cGy/min. The percentage of electron attenuation
efficiency (AE%), equivalent to the RPE factor mentioned in Section 2.1, was calculated
as follows:
C0 − Ct
AE(%) = × 100 (8)
C0
where C0 and C are the intensities of the original and transmitted electrons measured using
an ionizing chamber. The results unveiled that PDMS/BiO and PDMS/CNT/BiO nanocom-
posites have better shielding properties than aluminum, pure PDMS, and PDMS/CNT
samples for all areal densities (Figure 6).
For all the samples, the electron attenuation efficiency showed a similar trend for all
energies, with AE% values that increase at increasing areal densities. PDMS/CNT/BiO
samples showed the highest weight advantages and AE% values at any electron beam en-
ergies. The difference between the attenuation values of PDMS/CNT/BiO and aluminum
decreases for higher areal densities. Considering the density values of 0.5, 1, and 1.5 g/cm2 ,
the PDMS/CNT/BiO sample showed better shielding capabilities than aluminum. There-
fore, these PDMS-based materials can be potentially applied in space as shielding materials
instead of aluminum, which has disadvantages such as heavy weight
Polymers 2024, 16, x FOR PEER REVIEW 14 of and
38 generation of
secondary electrons.

Figure 6. Percentage of electron a enuation efficiency (AE%) of PDMS, PDMS/CNT,

Figure 6. Percentage of electron attenuation efficiency (AE%) of PDMS, PDMS/CNT, PDMS/CNT/BiO,
PDMS/CNT/BiO, and aluminum samples tested under electron beam energies of (a) 9, (b) 12, (c) 16,
and
and (d) 20 MeV insamples
aluminum a enuation tested
mode.under
Dashedelectron
lines: AE%beam energies
difference betweenofsamples
(a) 9, (b)
with12,
the (c)
same16, and (d) 20 MeV
areal density (horizontal lines) and areal densities difference for the same AE% (vertical
in attenuation mode. Dashed lines: AE% difference between samples with the same areal density lines).
Adapted with permission from Ref. [49].
(horizontal lines) and areal densities difference for the same AE% (vertical lines). Adapted with
permission
For allfrom Ref. [49].
the samples, the electron a enuation efficiency showed a similar trend for all
energies, with AE% values that increase at increasing areal densities. PDMS/CNT/BiO
samples showed the highest weight advantages and AE% values at any electron beam
energies. The difference between the a enuation values of PDMS/CNT/BiO and
aluminum decreases for higher areal densities. Considering the density values of 0.5, 1,
and 1.5 g/cm2, the PDMS/CNT/BiO sample showed be er shielding capabilities than
aluminum. Therefore, these PDMS-based materials can be potentially applied in space as
shielding materials instead of aluminum, which has disadvantages such as heavy weight
and generation of secondary electrons.
Polymers 2024, 16, 382 14 of 35

Borjanovic et al. fabricated PDMS-matrix nanocomposites filled with single-walled

carbon nanotubes (SWCNTs), detonation nanodiamond (DND), and zinc oxide (ZnO)
and tested their radiation-shielding behavior under proton exposure [50]. Irradiation
experiments were performed using a 2 MeV proton beam and low fluence conditions with
currents ranging from 30 to 100 nA. The samples were irradiated in the fluence range of
1013 to 1015 protons/cm2 in four regions (D1-D4) with different conditions. In particular,
the fluence associated with regions 1 (D1) and 2 (D2) is 5.7 × 1013 protons/cm2 . In region
1, a beam current of 30 nA was used, while in region 2, a beam current of 50 nA was
applied. The total charge for both regions 1 and 2 was kept constant at 5.6 µC. For region
3 (D3), a fluence of 5.7 × 1014 protons/cm2 was achieved with an 80 nA beam current,
resulting in a total charge of 56 µC. In region 4 (D4), a fluence of 1 × 1015 protons/cm2 was
provided using a 100 nA beam current, with a total charge of 100 µC. The proton irradiation
was conducted at room temperature. The study emphasized the influence of particle size
on ionizing radiation protection, with smaller particles showing enhanced stability in
high irradiation environments. Raman and FTIR-ATR spectra revealed that PDMS-DND
nanocomposites with 40 nm DND aggregates were more stable under high proton fluences
compared to pure PDMS or other nanocomposites. The introduction of ZnO nanoparticles
into the PDMS matrix (PDMS-ZnO) showed even better high-energy ionizing radiation
resistance than the DND-filled materials. The multifunctionality of ZnO, including energy
absorption and dissipation, contributed to its effectiveness in protecting the nanocomposite
under high fluences. Moreover, results indicated that PDMS-SWCNT nanocomposites
provided protection similar to other nanofillers under low proton fluences, while their
effectiveness decreased at higher fluences (D3, D4). In conclusion, the nanocomposites
with smaller filler sizes and those with ZnO exhibited the best shielding performance
against high-energy proton irradiation, making them suitable candidates for applications
in high-radiation environments.
Han et al. proposed a novel force-sensitive structure resistant to γ-rays exposure,
employing a sandwich configuration made of tungsten oxide (WO3 ), PDMS, and carbon
nanotube (CNT) sponge [51]. Tungsten oxide was used as a gamma-ray shielding material,
while the CNT sponge establishes a conductive network, and PDMS acts as a flexible
substrate. Irradiation experiments were conducted on four samples using 60 Co-γ rays with
an energy value of 1.25 MeV. The force sensitivity of samples irradiated with different
doses (0, 5, 20, 50, 100 KGy) was assessed and shown in Figure 7. Sensitivity was defined
as (∆R/R0 )/ε, where ε was indicated as ∆L/L0 . As reported in Figure 7a, the sensitivity
of the CNT sponge/PDMS sample decreased from 61.3 to 24.2, indicating a reduction of
approximately 60% after gamma irradiation. Conversely, samples containing tungsten
oxide particles exhibited a lower sensitivity attenuation after exposure (Figure 7b–d). The
sensitivity of the samples containing WO3 with particle sizes of 50 nm (Figure 7b), 100 nm
(Figure 7c), and 1 µm (Figure 7d) decreased by 17%, 28%, and 35.6%, respectively. With
an increase in the WO3 particle size, the fluctuations in the force-sensitive curves after
irradiation gradually became more pronounced. A more significant impact of gamma rays
on the force-sensitive performance of the samples was observed when larger WO3 particles
were used. Differently, the use of smaller particles of WO3 induced more protection against
gamma rays, and this can be ascribed to the presence of more gaps in the composite.
Using smaller WO3 particles, the specific surface area increases, leading to the formation
of more gamma loss interfaces and reducing the impact of gamma rays on the composite.
Overall, this work proposed a promising flexible stress sensor with gamma-ray-shielding
effectiveness, which could be potentially used in space.
 Polymers 2024, 16, x FOR PEER REVIEW 16 of 38
Polymers 2024, 16, 382 15 of 35

Figure7.7. Plots
Figure Plots from
fromforce-sensitive
force-sensitivetests after
tests different
after doses
different of gamma
doses irradiation
of gamma performed
irradiation on (a) on
performed
CNT sponge/PDMS samples and CNT sponge/PDMS samples containing
(a) CNT sponge/PDMS samples and CNT sponge/PDMS samples containing tungsten oxide tungsten oxide withwith
particle sizes of (b) 50 nm, (c) 100 nm, and (d) 1 µm. Adapted with permission from Ref. [51].
particle sizes of (b) 50 nm, (c) 100 nm, and (d) 1 µm. Adapted with permission from Ref. [51].

2.4.Other
2.4. OtherPBMsPBMs
Prabhuet
Prabhu etal.
al. developed
developed epoxy-based
epoxy-basedmaterials
materialsfilled with
filled with micro
microandandnano-tantalum
nano-tantalum
oxide (Ta 2O5) particles and demonstrated their effectiveness in γ-ray shielding [16]. A
oxide (Ta2 O5 ) particles and demonstrated their effectiveness in γ-ray shielding [16]. A
diglycidyl ether
diglycidyl ether ofof bisphenol
bisphenol A A (DGEBA)
(DGEBA)epoxy epoxyresin
resinwas
wasusedused asasa matrix.
a matrix.TheThe
study
study
determined µ/ρ values for composites loaded with 10%, 20%,
determined µ/ρ values for composites loaded with 10%, 20%, and 30 wt% of filler and 30 wt% of filler andand
irradiatedusing
irradiated using energy
energy values
values ofof0.356,
0.356,0.511,
0.511,0.662,
0.662,1.173,
1.173,1.275,
1.275, and 1.332
and MeV.
1.332 MeV.Samples
Samples
with the highest filler content (30 wt%) showed the best shielding ability.
with the highest filler content (30 wt%) showed the best shielding ability. Considering Considering the the
same filler content and energy level, the µ/ρ values of the nanocomposites are higher than
same filler content and energy level, the µ/ρ values of the nanocomposites are higher than
those detected for the micro-composites. In particular, samples containing nano-Ta2O5
those detected for the micro-composites. In particular, samples containing nano-Ta2 O5 with
with lower filler content provided shielding performance comparable to that of high-
lower filler content provided shielding performance comparable to that of high-loaded
loaded micro-composite systems. This can be justified by the high number of
micro-composite systems. This can be justified by the high number of nanoparticles, with
nanoparticles, with shorter interparticle distances than those of microparticles for the
shorter interparticle distances than those of microparticles for the same volume fraction of
same volume fraction of fillers. This involves fewer void paths for photons from γ-rays,
fillers. This involves fewer void paths for photons from γ-rays, resulting in greater photon
resulting in greater photon a enuation. The results unveiled that nano-Ta2O5 epoxy
attenuation. The results unveiled that nano-Ta2 O5 epoxy
composites have higher thermal stability, flame
composites have higher thermal
retardance, and tensile properties
stability,
compared flame retardance, andattensile
to micro-composites the sameproperties compared
loading. Overall, theseto nanocomposites
micro-composites can at
bethe
same loading. Overall, these nanocomposites can be
considered promising materials for effective γ-ray shielding in space. considered promising materials for
effective γ-ray shielding in space.
A DGEBA epoxy resin was also used by Adeli et al. to fabricate neutron-shielding
A DGEBA
composites [52].epoxy
Boron resin
carbide was
was also used
used by Adeli
as filler, and theet al. to of
effect fabricate neutron-shielding
the particle size (20 and
composites [52]. Boron carbide was used as filler, and the effect of the
150 µm) and loading amount (1, 3, 5 wt%) on the shielding effectiveness was investigated. particle size (20 and
150 µm) and loading amount (1, 3, 5 wt%) on the shielding effectiveness
The results confirmed a shielding enhancement using smaller boron carbide particles. was investigated.
The results
Other confirmed
composites were a shielding
prepared enhancement using smaller
by adding tungsten oxide (WO boron carbide
3) and particles.
aluminum
Other composites
trihydrate (ATH) were prepared
into the polymer by matrix.
addingThetungsten oxide
presence of (WO
WO33 )provides
and aluminum trihy-
protection
drate (ATH)
against gamma intorays,
the whereas
polymerATH matrix. The presence
improves of WO3 provides
the heat resistance protection
of the material. against
Moreover,
gamma
ATH couldrays,alsowhereas ATH to
contribute improves
gamma-ray the heat resistance
a enuation dueoftothe
its material. Moreover,
higher atomic number ATH
could also contribute to gamma-ray attenuation due to its higher atomic number than
carbon and hydrogen in the epoxy matrix. Composites filled with WO3 and ATH showed
an enhancement of more than 60% in neutron shielding compared to those filled only
Polymers 2024, 16, 382 16 of 35

with boron carbide. Overall, these findings can be exploited for designing efficacious
space shields.
Bel et al. tested composites based on poly(methyl methacrylate) (PMMA) reinforced
with colemanite (CMT) as shielding materials for gamma rays and neutrons [53]. Samples
with different CMT loadings (5, 15, 30, and 40 wt%) were irradiated using 137 Cs and 239 Pu-
Be as gamma-ray and neutron sources, respectively. At higher filler contents, enhancements
in the shielding effectiveness were found. Considering the gamma-ray irradiation tests,
the addition of CMT at 40 wt% into the matrix led to an increase in terms of µ values from
0.098 to 0.138, which corresponds to 11.1% enhancement in shielding performance for the
composite with respect to the neat PMMA. The results from neutron exposure experiments
also confirm the best shielding effectiveness for the composites loaded with 40 wt% of
CMT. This effect can be ascribed to the increase in terms of boron and hydrogen that are in
the filler, thus allowing an increase in neutron attenuation. The PMMA/CMT composites
were proposed as potential shields for satellites and space shuttles after further tests to be
carried out on the International Space Station (ISS).
Composite materials based on poly-ether-ether-ketone (PEEK) and tungsten were
fabricated for potential use as gamma-ray shields [54]. Samples were prepared by fused
deposition modeling (FDM) 3D printing. The functional properties and shielding effective-
ness of samples containing 50, 60, and 70 wt% of tungsten were investigated and compared
with those of neat PEEK. 60 Co and 137 Cs were used as gamma-ray radiation sources. µ
value of the neat PEEK exposed to 137 Cs source was found to be 0.0728 cm−1 . An increase in
the µ value by 54.81%, 64.45%, and 68.70% was observed for samples filled with 50, 60, and
70 wt% of tungsten, respectively. After exposure to a high-energy 60 Co source, the µ value
of the samples reinforced with 50, 60, and 70 wt% of filler increased by 48.84%, 57.91%,
and 62.91%, respectively, with respect to the pure polymer. The fabrication of multilayered
hetero-structures based on PEEK/tungsten and PEEK/boron carbide was proposed for a
contemporary shielding of neutrons and secondary gamma-ray radiations. The effective
application of these composites in space could be evaluated, taking into account the advan-
tages offered in terms of weight and costs. Polyether-polyurethane (PUR)-based composites
filled with hexagonal boron nitride and amorphous boron were tested as neutron-shielding
materials [55]. In particular, PUR composites loaded with 21% amorphous boron and boron
nitride were fabricated. They showed suitable flexibility despite the high filler content
and unveiled shielding effectiveness toward neutrons. These shielding properties and the
possibility of using PUR matrix partly derived from renewable resources are factors that
can be advantageously exploited in space applications.
Shemelya et al. fabricated 3D-printed polycarbonate (PC) composites filled with
tungsten oxide for X-ray shielding [56]. Low loadings of filler were used to obtain a
composite with suitable mechanical strength and reduced weight. After irradiation tests, an
increase in X-ray attenuation (~10%) was observed for the composite with respect to pure
PC. At low X-ray energies (40 keV to 70 keV), a tungsten volume loading of 0.3% results
in an attenuation factor of 96 to 98 (rad/rad). The increase in terms of mass is ~5%, thus
relatively low. Moreover, no significant changes in elongation to break or impact resistance
were detected. Based on the results of this study, PC-based composites could be applied in
space as shielding materials with suitable mechanical properties and low weight.
Table 1 summarizes the different PBM systems developed for space radiation shielding.
The comparison is based on the type of polymer and filler that were used and on the
shielded radiation.
Polymers 2024, 16, 382 17 of 35

Table 1. Comparison of PBMs for space radiation shielding.

Polymer Filler Type of Shielded Radiation Ref.

MDPE Multiwalled carbon nanotubes, graphene nanoparticles Protons [22]
UHMWPE fibers, PU Boron nitride Neutrons [23]
HDPE Boron nitride, boron carbide Neutrons [25]
HDPE, LDPE Hexagonal boron nitride Neutrons [27]
HDPE Aluminum oxide, iron oxide, lead oxide Gamma rays [28]
PI Bismuth oxide Gamma rays [33]
PI Gadolinium oxide, hexagonal boron nitride Gamma rays, neutrons [34]
PI Hexagonal boron nitride Neutrons [35]
PI Lead Electrons [36]
FPI Allomelanin nanoparticles Ultraviolet [37]
PDMS Tungsten oxide, barium oxide Gamma rays [48]
PDMS Bismuth oxide, multiwalled carbon nanotubes Electrons [49]
Single-walled carbon nanotubes, detonation
PDMS Protons [50]
nanodiamond, zinc oxide
Tungsten oxide, carbon nanotube sponge (sandwich
PDMS Gamma rays [51]
configuration)
DGEBA resin Tantalum oxide Gamma rays [16]
DGEBA resin Boron carbide, tungsten oxide, aluminum trihydrate Neutrons [52]
PMMA Colemanite Gamma rays, neutrons [53]
PEEK Tungsten Gamma rays [54]
PUR Hexagonal boron nitride, amorphous boron Neutrons [55]
PC Tungsten oxide X-rays [56]
Abbreviations MDPE: medium-density polyethylene; UHMWPE: ultrahigh-molecular-weight polyethylene; PU:
polyurethane; HDPE: high-density polyethylene; LDPE: low-density polyethylene; PI: polyimide; FPI: fluori-
nated polyimide; PDMS: polydimethylsiloxane; DGEBA: diglycidyl ether of bisphenol A; PMMA: poly(methyl
methacrylate); PEEK: poly-ether-ether-ketone; PUR: polyether-polyurethane; PC: polycarbonate.

3. Numerical Studies
The space environment poses significant hazards to both astronauts’ health and elec-
tronic devices, attributed to ionizing and non-ionizing radiation. Radiation transport codes
are crucial in evaluating material shielding effectiveness before missions in the selection of
appropriate radiation countermeasures. These codes are used for numerical simulations,
offering insights into the interaction between charged particles and matter in space.
The radiation transport codes are broadly categorized into two types. First, deter-
ministic codes are mainly used for one-dimensional (1D) problems but are adaptable to
three-dimensional (3D) geometries, providing averaged dosimetric quantities. Then, Monte
Carlo codes are exclusively employed for 3D investigations, and conducting statistical
analysis when solving high-dimensional integral equations becomes challenging for deter-
ministic methods [57]. The difference between deterministic and Monte Carlo approaches is
significant. Deterministic codes are less demanding, but they can be used only if transport
equations have analytical solutions. This is a disadvantage if the satellite has complex
shielding geometries because of systematic errors in space discretization of the protective
structure. On the other hand, Monte Carlo predictions are more difficult to implement
because they require high processing power. Even if they cannot produce accurate results
in radiation deep penetration problems, they are also able to simulate complex shielding
geometries. Indeed, the main advantage of this method consists of creating numerical
statistical solutions using “random” variables (of which the probability distribution is
known) for a problem whose solution in closed form does not exist. Globally, determin-
istic and Monte Carlo methods complement each other and provide accurate results in
space applications [58].
Different space agencies rely on codes developed by their national engineers that are
tailored to their specific needs. Despite similar applications, these codes differ in aspects
such as energy range and types of projectiles considered. A variety of software options
can be found in the literature: the High charge (Z) and Energy TRaNsport (HZETRN)
code and Online Tool for the Assessment of Radiation in Space (OLTARIS) software used
Polymers 2024, 16, 382 18 of 35

by NASA, the SHIELD code by the Russian Space Agency, the GEometry ANd Tracking
(GEANT4) code by ESA, the FLUctuating KAscade (FLUKA) code by the Italian Institute
for Nuclear Physics (INFN) and the European Laboratory for Particle Physics (CERN),
the Particle and Heavy Ion Transport code System (PHITS) code by the Japan Atomic
Institute (JAERI), and the Monte Carlo N-Particle eXtended (MCNPX) code by Los Alamos
National Laboratory [58–60].

3.1. Radiation Transport Codes

3.1.1. HZETRN Codes
The HZETRN is a deterministic suite of Fortran codes pioneered at NASA Langley
Research Center, which includes interactions and transports of ions from the galactic cosmic
rays (GCRs), the trapped protons within the Earth’s magnetic field, and the energetic
protons from solar particle events (SPEs). The codes work using high-charged particles
to create different cross-sections as the first output for the selected materials and then
transport energy inside the materials in free space and low earth orbit (LEO) [59,61,62]. The
process is described by the 1D formulation of the Boltzmann transport equation obtained
from conservation principles by considering a region of space filled with matter described
by appropriate atomic and nuclear cross-sections [63]:
" #
1 δ
Z
Ω·∇ − Sj (E) + σj (E) φj (x, Ω, E) = ∑k σjk E, E′ , Ω, Ω′ φk x, Ω′ , E′ dΩ′ dE (9)



Aj δE

where φj (x, Ω, E) represents the flux of ions of type j with atomic mass Aj at position x
moving in direction Ω. Sj(E) denotes the linear energy transfer (LET) as a function of energy
E. σj and σjk (E, E′ , Ω, Ω′ ) correspond to the reaction cross-sections for particle j with energy
E and direction Ω, as well as the collision cross-sections between particles of type j with
energy E and direction Ω, and type k with energy E′ and direction Ω′ , respectively.
The code is structured into two sequential modules. In the initial “cross sections”
module, input data related to the shielding material is processed to calculate atom frag-
mentation within the material. Subsequently, the “transport module” takes over and is
responsible for guiding radiation energy through the shielding material. This module
not only facilitates the transportation of radiation but also computes various dosimetric
quantities based on the interactions between the material and the radiation that traverses it.
By employing these modules in sequence, the code effectively models and analyzes the
intricate behavior of radiation as it interacts with the selected shielding materials.
The HZETRN code has seen regular updates, with significant releases in 2010, 2015,
and 2020, denoted as HZETRN 2010, HZETRN 2015, and HZETRN 2020, respectively. In
HZETRN 2010, a 1D approach was employed using the straight-ahead approximation,
which consists of transporting particles along a single ray (N = 1) representing the incident
radiation. It also allowed for forward–backward (N = 2) propagation, where particles were
propagated along a second ray at 180◦ relative to the incident beam direction [59]. HZETRN
2015 introduced 3D transport capabilities, allowing light ions (Z ≤ 2) to be propagated in
three dimensions with an arbitrary number of rays (N) [59]. In contrast, HZETRN 2020
introduced a double solution, updating 1D and 3D transports. This version fully coupled
muons and pions with neutrons and light ions and incorporated the Badhwaar–O’Neill
(BON) 2020 model to accurately depict solar activity. Notably, the BON2020 model showed
significant improvement over BON2014, eliminating systematic biases associated with the
earlier version. The average relative error of the BON2020 model compared to available
measurements was found to be lower than 1%. For heavy ion fragmentation studies,
HZETRN 2020 offered two distinct models. The NUClear FRaGmentation (NUCFRG)
model evaluated fragmentation cross-section products from nucleus–nucleus collisions,
while the Relativistic Abrasion-Ablation FRaGmentation (RAADFRG) model predicted
pre-fragment cross-sections [59,64,65].
Polymers 2024, 16, 382 19 of 35

3.1.2. OLTARIS Software

The OLTARIS is a web-based space radiation analysis tool developed by NASA that
employs the HZETRN code for radiation transport calculations and relies on the NUCFRG
model for input data [60]. The software allows the investigation of the materials’ behavior
considering different environmental conditions. Similar to the HZETRN code, OLTARIS
simulates free space conditions, investigating the effects caused by GCR and SPEs at 1 AU.
GCR is investigated using the BON model based on fitting the measured energy spectra.
Furthermore, OLTARIS explores the behavior of materials on Martian and lunar soils
through a 3D transport simulation. It enables the investigation of the combined effects of
GCR and regolith (RG) on both Mars and the Moon. Specifically for Mars, the simulation
also incorporates the combined influence of the atmosphere and RG in the boundary
conditions. Furthermore, the software allows for the observation of radiation effects in LEO
by considering circular orbits or customized trajectories. In this case, OLTARIS considers
that the impact of galactic cosmic radiation (GCR) is influenced by orbit parameters,
including inclination and altitude. Additionally, it accounts for the effects of trapped
protons and neutrons reflected by the Earth’s albedo.
The software is divided into two main components. First, the website interface
facilitates project creation and allows users to define custom materials and thickness
distributions. The website interface is composed of five elements: radiation environment for
definition of boundary conditions, material properties for user-defined materials, geometry
of slabs, spheres, or vehicle thickness distribution, transport, and output results in terms
of dosimetric quantities. Then, in the execution environment, Fortran executables are
compiled on a computational cluster [66]. All user data are passed to the web server using
Extensible Markup Language (XML) files.

3.1.3. SHIELD Codes

The SHIELD was one of the first transport codes used in modern simulations. It is a
Monte Carlo code developed by the Russian State corporation (ROSCOSMOS) for space
flights and cosmonautics programs. The SHIELD code is tuned for space shielding and
environment applications and was used for the simulation of radiation effects in 55 long-
term spacecraft missions. The SHIELD code enables the transport of various particles,
including nucleons, pions, kaons, anti-nucleons, and muons, along with nuclei having
arbitrary proton and mass numbers at energies up to 1 TeV [67]. For charged particles,
the code operates from a lower limit of 1 MeV, while for neutrons, it functions from their
thermal energy level [58,59,67].
SHIELD operates through a simulated hadron cascade, where subatomic particles
are transported to analyze the resulting secondary particles. These particles are stored
in specific arrays with their individual parameters. Once the hadron cascade simula-
tion concludes, SHIELD performs the transfer of neutrons with energies below 14.5 MeV
from the source array using the original neutron transport code, LOw Energy Neutron
Transport (LOENT) [68].

3.1.4. GEANT4 Codes

GEANT4 is an open-source suite of codes written in C++, which uses Monte Carlo
methods. It simulates a variety of physical interactions for high-energy nucleons, pions,
and nuclei [59]. The codes contain different packages from the Quark Gluon String (QGS)
model used for nucleons, pions, and nuclei to the Precompound (P) model referred to
as nuclear de-excitation and the Bertini cascade (BERT) used for interactions below an
energy of 10 GeV. Heavy ion collisions are modeled from the quantum molecular dynamics
(QMDs) [69]. A novel package is PLANETOCOSMICS, which provides a description of
several interesting features of a planetary body, including its geometric shape, the soil, the
atmosphere, and the magnetosphere. It is mainly used for Mars, which is the current target
of space exploration missions [58,70].
Polymers 2024, 16, 382 20 of 35

3.1.5. FLUKA Code

FLUKA [71,72] is a Monte Carlo transport code written in Fortran by CERN and
INFN [59], which is behind all beam-accelerator calculations [73]. It investigates the
interaction and transport of hadrons, light and heavy ions, and trapped particles in electro-
magnetic fields in arbitrary materials (even with complex geometries). It is also used both
for medical treatments and GCR and SPE environments [61]. Particle flux of protons and
ion beams from 50 MeV/c to 450 GeV/c is simulated according to experimental data of the
CERN accelerator [74].

3.1.6. PHITS Code

PHITS [75] is a Monte Carlo suite of codes developed by JAERI and subdivided into
two categories: transport and collision process. In the transport process, PHITS can simulate
a motion under external fields, such as magnetic fields and gravity. One hypothesis is
that without the external fields, neutral particles move along a straight trajectory with
constant energy up to the next collision point. However, charge particles and heavy ions
interact many times, with electrons in the material losing energy and changing direction.
A secondary assumption is that the ionization process is not treated as a collision but as a
transport process under an external field. The collision process occurs with the nucleus in
the material and considers the decay of the particle.

3.1.7. MCPNX Code

MCPNX is a Monte Carlo transport code distributed by the Radiation Safety Infor-
mation Computational Center (RSICC) for the simulation of light-ion and particle inter-
actions [60]. MCNPX has followed different updates denoted as MCNP5 and MCNP6.
During energy transport, MCNP5 behaves like a stable code tracking neutrons, photons,
and electrons. The output results are evaluated through nuclear data libraries, taking ac-
count of low-energy interaction probabilities [76]. The last version, called MCNP6, is clearly
described by Rising et al. [77]. The code considers new neutron-induced fission systems
and isotopes like 240,242 Pu and 252 Cf. In this way, MCNP6 can simulate secondary neutrons
and γ-rays starting from a selected isotope through the default LLNL Fission Library [78].

3.1.8. UPROP Code

The UPROP code is a deterministic transport code designed to model the nuclear
fragmentation process using the straight-ahead approximation [61]. This approach in-
volves numerically solving the one-dimensional propagation equation, assuming that all
fragments maintain the same direction and energy per nucleon as the projectile nucleus.
Notably, the code excludes considerations for the production or propagation of neutrons,
leptons, or mesons.

3.2. Comparison of Strengths and Weaknesses of Radiation Transport Codes

The aforementioned codes are employed in radiation transport simulations, each with
a distinct modeling approach. The effectiveness of each code varies, with strengths and
limitations related to modeling capabilities and simulation speed. HZETRN may exhibit
limitations in handling specific particle types or energy ranges, lacking detailed modeling of
all secondary particle processes [79]. Similar issues are observed in OLTARIS, a web-based
tool utilizing HZETRN codes. Both codes employ deterministic methods to simulate the
transport of heavy ions and other particles in materials pertinent to space exploration [60,63].
GEANT4 models employ Monte Carlo methods to simulate the stochastic interactions of
particles with materials, offering a detailed and adaptable tool for particle transport that
can be used with multiple geometries and boundary conditions [58]. FLUKA utilizes Monte
Carlo techniques to simulate electromagnetic and hadronic interactions for application in
high-energy radiation shielding [80]. MCNPX and SHIELD utilize Monte Carlo methods to
investigate nuclear reactions [78]. PHITS exploits Monte Carlo methods to simulate particle
Polymers 2024, 16, 382 21 of 35

transport, incorporating physics models of magnetic and hadronic interactions [58]. UPROP
simulates the proton transport but with lower performance than the other codes [81].
Lin et al. simulated the shielding behavior of polyethylene and aluminum semi-infinite
slab shells of thickness between 0 and 160 g/cm2 [61]. Dose and equivalent dose were
computed to assess differences between deterministic (HZETRN and UPROP) and Monte
Carlo (GEANT4 and FLUKA) codes in SPE and GCR environments. For each thickness
value, both materials consistently exhibited similar dose and equivalent dose values when
computed using HZETRN, GEANT4, and FLUKA. However, these quantities are lower
when calculated with UPROP for thicknesses exceeding 40 g/cm2 . This discrepancy is
attributed to the particles’ spectra sharing similar trends but featuring different energy
values for each code. Proton fluence in HZETRN and in the two Monte Carlo codes
is closely aligned, while UPROP showed significantly lower values, particularly below
10 MeV. As UPROP does not account for neutron transport, it is less accurate in computing
dosimetric quantities and has not been actively utilized. Moreover, the neutron spectra
provided by FLUKA and GEANT4 disagreed with HZETRN at low energies, specifically
below approximately 5 MeV. Thus, a primary distinction among radiation codes arises
from the energy values used to model particles’ spectra.
Aghara et al. investigated the primary and secondary particles resulting from inter-
actions with an aluminum slab, specifically with average shielding thicknesses of 10 and
20 g/cm2 [60]. They conducted a comparative analysis involving the deterministic code,
OLTARIS, and two Monte Carlo codes (MCNPX and PHITS). The study incorporated four
models of SPE spectra: 56 Webber, 72 LaRC, 89 Weibull, and 91 Carrington. The fluence
spectra of particles modeled by MCNPX and PHITS demonstrated significant agreement
with OLTARIS results, particularly for protons and neutrons across all SPE environments.
However, at lower energies (below 100 MeV), OLTARIS exhibited a lower neutron spectrum
compared to MCNPX and PHITS. This difference is attributed to variations in atomic cross-
sections and transport algorithms among the compared codes. Nuclear physics models in
deterministic codes (such as HZETRN and OLTARIS) are limited, as they do not incorporate
light-fragment particles in their cross-section models [59]. In contrast, Monte Carlo codes
like SHIELD consider all generations of secondary particles, offering a comprehensive
description of nuclear reactions across the entire energy spectrum of primary hadrons
and nuclei up to 1 TeV/n. A comparison of the strengths and weaknesses of the codes is
reported in Table 2.

Table 2. Strengths and weaknesses of radiation transport codes.

Radiation Transport Codes Strengths Weaknesses Ref.

HZETRN Basic modeling of secondary
Accurate heavy ion transport simulation [79]
OLTARIS radiation
Simulation considers stochastic interactions
GEANT4 Computationally intensive [58]
between particles and materials
Simulation of magnetic and hadronic Underestimation for proton
FLUKA [58,82]
interactions irradiations below 10 MeV
Energy threshold level lower than 1
SHIELD Well-simulated nuclear reactions [58,59]
MeV for charged particles
Simulation of magnetic and hadronic Ionization process is not treated as a
PHITS [58,75]
interactions collision but as a transport process
MCNPX Well-simulated nuclear reactions Time-consuming simulations [68,83]
UPROP Proton transport simulation No neutron modeling [81]

Overall, radiation transport codes enable us to assess the combined effect of the radia-
tion sources that characterize the space environment. The possibility to simulate different
conditions that could be really experimented with during space missions represents one of
the main strengths of the numerical approach.
Polymers 2024, 16, 382 22 of 35

3.3. Shielding Simulations for Radiative Environments

3.3.1. GCR Environment
The fundamental task of numerical simulations performed in the GCR environment is
the use of hydrogen-rich materials in order to amplify the attenuation of radiation passing
through the matter [84]. This evidence comes from the Bethe–Bloch theory of materials’
stopping power based on experimental tests [85]. It was demonstrated that liquid hydrogen
provides high shielding performance at minimizing the secondary particles produced from
interaction with high atomic number energy (HZE) ions of GCR particles thanks to its
elevated charge-to-mass ratio [9].
Polyethylene (PE) is considered the best solution for having hydrogen in a solid state
because it is a non-toxic and stable material, even if it has flammability and outgassing
problems [9]. The results in terms of linear energy transfer (LET) and dose were provided
by Guetersloh et al. [20], performing simulations with Monte Carlo codes on the full GCR
spectrum using a 1D transport model. Bragg curves were computed using a semiempirical
model called BBFRAG [86,87] based on the Bethe–Bloch equation for energy-loss calcu-
lations and validated with the results of the accelerator experiment. The model has a
single free modulation parameter Φ that defines solar activity, determining the GCR energy
spectrum at the selected distance from the Sun [88]. They used Φ corresponding to the
2002–2003 period after the solar maximum to simulate a spectrum with a large fraction
of the flux at high energy closer to the solar minimum. It was observed that fragments
produce a dose absorption at depths beyond the Bragg peak as heavy-charged fragments
are generated, demonstrating the shielding capability of PE.
Laurenzi et al. [89] investigated medium-density polyethylene (MDPE) using HZETRN
2015. A model of deep space (1 AU from Earth) based upon a 1D formulation of the Boltz-
mann equation for transport with a modulation parameter of 450 MV at solar minimum
activity was adopted. They proposed a comparison between equivalent doses for MDPE,
aluminum (Al), liquid hydrogen, and other polymers like Kapton, polyphenylene sulfide
(PPS),
Polymers 2024, 16, x FOR PEER REVIEW polyether ether ketone (PEEK), and RTM6 epoxy resin. The materials24were of 38modeled
considering the constituent atomic species, calculating the number of each atom per gram
of material and the respective density. The results of numerical simulations are reported
in Figure simulations
numerical 8. A decreasing trend in
are reported ofFigure
the equivalent dosetrend
8. A decreasing can be observed
of the as dose
equivalent the depth of
the
can material
be observedincreases. However,
as the depth the shielding
of the material capability
increases. However,is the
far shielding
from thecapability
ideal behavior of
liquid hydrogen.
is far from the idealAl behaves
behavior ofworse than otherAlmaterials,
liquid hydrogen. reaching
behaves worse thanaother
necessary mass that is
materials,
reaching
two timesa necessary
higher thanmass thatofisMDPE.
that two times higher than that of MDPE.

Figure 8.
Figure 8.Equivalent
Equivalentdose forfor
dose different materials
different as a function
materials of thickness.
as a function AdaptedAdapted
of thickness. with permission
with permission
from Ref.[89]
from Ref. .
[89].

Similar results were provided for high-density polyethylene (HDPE) investigated by

Barthel et al. [90] using HZETRN 2010. A comparison of slab and sphere models was
obtained both for Al and HDPE, considering solar minimum conditions for a 500-day
Mars mission. They found that 40–80 g/cm2 HDPE shows suitable shielding effectiveness
against HZE ions simulating a human-manned mission if used as slab shells. In fact, the
neutron flux generated from the interaction between GCR particles and Al (the main
Polymers 2024, 16, 382 23 of 35

Similar results were provided for high-density polyethylene (HDPE) investigated by

Barthel et al. [90] using HZETRN 2010. A comparison of slab and sphere models was
obtained both for Al and HDPE, considering solar minimum conditions for a 500-day Mars
mission. They found that 40–80 g/cm2 HDPE shows suitable shielding effectiveness against
HZE ions simulating a human-manned mission if used as slab shells. In fact, the neutron
flux generated from the interaction between GCR particles and Al (the main constituent
material of a spacecraft) appears attenuated from the HDPE shield, leading to a dose
absorbed by human tissue.
To enhance the mechanical properties of polyethylene, different researchers have tried
to incorporate lightweight fillers like boron nitride nanotubes and carbon nanotubes with
the aim of employing PE-based composites as structural and shielding materials. Specif-
ically, these materials can integrate multifunctional mechanical, electrical, and thermal
properties while demonstrating robust radiation-shielding capabilities in the space environ-
ment [91]. Relating to this objective, carbon and boron nanoparticles are incorporated in
multifunctional materials, reaching superior modulus and optimal electrical and thermal
conductivities [92]. Laurenzi et al. [89] have simulated composites made up of MDPE
matrix and nanoparticles such as single-walled carbon nanotubes (SWCNTs), graphene
oxide (GO), and boron carbide (CB4 ) reaching filler weight percentages of 1%, 2%, 5%,
10%, 15%, and 20%. They performed numerical calculations of the absorbed equivalent
dose to investigate radiation attenuation against Al using HZETRN 2015. The results
showed that the effects due to all fillers at low weight concentrations are negligible. It
was also demonstrated that B4 C and BN nano-powders provide suitable neutron shielding
to PE composites. Kim et al. [12] investigated neutron attenuation through Monte Carlo
simulations to evaluate the dependence of thermal neutron absorption on filler size for
a boron-containing polymer composite. They observed that the neutron transmission is
significantly less for an atomic cross-section of 300 µm, confirming the shielding efficiency
of boron compounds.
Recently, micro- and nanocomposites made up of cis-polyacetylene matrix were con-
sidered in radiation shielding because they are optimal nanostructured hydrogen-storage
materials [93]. Li-decorated polyacetylene and B-doped cis-polyacetylene can store up to
10.8 wt% and 9.8 wt% hydrogen, respectively [94]. For this reason, Yang et al. [95] have
performed simulations to assess their protective effectiveness using MULASSIS (GEANT4
codes). A model simulating GCR radiation in deep space was used. They performed a
1D analysis considering a multilayered shield (thickness ranges between 2 and 50 cm).
A comparison of the absorbed equivalent dose and fluences after shields in Al, liquid
hydrogen, and doped polyacetylene with titanium (Ti), lithium (Li), and boron (B) was
provided. It was denoted that Ti-doped polyacetylene plus 14% hydrogen was the most
effective shielding material. Increasing the hydrogen percentage contained in Ti-doped
polyacetylene, the production of neutrons decreases, reaching comparable particles’ flux to
that of liquid hydrogen. Furthermore, the maximum flux in PE was over 0.04 particle/cm2 ,
while the peak of Ti-doped polyacetylene was less than 0.03 particle/cm2 . Regarding
the comparison of equivalent doses, it was observed that polyacetylene composites have
intermediate behavior between liquid hydrogen and Al with the same trend of PE.
GCR radiation also includes considerable ionizing particles for planets with negligible
atmosphere and natural satellites. It is demonstrated that materials with low hydrogen
content are more sensitive to radiation on Mars and the Moon’s surface when compared
to polyethylene [96,97]. The inelastic collisions of neutrons and GCR ions with target
atoms in pour hydrogen materials as Al increases the neutrons flux as the shield thick-
nesses rise. According to the literature, the in situ resource utilization (ISRU) strategy
could reduce neutron damage by fabricating composite materials with Martian and lu-
nar RG [98,99]. Zaccardi et al. [100] performed simulations about the shielding power of
ultrahigh-molecular-weight PE (UHMWPE) composites. Simulations were conducted on
sphere geometries at different altitudes and for different shielding materials. Radiation
quantities at the target point (center of the sphere) were evaluated through a ray-by-ray
 thicknesses rise. According to the literature, the in situ resource utilization (ISRU) strategy
could reduce neutron damage by fabricating composite materials with Martian and lunar
RG [98,99]. Zaccardi et al. [100] performed simulations about the shielding power of
ultrahigh-molecular-weight PE (UHMWPE) composites. Simulations were conducted on
Polymers 2024, 16, 382 sphere geometries at different altitudes and for different shielding materials. Radiation
24 of 35
quantities at the target point (center of the sphere) were evaluated through a ray-by-ray
transport procedure with HZETRN. They also demonstrated the improvement in
mechanical properties by incorporating in situ Martian regolith in composite materials.
transport procedure with HZETRN. They also demonstrated the improvement in mechani-
Izod and flexural tests were carried out. The results of experimental analyses have
cal properties by incorporating in situ Martian regolith in composite materials. Izod and
validated the possibility of manufacturing structures with PE/RG composites. A
flexural tests were carried out. The results of experimental analyses have validated the
comparison between Al, PE, RG, and PE/RG materials using OLTARIS software is
possibility of manufacturing structures with PE/RG composites. A comparison between
reported in Figure 9.
Al, PE, RG, and PE/RG materials using OLTARIS software is reported in Figure 9.

Figure 9. Comparison
Figure 9.of dose and equivalent
Comparison of dose anddose for Al, dose
equivalent RG, PE, andRG,
for Al, PE/RG composites
PE, and in different
PE/RG composites in different
radiation fields at Mars ground level: (a) dose in the GCR spectra; (b) equivalent
radiation fields at Mars ground level: (a) dose in the GCR spectra; (b) equivalent dose in the dose
GCRin the GCR
spectra.
spectra. Adapted withAdapted withfrom
permission permission from Ref. [100].
Ref. [100].

All examined examinedshow

Allmaterials materials show aindecrease
a decrease in the absorbed
the absorbed dose withdose with increasing
increasing the the
shield thickness. However, a different behavior was denoted for the
shield thickness. However, a different behavior was denoted for the equivalent dose,equivalent dose,
showing the shielding ineffectiveness of Al in the Martian environment. In fact, the equiv-
alent dose increases with the areal density of the Al shield. This behavior determines
a shielding gap between the deep space environment and the Martian surface. For this
reason, PE/RG composites are considered protective materials since the absorbed equiv-
alent dose decreases as the shield thickness increases. This result was confirmed by the
neutron analysis. It was observed that neutron flux increases behind the Al shield while
it remains constant considering the RG shield and decreases with PE and PE/RG 50 wt%
shields. Al Zaman et al. [101] proposed innovative composites with Martian RG, whose
shielding effectiveness was investigated through GEANT4 and OLTARIS. RG composite
materials with poly-para-phenylene terephthalate (Kevlar), polyethylene terephthalate
(Mylar), lithium hydride (LiH), polystyrene, and polypropylene were investigated. A
preliminary analysis with GEANT4 was run to estimate the efficiency of radiation shielding
in homogeneous and composite materials. The model consists of a 10 g/cm2 thick slab
of RG placed outside, followed by a slab of selected materials (one by one) of variable
thicknesses (1–5 g/cm2 ), a vacuum region, and a 5 g/cm2 of tissue region. Then, a spherical
model was exploited in OLTARIS to calculate the effective equivalent dose for a female
adult voxel (FAX) phantom (with “never smoker population” weighted tissue). Similar
results regarding dose reduction have been noted in both the slab and sphere geometries.
It is noteworthy that LiH/RG composites provide the highest dose reduction of about 9%
with respect to the 15 g/cm2 Al shield. The other materials determine dose reductions
between 5% and 9% when compared to the 15 g/cm2 Al shield. In this work, the use of
3D-printed RG composites was proposed not only for radiation protection but also for
withstanding Martian storms and other harsh conditions on the planet.

3.3.2. SPE Environment

SPEs are unpredictable and sporadic radiation coming from the Sun that occur near
solar cycle maxima [102]. Liquid hydrogen is not only the best material to use against GCR,
but it can also be employed as a protective material for protons and electrons, the main
constituent particles of SPE spectra [103]. Different materials were simulated to assess
their shielding ability. Vuolo et al. [104] have provided numerical analysis of materials
Polymers 2024, 16, 382 25 of 35

for a wearable radiation protection spacesuit to mitigate the occurrence of acute radiation
effects on sensitive organs. Simulations were performed with the GRASv3.3 tool (GEANT4),
considering 1D and 3D setups. The SPE spectrum was calculated using the Emission of
Solar Protons (ESPs) model of the ESA SPENVIS software (2015) for a 1-year mission
without the Earth’s magnetic field to reproduce the deep space exposure [105]. Preliminary
results have been computed for different materials selected on the base of their material
index (MI) in 1D simulations. MI is defined as the ratio of the electronic stopping power to
Polymers 2024, 16, x FOR PEER REVIEW 27 of 38
the nuclear interaction transmission. Figure 10 reports the percentage reduction in dose as
a function of areal densities in g/cm2 .

Figure 10.10.
Figure Percentage dosedose
Percentage reduction in shielding
reduction materials
in shielding as a function
materials of thickness.
as a function Adapted
of thickness. with with
Adapted
permission from Ref. [104].
permission from Ref. [104].

It is
It noteworthy
is noteworthy thatthat
Al and Nextel
Al and 312, 312,
Nextel usually employed
usually employedin space structures,
in space offer offer
structures,
thethe
lowest dose reduction. At equal areal density, water, fa y acids,
lowest dose reduction. At equal areal density, water, fatty acids, and PE show and PE show be er better
shielding behavior. The highest MI was assigned to PE both from
shielding behavior. The highest MI was assigned to PE both from experimental and experimental and
numerical
numerical results thanks
results thanksto its
to high hydrogen
its high content,
hydrogen followed
content, by fa by
followed y acids
fatty and
acidsthen
and then
water. Organic compounds were classified after water, followed
water. Organic compounds were classified after water, followed by materials such by materials such as
asKevlar,
Kevlar, Nomex, and Mylar. Al and Nextel 312 have lower MI due to the high atomic
Nomex, and Mylar. Al and Nextel 312 have lower MI due to the high atomic number of
number of their constituent elements. Three-dimensional simulations were performed to
their constituent elements. Three-dimensional simulations were performed to compare
compare different models of spacesuits. Geometries were built using Geometry
different models of spacesuits. Geometries were built using Geometry Description Markup
Description Markup Language (GDML) both for phantom and suit models. They
Language (GDML) both for phantom and suit models. They considered a first model
considered a first model composed of water (ideal case) and a second multilayer made up
composed of water (ideal case) and a second multilayer made up of a containing layer of
of a containing layer of HDPE, Al or Kevlar, and an inner layer of water. Both models
HDPE, Al or Kevlar, and an inner layer of water. Both models show a dose reduction of
show a dose reduction of about 80% in extravehicular activity (EVA) and 44–57% in intra-
about 80% in extravehicular activity (EVA) and 44–57% in intra-vehicular activity (IVA)
vehicular activity (IVA) suits, reducing damage to blood-forming organs (BFOs).
suits,
PE reducing
and water damage to blood-forming
are considered organs
substantial (BFOs). in both experimental and
candidates
PE and water are considered substantial candidates
numerical studies. Laurenzi et al. [89] have investigated the shielding in both experimental and numeri-
properties of MDPE
and its compounds not only against GCR but also in the SPE environment using 1Dand its
cal studies. Laurenzi et al. [89] have investigated the shielding properties of MDPE
compounds
simulations not onlywith
conducted against GCR but also
HZETRN2015. in the SPEthe
In particular, environment using 1DMDPE,
difference between simulations
PEEK, PPS, and Kapton appears minimal when comparing the absorbed equivalent PEEK,
conducted with HZETRN2015. In particular, the difference between MDPE, dose PPS,
and Kapton appears minimal when comparing the absorbed equivalent
after the Carrington event. Models of shielding materials were slab shells with thicknesses dose after the
between 0 and 50 g/cm . The discrepancy in shielding performance of polymers and Al between
Carrington event. Models
2 of shielding materials were slab shells with thicknesses is
0 and 50 g/cm 2 . The discrepancy in shielding performance of polymers and Al is also
also reduced at high equivalent doses. However, it was demonstrated that reducing the
reduced
damage at high equivalent
associated with a singledoses. However,
event it was
requires demonstrated
a higher thicknessthatof reducing
materials the
withdamage
associated
respect withThe
to GCR. a single event properties
shielding requires a higher thickness of materials
of PE nanocomposites with with respect
CB4, GO, andto GCR.
The shielding
SWCNTs properties
were also exploredofby PEevaluating
nanocomposites with CBdose
the equivalent 4 , GO, and SWCNTs
deviation from purewere also
explored
MDPE. The by evaluating
curves the equivalent
are constant dose
at low filling deviation
loads from pureincreases.
as the thickness MDPE. The Abovecurves
2 are
wt% of filler concentrations, the increase in the equivalent dose is reduced as a function
of depth, demonstrating that fillers are less deleterious when larger thicknesses are
considered. These results are particularly visible for composites with SWCNTs and GO.
Iguchi et al. [106] developed a novel composite material consisting of benzoxazine resin
with ultrahigh-molecular-weight PE (UHMWPE) fibers in order to reach a suitable
compromise between shielding and mechanical performance. Materials were modeled
Polymers 2024, 16, 382 26 of 35

constant at low filling loads as the thickness increases. Above 2 wt% of filler concentra-
tions, the increase in the equivalent dose is reduced as a function of depth, demonstrating
that fillers are less deleterious when larger thicknesses are considered. These results are
particularly visible for composites with SWCNTs and GO. Iguchi et al. [106] developed a
novel composite material consisting of benzoxazine resin with ultrahigh-molecular-weight
PE (UHMWPE) fibers in order to reach a suitable compromise between shielding and
mechanical performance. Materials were modeled employing the slab geometry option.
Multiple simulations were conducted with slabs exhibiting an increasing areal density
from 1 to 30 g/cm2 . Equivalent dose of UHMWPE fiber/poly(3BOP-daC12) composite, Al,
UHMWPE, Cycom 934 resin was calculated using OLTARIS for SPE free-space simulations
of the August 1972 (King) event. It is evident that the hydrogen-rich poly-benzoxazine is
approaching that of UHMWPE. It provides superior radiation-shielding properties com-
pared to the Cycom 934 epoxy that is shifted even closer to the UHMWPE dose. To date,
these UHMWPE/poly(3BOP-daC12) composites have been tested on the ISS as part of
Materials International Space Station Experiment 12 (MISSE-12) from November 2019 to
March 2020. The samples were installed externally to assess their behavior over a one-year
period in space and to verify optical and tensile property degradation [107].
The shielding efficiency of water was primarily investigated in multilayered geome-
tries. Aghara et al. [60] studied the radiation behavior of SPE spectra transporting through
10 or 20 g/cm2 Al shield followed by 30 g/cm2 of water slab. The results were validated
using both deterministic (OLTARIS and HZETRN 2010) and Monte Carlo (MCNPX 2.7.0,
PHITS 2.64) transport codes. The 56 Webber, 72 LaRC, 89 Weibull, and 91 Carrington SPE
spectra were considered. The total particle fluence is similar for all SPE environments.
Proton fluence decreases as thickness increases. On the contrary, photon fluence increases
at high depths, leading to an increase in secondary photons produced from neutrons. The
total equivalent dose was computed, including the contribution of neutrons. They observed
that the contributions due to neutrons and photons are pronounced at higher thickness. The
91 Carrington event was more dangerous than the others, producing the highest amount of
absorbed radiation, followed by 56 Webber, 72 LaRC, and 89 Weibull.
To date, metals are usually employed in space for shielding SPE spectra, even if
they have low stopping power. Metal-based materials enriched with hydrogen and/or
boron have been developed to reduce the thicknesses and volumes occupied by metals
and achieve suitable shielding properties Rojdev et al. [108]. They investigated different
materials using HZETRN 2010: metal hybrids (MHs), metal–organic frameworks (MOFs),
and nano-porous carbon composites (CNTs) were loaded with hydrogen or methane for
radiation protection considering Carrington event SPE spectra. The spectra were fitted
using the band fitting method, and the differential spectrum was utilized as the input
environment. Doses in tissue (cGy) were calculated for material thicknesses ranging from
1 to 100 g/cm2 . All the materials perform better than Al, and only the hydrogen-loaded
compounds outperform HDPE. However, they are all relatively close to the performance
of HDPE.
Loffredo et al. [109] presented a study of protective materials made of Nomex doped
with boron at 10, 20, and 30 wt% using GEANT4 for numerical simulations. They devel-
oped a numerical system setup by modeling experiments conducted at the NASA Space
Radiation Laboratory. These experiments are based on the bombardment of an Al slab by a
1 GeV proton beam with the aim of reducing the dose from low-energy neutrons produced
during the interaction of a 1 GeV proton beam with pristine Nomex [110,111]. As protons
pass through the matter, there is a dose increase of 28% in the pure Nomex. This increase
was reduced with the addition of boron, corresponding to a dose drop of about 14% in the
best case (addition of boron at 10 wt%).
SPEs are dangerous for astronauts’ health also on Mars and the Moon’s surface even if
their effects on human tissues are less strong than GCR. Exposures on the lunar surface
are halved by the Moon itself, and on the Mars surface, they are reduced by over half
because of the planet and the Martian atmosphere [112,113]. Zaccardi et al. [100] have
Polymers 2024, 16, 382 27 of 35

examined absorbed dose on Mars’s surface using OLTARIS. The space environment was
simulated considering the NASA LaRC model of August 1972 for SPEs. A comparison of
Al, PE, and PE/RG composites was provided. As in the case of GCR, the absorbed dose
demonstrates a decreasing trend as a function of increasing thickness. However, analysis
of the equivalent dose shows the shielding ineffectiveness of Al. In fact, Al is effective only
for small thicknesses due to the presence of neutrons. In contrast, RG has slightly better
behavior than Al as the equivalent dose decreases. Overall, the effectiveness of PE/RG
composites is demonstrated by dosimetric results in protecting against Martian radiation.

3.3.3. LEO Environment

Radiation in LEO should be controlled by materials to implement passive shielding. In
fact, this environment is affected by different sources of radiation. GCR and SPE radiation
fields and trapped energetic electrons and protons (ERBs) are always present at these orbit
altitudes [114]. The GCR and SPE fluxes are generally mitigated by the geomagnetic field,
but they also depend on the solar activity [114,115]. The intensity of SPE spectra varies with
the sunspot cycle on the solar surface. When solar flares and coronal mass ejections increase
their periodicity and the radiation intensity emitted, the ionizing particles coming from
the Sun can penetrate the Earth’s magnetic field and increase human illnesses caused by
radiation exposure. The particle collisions with materials of space vehicles are dangerous
due to secondary particles (neutrons) generated and then reflected by Earth’s albedo [116].
Laurenzi et al. [89] investigated the behavior of PE-based nanocomposite materials in
LEO using HZETRN 2015. AP8 MAX trapped proton model for an orbit similar to the ISS
orbit (inclination of 51.6◦ and altitude of 400 km) was used in numerical simulations. From
a preliminary analysis, it was observed that polymers like PEEK, PPS, and Kapton have
similar values of equivalent dose to each other and are better than Al shield. On the other
hand, medium-density polyethylene (MDPE) shows the highest attenuation among solid
materials, and therefore, MDPE-based nanocomposites were selected for the simulations.
As in the case of SPEs, the equivalent dose of SWCNTs, GO, and CB4 composites decreases
with increasing thickness, demonstrating better protection.
As for other space environments, the use of polyethylene is also relevant in LEO.
Shavers et al. [117] developed a project to integrate PE into the International Space Station
(ISS) crew quarters (CQs). This design is based on the “as low as reasonably achievable”
(ALARA) requirement so as to ensure the safety of astronauts in space. A ray-tracing algo-
rithm was developed to generate a shielding distribution for 812 directions geometrically
placed around the center of each CQ. GCR and trapped particle fluxes were simulated
with HZETRN for the ISS at 400 km altitude and 51.6◦ inclination. ISS materials were
represented as Al. The results were reported only for the best case of PE shield with a
thickness of 4.8 g/cm2 . Simulations performed with HZETRN indicate that a 20% or more
reduction in the equivalent dose is achievable.
Emmanuel et al. [118] have realized a layered structure made up of PE matrix and
graphite (G) reinforcing fibers. This shield model was composed of alternating PE and
graphite with 2, 4, 8, and 16 layers and a silicone detector to measure the total ionization
dose (TID) using the GEANT4 codes. TID was simulated for a 15-year satellite mission in a
highly elliptical orbit (HEO), specifically a Molniya orbit. GCR and SPEs were accurately
modeled utilizing SPENVIS software, while trapped protons and electrons were defined by
AP-8 MAX and AE-8 MAX models, respectively. One composite configuration, indicated
as [PE/G]2 (with a 50% volume fraction of PE and an areal density of 1 g/cm2 ), has
resulted in a TID lower than that of unfilled PE, demonstrating the possibility of tailoring
the mechanical properties of PE-based composites with a minimal negative impact on its
radiation-shielding effectiveness.
Recently, materials to be integrated into spacesuits for the individual protection of
astronauts are being studied. Concerning EVA spacesuits, numerical simulations performed
by Waller et al. [119] have been carried out with HZETRN, considering an orbit that follows
that of the ISS for a duration of 10 years. The evaluated materials are summarized in Table 3.
Polymers 2024, 16, 382 28 of 35

Input data comprise information on the density, number of atoms, atomic and mass number
of each element. The results showed that only 9 cGy of equivalent dose is absorbed by
astronauts during a mission to Mars while staying in parking LEO for a few days.

Table 3. Materials and their function inside the spacesuit.

Materials Functions
Ortho-fabric External cover
Aluminized Mylar Insulator
Neoprene-coated nylon Liner
Dacron Restraint
Urethane-coated nylon Pressure garment bladder (PGB)
Nylon Liquid and cooling ventilation garment (LCVG)

Atxaga et al. [11] fabricated graphite carbon composites with carbon nanotubes (CNTs)
and tungsten nanoparticles as fillers and simulated their behavior for radiation shielding
using GEANT4. Materials were defined using correction factors derived from experimental
tests to estimate impurities in the layers. The simulations aimed to capture the overall dose
absorbed from the electronic components of spacecraft in LEO. Specifically, the simulation
setup involved slab geometries of shielding materials with different thicknesses (Al of 1
and 2 mm, tungsten of 50 and 100 µm, stainless steel of 50 µm and prepreg composite of
215 µm) followed by a silicon layer with a thickness of 300 µm. Promising results have
been obtained for proton shielding (20 MeV). As predicted, the high-Z material, tungsten,
had the most effect on the kinetic energy of the input protons. Layers made of prepreg
have the same effect on particle energies as 50 µm tungsten. Overall, the prepreg layer is
better or equal to that of 50 µm steel.

4. Summary and Challenges on the Design of Radiation-Shielding PBMs

4.1. Radiation Sources and PBM Design
High-energy photons from X-rays and gamma rays interact with matter, leading to
absorption through energy transfer. These interactions are related to the atomic compo-
sition of the target materials and involve three main mechanisms: photoelectric effect,
Compton scattering, and pair production. The photoelectric effect is most pronounced
in high-Z materials at low energies (typically <500 keV) [92]. In the design of PBMs for
radiation shielding, the use of nanofillers can be convenient to shield low-energy X-rays.
In fact, several studies have demonstrated that nanostructured PBMs are able to absorb
more low-energy photons compared to those reinforced with larger particle sizes [14,15].
This behavior can be ascribed to the increase in electron density within the material in
the presence of nanoparticles. Similarly, for low-energy gamma rays, smaller, uniformly
dispersed particle sizes offer greater photon blocking [16]. However, at higher energies,
this effect decreases due to the transition from the photoelectric effect to Compton scat-
tering. Lightweight and shielding-effective PBMs could be fabricated by incorporating
suitable concentrations of high-Z fillers into a flexible matrix [92]. These fillers are able
to attenuate radiation, whereas the use of a polymer matrix contributes to reducing the
overall weight with respect to conventional shielding materials. Nevertheless, the use of
high atomic number materials for shielding against GCR or SPE particles can lead to the
emission of highly penetrating and detrimental gamma rays. Considering this, shielding
PBMs should include elements that maximize projectile fragmentation while minimizing
fragmentation of the target material. Polymer-based composites made of low-Z materials,
particularly hydrogen or boron, have demonstrated efficacy in this regard [92]. Hydrogen,
with its small atomic diameter, offers numerous interaction points in polymers for projectile
fragmentation. Additionally, the absence of elements heavier than carbon minimizes the
production of target fragments and, consequently, reduces the risk of secondary radiations.
Overall, the aim is to strike a balance between effective shielding, reduced energy loss, and
risks associated with secondary radiations during space missions.
Polymers 2024, 16, 382 29 of 35

Regarding neutrons, they interact mainly with atomic nuclei, penetrating deep into
materials. In this case, interactions include scattering and trapping. Interactions with
matter can lead to the generation of other radiations, such as protons, alpha particles, and
gamma rays. In neutron shielding, hydrogen-rich polymers, such as PE, prove effective
in attenuating fast neutrons. Boron-filled composites show remarkable thermal neutron-
shielding efficiency. The balance between elements with light and heavy nuclei is crucial
to fabricating effective neutron-shielding materials, although the difference in density
between high and low-Z fillers poses challenges in achieving interfacial compatibility.
Structurally optimized designs with homogeneously dispersed fillers represent a
challenge for the development of advanced radiation-shielding PBMs with multifunctional
properties. The fabrication of these materials involves problems of agglomeration and non-
uniform distribution of the functional reinforcement selected for shielding, compromising
both efficiency in radiation protection and mechanical properties [120]. In this perspective,
novel strategies to improve interface interactions can be adopted, such as opportunely
mixing different fillers, surface modifications, and hybrid filler designs with shell structure.
Nevertheless, considering the thermal scattering capacity, a multilayer structure could be
adopted for realizing radiation-shielding PBMs, exploiting the ability of the different layers
to efficiently scatter, reflect, absorb, and attenuate radiation.

4.2. Effects of Space Radiation on Polymers

Space radiation can potentially affect the properties of polymers, leading to alterations
in their mechanical, thermal, and optical behavior [121]. Mechanical degradation can take
place, with losses in flexibility and tensile strength. Thermal properties may be modified
in terms of thermal conductance and energy stored in the material. Additionally, optical
properties can be altered with changes in terms of emissivity and absorbance.
Typically, radiation interactions with polymers induce free-radical reactions [122].
Cross-linking and scission can take place with the generation of intermolecular bonds or
backbone breaks, respectively. In particular, the presence of unsaturated bonds favors the
occurrence of cross-linking after radiation exposure. Considering these effects, the addition
of suitable fillers into the polymer matrix enables improved performances under ionizing
radiation and effective shielding materials.

4.3. Other Constraints for the PBM Design

Strength, durability, and low weight are the additional requirements expected for
space radiation-shielding materials. Moreover, these materials should maintain high
performance until the end of the space mission. As explained by Shehab et al. [123],
the total cost of the material includes recurring and nonrecurring fees. Recurring costs
include raw materials, direct costs of working, and energy, while nonrecurring costs include
indirect costs of working, equipment, tools, and facilities. In this context, PBMs can offer
substantial advantages such as weight reduction, multifunctional properties, reduced
number of parts needed to make the shielding component, and customizable strength and
stiffness, which can lead to significant reductions in maintenance costs. PBMs can achieve
a low “buy-to-fly” ratio, which indicates the amount of material used with respect to the
final weight of the material after the fabrication process. Moreover, improved material
testing is needed to better predict the long-term performances of these materials based on
short-term testing [124]. In this perspective, advances in computational tools play a crucial
role in predicting the response of materials to the combined effects of radiation in the harsh
space environment.
Figure 11 summarizes the main issues related to the design of PBMs for space applica-
tions, reporting the two approaches for evaluating their shielding effectiveness.
16, x FOR PEER REVIEW 32 of 38
Polymers 2024, 16, 382 30 of 35

Figure 11. Graphical representation of the main issues related to the design of PBMs for space
Figure 11. Graphical representation of the main
applications, reporting the issues related to for
two approaches the evaluating
design of PBMs for space effectiveness.
their shielding ap-
plications, reporting the two approaches for evaluating their shielding effectiveness.
5. Conclusions
5. Conclusions Recent advances in the development of polymer-based materials (PBMs) with radiation-
shielding properties were
Recent advances in the development discussed, focusing
of polymer-based materialson (PBMs)
their potential application in the harsh
with radia-
tion-shielding properties were discussed, focusing on their potential application in theof polyethylene (PE),
space environment. The latest experimental studies on PBMs made
polyimide
harsh space environment. (PI), polydimethylsiloxane
The latest experimental studies on(PDMS), PBMs made and ofother functional matrices were de-
polyethylene
scribed, considering the incorporation of different
(PE), polyimide (PI), polydimethylsiloxane (PDMS), and other functional matrices fillers. The effects of reinforcements such
were
as boron
described, considering nitride, boron
the incorporation of carbide,
differentcarbon-based
fillers. The effects nanoparticles, and metals were considered.
of reinforcements
such as boron nitride, boron carbide, carbon-based nanoparticles, and metals were con-of the reinforcement,
The optimization of the PBM design, as well as the suitable dispersion
were taken
sidered. The optimization of theinto
PBM account
design,forasevaluating
well as thethesuitable
overall dispersion
performance ofofthethe
re-PBMs. The role of the
fillers on the radiation-shielding properties was widely
inforcement, were taken into account for evaluating the overall performance of the PBMs. discussed, and results compared
The role of the fillers on the radiation-shielding properties was widely discussed, and re- radiation exposure.
with them were obtained for the neat polymer matrix under the same
sults compared with them Numerical studies
were obtained foronthePBMs, carried out
neat polymer by radiation
matrix under thetransport
same ra- codes, were argued.
diation exposure. The codes were described as fundamental instruments for evaluating the material shielding
effectiveness
Numerical studies on PBMs,before
carriedspace
out missions, as well
by radiation as for the
transport selection
codes, wereof the most suitable radiation
argued.
countermeasures. Numerical analyses on PBMs in different space environments, such as
The codes were described as fundamental instruments for evaluating the material shield-
GCR, SPE, and LEO, were examined. The results confirm the crucial role of the codes in
ing effectiveness before space missions, as well as for the selection of the most suitable
predicting the shielding behavior of materials under different radiation conditions.
radiation countermeasures. Numerical analyses on PBMs in different space environments,
The relation between the different radiation sources and the development of efficacious
such as GCR, SPE, and LEO, were examined. The results confirm the crucial role of the
shielding PBMs was discussed. Moreover, the main constraints on the design of suitable
codes in predicting the shielding behavior of materials under different radiation condi-
shielding materials were highlighted. New challenges are the optimization of the filler
tions.
integration processes in the polymer matrix, the use of different fillers, and balancing the
The relation between the different radiation sources and the development of effica-
shielding effectiveness of the reinforcements and the multifunctional properties, which
cious shielding PBMs was discussed. Moreover, the main constraints on the design of suit-
should be durable throughout the space mission. Furthermore, the development of novel
able shielding materials were highlighted. New challenges are the optimization of the
advanced computational tools able to simulate the combined effect of the different radiation
filler integration processes in the polymer matrix, the use of different fillers, and balancing
sources on spacecraft materials and biological tissues represents a further challenge for the
the shielding effectiveness
definition ofofthe reinforcements
performing PBMs. and the multifunctional properties,
which should be durableOverall,
throughout experimentalmission.
the space studies Furthermore,
are efficacious theindevelopment of
providing detailed results on the
novel advanced computational tools able to simulate the combined effect of the different
effect of a specific radiation source on PBMs. Nevertheless, the combined effect of space
radiation sources onradiation
spacecraft canmaterials and biological
be assessed tissues represents
using computational a further
tools. The chal- between these two
interaction
lenge for the definition of performing PBMs.
approaches is essential for the development of PBMs that can be successfully applied in the
Overall, experimental studies are efficacious in providing detailed results on the ef-
space environment.
fect of a specific radiation In source
summary, on this
PBMs. Nevertheless,
review provided an the combined
overview effect
of the of multifunctional
latest space PBMs that
radiation can be assessed using computational tools. The interaction between these
can be potentially applied in the harsh space environment as radiation-shielding two materials.
Crucial points in the definition of these materials and future challenges to improve them
Polymers 2024, 16, 382 31 of 35

were also identified. By recognizing the evolving advances in this field, the objective
of this review is to add value to the continuous endeavors aimed at defining the most
effective PBMs for safeguarding both human health and spacecraft performance during
space exploration.

Author Contributions: Conceptualization, M.G.S.; methodology, E.T., S.L. and M.G.S.; validation,
M.G.S. and S.L.; writing—original draft preparation, E.T. and L.L.; writing—review and editing,
M.G.S. and S.L.; supervision, M.G.S. All authors have read and agreed to the published version of
the manuscript.
Funding: The authors kindly acknowledge funding from the Sapienza University of Rome (grant
number RG1221816C43DA9B).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflicts of interest.

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