Advanced Aramid Fibrous Materials: Fundamentals, Advances, and Beyond

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Advanced Aramid Fibrous Materials: Fundamentals, Advances, and Beyond
Article in Advanced Fiber Materials · October 2023

DOI: 10.1007/s42765-023-00332-1
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Advanced Fiber Materials
https://doi.org/10.1007/s42765-023-00332-1
REVIEW
Advanced Aramid Fibrous Materials: Fundamentals, Advances,

and Beyond
Annan He1 · Tonghe Xing1 · Zihui Liang1 · Yuxin Luo1 · Yu Zhang1 · Mengqi Wang1 · Zhiyu Huang1,2 · Jie Bai3 ·
Liuyan Wu1 · Zhicheng Shi1 · Hongmei Zuo4 · Wenshuo Zhang1 · Fengxiang Chen1 · Weilin Xu1
Received: 16 May 2023 / Accepted: 6 September 2023

© Donghua University, Shanghai, China 2023
Abstract
Aramid fibers (AFs) are widely applied in many cutting-edge fields, due to their excellent comprehensive performance. Ongo-
ing research efforts are therefore underway to expand the applicability by designing more environmentally friendly and
low-cost synthesis methods, incorporating new chemical components in the skeletons or internal structures of polyamide to
enhance their processability and functionality. Despite being at the forefront of scientific research, there are fewer reviews
that comprehensively summarize the latest progress of AFs. This review focuses on the fundamental research of AFs since
their inception and summarizes the advanced progress and applications of AFs. Firstly, the synthesis mechanism and meth-
ods of AFs and their structure–property relationship are comprehensively discussed. Subsequently, we review the recent
progress in surface functionalization of AFs by using advanced micro-nanoscale modification strategies to enhance the
interface properties and ultraviolet (UV)-resistance properties, and summarize the advantages and disadvantages of vari-
ous modified methods. Then, applications of AF and aramid nanofiber (ANF) in various fields are discussed. Finally, the
possible challenges and outlooks toward the future development of AFs are highlighted, which is expected to provide new
insights for the next-generation advanced functional AF materials and facilitate the industrialization development level for
high-performance AFs and their composites.
Keywords Aramid fiber · Surface functionalization · Application · Challenges and outlooks
Introduction vehicle industries, individual protection, leisure sports,

electrical insulation, asbestos substitutes, industrial filters,
As a typical high-performance organic fibrous material, as well as in other high-grade civil products due to their
aramid fibers (AFs) and their composites are widely used exceptional properties, such as high mechanical properties,
in aerospace, armament industry, bullet-proof body armor, light-weight, high-temperature resistance, flame retardant,
chemical stability and insulating [1–5]. It is a landmark
achievement of human beings in the history of chemical fiber
Annan He, Tonghe Xing, and Zihui Liang have contributed equally development and has therefore drawn increasing attention
to the work. since its invention in 1964. With the continuous expansion
of demand in various fields and the rapid development of
* Fengxiang Chen
fxchen_czx@wtu.edu.cn science and technology, AFs have evolved into a massive
family with massed varieties, including poly (p-phenylene
1
State Key Laboratory of New Textile Materials terephthalamide) (PPTA, also known as Aramid 1414, para-
and Advanced Processing Technologies and Hubei Key AF, and p-AF), poly(m-phenylene isophthalamide) (PMIA,
Laboratory of Digital Textile Equipment, Wuhan Textile
University, Wuhan 430200, China also known as Aramid 1313, meta-AF, and m-AF), heterocy-
2 clic AFs such as poly(p-phenylene benzobisthiazol) (PBO)
College of Textiles and Clothing, Qingdao University,
Qingdao 266071, China and hyperbranched AFs [6–10]. Despite these remarkable
3 properties over ordinary organic polymer fibers, AFs are still
China Textile Engineering Society, Beijing 100025, China
prone to inherent defects that can limit their utility. These
4
School of Textile and Garment, Anhui Polytechnic terrible situations can be attributed to the fact that ultraviolet
University, Wuhu 241000, China
13
Vol.:(0123456789)
(UV) radiation from the sunlight is capable of deteriorating an overview of the various synthetic routes since its inven-
the integrity of the chemical structure in the AF molecular tion. Then, we analyzed and discussed the structure–activ-
chain skeleton [11, 12]. What's more, the dense, smooth, ity relationship of AFs structures and properties. Significant
and inert surface of AFs, which results from the conjuga- advances that have been made in surface functionalization
tion effects and steric hindrance effects between benzene and applications of AFs and aramid nanofibers (ANFs) were
rings and carbonyl groups in the aramid molecule, hinders reviewed, most in the past decade. Finally, the challenges
its adhesion to the resin matrix in its composites [13–15]. in the future development of these high-performance AFs
Consequently, the outstanding properties of AFs cannot be materials were prospected to maximize the technological
adequately reflected in their composites, and their applica- benefits.
tion is limited.
Currently, extensive research has been conducted on
surface inert optimization and surface functionalization Development History of Aramid Fibers
to enhance UV resistance and culminating in significant
progress. Improving the wettability and affinity between Prior to the 1960s, a form of special fiber that could combine
the fiber and matrix by chemical bonding and mechanical the heat resistance of asbestos and rigidity of glass fibers
interlocking necessitates a chemical modification that intro- was urgently required by the industry for application in many
ducing active oxygen-containing groups such as hydroxyl, fields such as tires, parachutes, and body armor. DuPont, a
carboxyl, amino groups, and surface roughness onto the well-known American multinational chemical company, was
surface of AFs [16–18]. Hence, various methods, includ- the first to achieve a breakthrough in response to this need.
ing physical modification (ultrasonic impregnation, plasma It developed an m-AF known as Nomex, in 1963. DuPont
treatment, high-energy-ray modification, and supercritical began commercializing it in 1967 after an extensive test-
fluid modification) [19, 20], chemical modification (etching, ing procedure (Fig. 1a). Subsequently, Kevlar, a yellow p-
chemical grafting, and complexation modification) [21, 22], AF with improved mechanical capabilities, was developed
and other approaches (coating method and nanomaterials) in 1970. It has been widely adopted for commercial use.
[23, 24] have been utilized to improve the interface perfor- DuPont then produced a series of Kevlar fibers with vari-
mance of AFs. Introducing inorganic UV absorber/shielding ous mechanical properties for diverse applications. These
coatings onto AF surfaces is the mainstream approach of include Kevlar-29, Kevlar-49, Kevlar-49 AP, Kevlar-149,
improving UV resistance for AFs by using in-situ chemi- and Kevlar-KM. Similar products were released in other
cal grafting, sol–gel method, hydrothermal, hydrothermal nations following Kevlar's initial invention by DuPont.
reduction, hydrothermal crystallization, co-polymerization, The All-Union Scientific Research Institute of Artificial
layer-by-layer (LBL) self-assembly as well as atomic layer Fiber (VNIIV) in the Soviet Union was the first to success-
deposition [25]. The most commonly used inorganic UV fully develop heterocyclic AF, named SVM. This type of
absorbers/shielding are graphene, graphene oxide (GO), AFs was semi-industrialized in 1973. In 1978, a ternary
metal–organic frameworks (MOFs), and other metal oxide- copolymerization para-heterocyclic aramid with enhanced
based photocatalysts [26]. However, these methods men- mechanical properties, known as Armos, was developed on
tioned above can considerably increase the weight of the the basis of SVM. However, it was highly challenging to
AFs and seriously compromise their flexibility. What's compete with Kevlar in the civilian field owing to the com-
worst, most inorganic UV absorption and shielding materials plexity of the synthesis process of the heterocyclic mono-
can even generate oxidizing species derived from oxygen- mers of SVM and Armos. Meanwhile, the concentration
rich vacancies, nanogranular crystals, and electronic defects of the spinning solution was low. This further lowered the
under UV irradiation, which inflict damage to the amide speed of fiber formation and the fiber yield in the manufac-
bond in the chain structure of the AF molecule, thus leading turing process. The high heat-treatment energy consump-
to accelerated aging of the AFs bulk. tion further increased the production costs. These manu-
With the rapid development and upgrading of advanced facturing constraints significantly increased the production
fiber materials, AF has become an indispensable component costs and reduced the competitiveness of their products. To
of advanced engineering materials, even guiding the mate- overcome existing manufacturing restrictions and produce
rial design for future innovations. However, few literatures high-quality fibers with lower costs, Soviet Union's scientists
have comprehensively summarized the fabrication, struc- developed a new method to fabricate p-aramid Terlon in the
ture–activity relationship, applications, and prospective 1980s. It overcame the shortcomings of the conventional
challenges regarding such an exciting material. It is neces- method and enabled the production of fibers with high spin-
sary to review the recent advances of AFs for accelerating ning dope concentration and spinning speed. This rendered
the industrialization process. In this manuscript, we first its production cost and performance comparable to those
summarized the development history of AFs, followed by of Kevlar. In 1985, a pilot production line was constructed
13
Fig. 1 a The history of commercial AFs. b and c Summary of publications (b) and citations (c) relating to AFs. The number of publications and
citations was collected from the Web of Science between 1975 and 2022.
successfully. In the 1990s, Russia successfully developed was developed by AkzoNobel in the Netherlands in 1986
and mass-produced a new type of heterocyclic AF known and acquired by Teijin in 2000. These commercial activities
as Rusar, using the dry-jet wet spinning method. Since then, have significantly promoted the manufacturing of advanced
several upgraded products on the basis of Rusar have been AF products in Japan. In the 1980s, PBO fibers were devel-
developed. These include the high-strength and high-model oped in the United States for aerospace applications. Their
Rusar-S (which exhibits a tensile strength of 5.5–6.4 GPa mechanical, flame-retardant, and chemical stability proper-
and Young`s modulus of 160 GPa) and heat-resistant and ties are better than those of conventional AFs such as Kevlar
flame-retardant Rusar-O (with a limiting oxygen index (LOI) and Nomex produced by DuPont. Moreover, the production
value of approximately 40–45). After the turn of the twenty- cost is lower than that of high-performance Russian AFs. It
first century, several Russian research units successfully is considered the most potential member of the polyamide
developed a quaternary copolymerized Rusar-NT fiber based family containing heterocyclic aromatics and is thus referred
on Armos products. It demonstrated a higher mechanical to as the super fiber of the twenty-first century. Toyobo,
performance such as a tensile strength of 7 GPa, a Young's another Japanese company, constructed a PBO monomer
modulus of 180–200 GPa, and an LOI value exceeding 40. and spinning production line in 1994. It successfully pro-
Notably, the fiber displayed remarkable flame retardancy duced PBO fibers in 1995. Toyobo is the only company that
properties, representing the highest level of heterocyclic can commercially produce PBO fibers and continues to hold
AFs produced in Russia [27]. confidential technological information. In the twenty-first
The commercial development of advanced AFs products century, Korea became a noteworthy player in the production
has significantly improved the capability for manufacturing of AF fibers with the introduction of p-AF Heraron by the
such fibers, particularly in Japan. In 1972, Teijin, a Japa- Kolon Group in 2006 and the starting of the production of
nese chemical technology company, began manufacturing p-AF Alkex by the Hyosung Group in 2009.
Conex fibers (a type of p-AF). In 1978, this company suc- The research on AFs in China began relatively late. The
cessfully developed more flexible Technora fibers contain- chemical composition of aramid 1414 was identified inde-
ing -O-groups and started mass production in 1987. Twaron pendently in 1985. Nonetheless, Chinese companies have
is a type of poly(isophthaloyl p-phenylenediamine) fiber. It achieved mass production of various types of AFs, and
13
remarkable achievements have been made in the twenty-first The TPC/IPC solution was then added to an aqueous solu-
century. Tayho, a Chinese company located in Shandong tion of aromatic diamines with stirring. When the TPC/IPC
province, successfully mass-produced m-AF Tametar. It solution was introduced into the aromatic diamine solu-
subsequently released p-AF Taparan to the market in 2011. tion, a polycondensation reaction occurred at the interface
Other Chinese manufacturers such as Handsomes also pro- between the two solutions. This resulted in the formation of
duced AFs in 2018. With the escalation of trade restrictions polymeric films [29, 30]. This method provides a theoreti-
in recent years, an increasing number of Chinese enterprises cal basis and an intuitive means for synthesizing p-aramid.
and academic institutions have begun to research, produce, However, a critical drawback of interfacial polycondensation
and apply AF, and have achieved effective results. is that it should be performed at room temperature. However,
With the continuous development and maturity of the polycondensation reaction is an exothermic process. This
AF technology, the strength of AF fibrous products has results in an increase in the reaction system temperature,
improved. This has made them essential for developing cut- which could be increased to 50–60 °C. The variation in
ting-edge applications. An increasing number of countries temperature severely hinders the continuous process of the
are manufacturing AFs and related composites. Figure 1a reaction, thereby resulting in a reduction in the production
depicts a timeline for the development of commercial AFs. efficiency [31]. Therefore, it is necessary to synthesize AF
At present, there is an increasing need for AFs in ballistic materials efficiently and rapidly by optimizing the reaction
protection, energy, equipment manufacturing, intelligent process.
wearables, and other fields. This indicates the broad range
of application prospects for the further development of such Low‑Temperature Polycondensation
materials. The number of annual publications (Fig. 1b) and
citations (Fig. 1c) associated with AFs over the past few As an alternative method, low-temperature polycondensation
decades has increased accordingly. This provides further was developed by DuPont during the 1960s to overcome the
evidence to support this observation. temperature increase described above during the interfacial
polycondensation process. Both m-aramid and p-aramid can
be prepared using this method. Figure 2a and b depicts their
Synthesis of Aramid Fibers reaction mechanisms, respectively. This methodology uses
various chemicals such as N-methylpyrrolidone (NMP),
Aromatic diacyl chlorides are typically utilized to synthe- N, N-dimethylacetamide (DMAc), and hexamethylphos-
size AFs because of the difficulty of the chemical reactions phoric triamide (HMPA; it is being phased out owing to
between aromatic diamines and aromatic dicarboxylic its carcinogenicity and difficult recyclability). Typically,
acids [28]. Aramid is synthesized based on a polyconden- the synthetic process starts with the complete dissolution
sation reaction between the amino group (-NH2) and acid of PPD, anhydrous LiCl/CaCl2, and pyridine in the selected
chloride group (-COCl), the formation of the amide group solvent. The mixture is then cooled to 258 K (− 15.15 °C)
(-NH-CO-), and HCl. Over the past 50 years, scientists have in a N2 atmosphere before being stirred vigorously. An equal
experimented with several aramid synthesis methodologies molar amount of TPC is added. As the reaction progresses,
including interfacial polycondensation, low-temperature a viscous paste-like gel product is produced. After stirring,
polycondensation and direct polymerization, ring-opening the reaction mixture is permitted to stand overnight before
polymerization, non-aqueous suspension polymerization, being heated to room temperature. Finally, the obtained mix-
and microchannel reactors. In this section, a detailed review ture is washed with deionized water to remove any remain-
of several synthetic techniques used for AFs production is ing solvent and HCl [32, 33]. The synthesis method for
provided. It includes their mechanisms, synthetic raw chemi- m-aramid is similar to that for p-aramid. Figure 2c shows
cals, advantages, and drawbacks. the reaction mechanism for producing PBO. Specifically,
this process includes the addition of equal molar amounts
Interfacial Polycondensation of 1,4-diaminoresorcinol dihydrochloride and TPC and a
certain amount of phosphoric acid in a container with N 2
DuPont developed a method for aramid synthesis by inter- gas, stirring, and dehydrogenation at 65 °C and 80 °C for
facial polycondensation in the 1950s [28]. In their synthe- a certain period before being cooled to room temperature.
sis, aromatic diamines such as p-phenylenediamine (PPD) Then, P2O5 is added to achieve a concentration of 75–80%
and m-phenylenediamine (MPD) were dissolved in deion- and generate poly (phosphoric acid). Poly can function as a
ized water combined with a marginal amount of NaOH or solvent, catalyst, and dehydrating agent. Subsequently, the
Na2CO3 as additives. Terephthaloyl chloride (TPC) and mixture is stirred at 80 °C for 2 h and cooled to room tem-
isophthaloyl chloride (IPC) were dissolved in water-insolu- perature. Then, P 2O5 is added again to increase the concen-
ble organic solvents such as benzene and tetrachloromethane. tration to 83%. The stirring process is maintained while the
13
Fig. 2 Synthesis mechanism of the a m-aramid, b p-aramid, and c PBO (Zylon)
temperature is increased at predetermined intervals (16 h at synthesizing PPAT using transesterification. They employed
160 °C and 4 h at 190 °C). Finally, the product is washed sulfobenzides to facilitate the polycondensation of aromatic
with water and dried to obtain PBO. Currently, this method diesters and diamines. This ultimately resulted in the suc-
is efficient for commercially synthesizing AFs [34–36]. cessful synthesis of PPTA. New synthetic reactions and
advanced reaction systems continue to be active research
Direct Polymerization areas for the development of novel PPTA synthetic meth-
odologies. However, owing to their cost and controllability,
In addition to low-temperature polycondensation, direct the aforementioned methods proposed by Yotsumoro and
polymerization is a technique that has been utilized suc- Shin are not universally accepted by the industry. Yamazaki
cessfully in industrial production [37, 38]. This method has et al. [43] obtained poly-p-benzamide with a high molecu-
several advantages including the straightforward operational lar weight. It could be spun by a direct polycondensation
process, rapid reaction, and relatively low manufacturing reaction of p-aminobenzoic acid (PABA) with diphenyl and
costs. Moreover, the direct polymerization process ena- triaryl phosphite in NMP-pyridine solutions containing LiCl
bles the manufacture of multiple species of AF products and CaCl2. Higashi et al. [44–46] also synthesized polyam-
via diverse raw chemical combinations. This significantly ides utilizing triphenyl phosphite by performing an identical
increases the variety of products that can be produced. direct polycondensation reaction in the presence of poly(4-
Technora is a new product manufactured by Teijin, Japan. vinylpyridine) (P4VP) and LiCl. The chemical reaction for-
It is synthesized via direct polymerization. This product is mula used in this study is shown in Fig. 3a. The authors
obtained by the polycondensation of 3,4ʹ-diaminodiphenyl prepared two solutions: terephthalic acid (TPA), 4,4-diami-
ether (3,4'DAPE), PPD, and TPC. After dissolving nodiphenylmethane (MDA), triphenyl phosphite, and P4VP
40–60 mol.% of 3,4'DAPE and 60–40 mol.% of PPD in a in NMP, and pyridine containing LiCl. The mixture was
mixture of NMP and DMAc, TPC was added while the mix- heated while being stirred under a nitrogen atmosphere. The
ture was stirred vigorously. It is noteworthy that inorganic well-mixed reaction mixtures were added to methanol. The
salt co-solvents such as LiCl or C aCl2 are eliminated from precipitate was separated by centrifugation and washed thor-
the Technora® polymer solution throughout the process. oughly in methanol. Finally, the polymers were washed with
This removal is a key advantage of direct polymerization. It boiling methanol. Silver [47] developed a method to syn-
results in a considerable reduction in the production costs. thesize p-aramid using a direct polycondensation reaction
After stirring, a type of inorganic salt such as Ca(OH)2, with SO3, which is an inexpensive and commercially avail-
CaO, CaCO3, or Li2CO3 is dissolved in the NMP to func- able chemical (Fig. 3b). However, this method is hindered
tion as a neutralizing agent. The polymer obtained is washed by undesired secondary reactions such as sulfonation. Shoji
and dried using Technora [39]. However, notwithstanding [48] reported a strategy for directly synthesizing aramids by
the use of these techniques, exothermic issues remain unre- successfully polymerizing aromatic dicarboxylic acids with
solved. In addition, the use of highly toxic organic solvents aromatic diamines containing ether linkages, as shown in
such as HMPA and NMP poses a significant challenge to Fig. 3c. These AFs have a higher polymer chains mobility,
safe and environmentally friendly production processes [40]. lower glass transition temperatures (Tg), and melting points.
Yotsumoro [41] and Shin [42] proposed similar methods for This is suitable for synthesizing AFs with Tg of 250 °C. The
13
Fig. 3 a Direct Polymerization in phosphite solution for aromatic uct pictures and mechanism of PPTA generated in ionic liquids.[50],
polyamide. [44], Copyright 1980. Reproduced with permission from Copyright 2018. Reproduced with permission from American Chemi-
John Wiley & Sons, Inc. b Direct polymerization of aromatic poly- cal Society. f Schematic diagram of the non-aqueous suspension poly-
amide by Para-phenylenediamine and TPA in SO3. [47], Copyright condensation process for aromatic polyamide. [51], Copyright 2015.
1979. Reproduced with permission from John Wiley & Sons, Inc. c Reproduced with permission from Chinese Chemical Society, Insti-
Direct polymerization of aromatic polyamide by aromatic dicarbo- tute of Chemistry, Chinese Academy of Sciences and Springer-Verlag
xylic acids and aromatic diamines containing ether linkages. [48], Berlin Heidelberg. g Synthesis of PPTA in a micro-channel reactor
Copyright 2008. Reproduced with permission from the Society of and the structure diagram of the micro-sieve mixer of the reactor.
Polymer Science, Japan. d Synthesis mechanism of aromatic polyam- [52], Copyright 2015. Reproduced with permission from Royal Soci-
ide with palladium catalyst.[49], Copyright 1993. Reproduced with ety of Chemistry
permission from American Chemical Society. e Diagram and prod-
abovementioned synthesis strategies have established a foun- catalyst synthesis of AFs. Yoneyama [55] synthesized a
dation for the industrial production of AFs. Nevertheless, series of aramids in the presence of a palladium catalyst
direct polymerization has gradually been replaced because via carbonylation polymerization of aromatic dibromides
of the high cost of raw materials, reaction conditions, and and diamines with carbon monoxide (CO). This technique
secondary reactions. was developed by Yoneyama. It paved the way for the syn-
thesis of AFs using Pd catalysts. Producing aromatic poly-
Ring‑Opening Polymerization amides with high molecular weights and determining the
optimal ratio of reacting materials are challenging indus-
Metal-based catalysts play a pivotal role in ring-opening trial tasks. Based on the method of Yoneyama, Perry [49]
polymerization. This is because these are highly active optimized the procedure of synthesizing aramids through
and enable a precise control over polymer characteristics 4,4ʹ-oxybisbenzenamine and m-dibromobenzene or m-diio-
such as dispersion, microstructure, and regularity [53, dobenzene without CO in the presence of a palladium cata-
54]. Many studies have been conducted on the palladium lyst (as shown in Fig. 3d). He determined that two important
13
parameters are integral to optimal manufacturing productiv- polycondensation method provides distinct advantages.
ity: (1) a marginal excess of diamine monomers and (2) a These include a hermetically sealed reaction environment
high final molecular weight of m-diiodobenzene monomers that effectively isolates the reactants from oxygen and water,
compared with that of brominated monomers. Because of simple elimination of HCl to facilitate the reaction, well-
the remarkable properties of the as-prepared samples, this controlled temperature, and low viscosity. These result in
technique is an attractive alternative for synthesizing high- decreased energy costs. However, the viscosity of the prod-
molecular-weight aromatic polyamides. uct increased during the subsequent stages of the reaction,
Ionic liquids exhibit unique physical and chemical prop- thereby hindering effective stirring. The product quality
erties such as nonvolatility, good solubility, and strong elec- should be improved further.
trical conductivity. In addition, these have the following
advantages: relatively stable chemical properties, negligible Microchannel Reactors
vapor pressure, adjustable acidity, and remarkable recov-
erability and recyclability. These advantages significantly A microchannel reactor is a continuous-flow reactor whose
expand the range of applications of ionic liquids [56–58] internal structure has dimensions of the order of millim-
and induce scientists to study the synthesis of polyamides, eters–micrometers. It has the advantages of a precise feed
particularly PPTA, using ionic liquid [59, 60]. However, control and high specific surface area. These allow for the
negligible information is available on the synthesis of PPTA rapid mixing of materials and rapid heat dissipation of the
in pure ionic liquids. Moreover, the use of an ionic liquid reaction [63]. Microchannel reactors have been used exten-
as a polymerization medium can only yield low-molecular- sively in microwave-enhanced reaction processes [64], nan-
mass PPTA. Dewilde et al. [50, 61] developed a technique oparticle preparation [65, 66], biomedical synthesis [67],
for synthesizing PPTA in ionic liquids. It was an improve- and green organic catalysis [68]. In recent years, continuous
ment over previous approach. Figure 3e illustrates the syn- production using the microchannel reactor technology has
thesis mechanism, optical images of the products, and their been widely employed for organic synthesis and polymeriza-
chemical formulas. The NMP/CaCl2 solution was substi- tion [69, 70]. During polycondensation, the rapid heat dis-
tuted by 3-methyl-1-octylimidazolium chloride ([C8MIM] sipation in the microchannel reactor effectively prevented
[Cl]) as the solvent for synthesizing PPTA. These polycon- the wide molecular weight distribution of PPTA induced
densation reactions proceeded via a mechanism similar to by the temperature increase. Wang et al. [52] designed a
that in which NMP and CaCl2 are combined as solvents. microstructured chemical system (Fig. 3g) for synthesizing
The PPTA polymer obtained through this approach at 0 °C PPTA polymers. NMP was used as the solvent, and anhy-
showed an inherent viscosity of 1.95 dL/g. In addition, the drous CaCl2 was used as the co-solvent. PPD and TPC were
highest recorded molecular weight of PPTA was obtained dissolved in a NMP/CaCl2 mixture to be used as precursors.
by polymerization in ionic liquids. Therefore, ionic liquids The forward reaction was promoted by introducing N 2 into
are regarded as effective media for manufacturing polymers the system to remove the HCl produced during the reaction.
with macromolecular masses. The PPTA prepolymer reacted rapidly in the microchannel
reactor after the reaction solution was mixed in a microsieve
Non‑aqueous Suspension Polymerization mixer through the feeding pipeline. By adjusting the synthe-
sis conditions, a polymer with a weight-average molecular
The non-aqueous suspension polymerization method range of 4000–16,000 was obtained. This innovative pro-
involves the use of a nonreactive solvent to surround the cedure can enhance the safety and convenience of polycon-
reactants in the system. This prevents them from coming densation processes. However, microchannel reactors have
in contact with the water and oxygen in the air, thereby several limitations. The viscosity of the reaction mixture is
generating a favorable environment for polycondensation positively related to the chain length of the polymer. This
reactions [62]. Wang [51] proposed a method for prepar- phenomenon causes an increase in the flow resistance, which
ing PPTA via nonaqueous suspension polycondensation impedes the synthesis of polymers.
(Fig. 3f). In this system, the dispersed phase consisted of a
solution of NMP-CaCl2, which was prepared by dissolving
CaCl2, PPD, and pyridine in dried NMP. Meanwhile, inert Structure and Properties of Aramid Fibers
liquid paraffin served as the continuous phase. The reac-
tion was initiated immediately after TPC was incorporated Structure of Aramid Fibers
into the non-aqueous suspension. After a certain period,
the reaction system was flushed with deionized water to The chemical structure of AFs consists of amide bonds
quench the reaction. Compared with the conventional solu- (> 85%) and aromatic rings connected on both sides of
tion polycondensation method, this non-aqueous suspension amide bonds [71]. As organic materials with remarkable
13
properties, AFs have been the subject of extensive research. model for Kevlar-49 based on the corresponding diffraction
Various types of AFs exhibit unique microscale structures. patterns and dark-field transmission electron microscopy
Figure 4a is an optical photograph of the PPTA fibers. To (TEM) micrographs. As shown in Fig. 4b, c, the AF has a
thoroughly understand the characteristics and predict the skin–core morphology. The authors stated that the skin layer
physical performances of AFs, a comprehensive understand- of the fiber was less crystalline than the core layer, and its
ing of their microscale structures is essential. The devel- thickness was approximately 0.1–1 μm [73]. As indicated
opment of microdetection techniques has made it feasible in Fig. 4c [74] and as proposed by Morgan, the core layer is
to observe the inner structures of fibers of various sizes in composed of crystallites aligned along the fiber axis, which
detail. Nevertheless, examining only the microstructure is are less oriented than the skin layer. This may be caused
insufficient to satisfy the trans-scale correlation of developed by the variance in the evaporation rate of the skin and core
materials and contribute to the development of innovative solvents during the spinning process [75]. In addition, the
textiles. Thus, numerous scientists have proposed many image reveals wrinkles inside the fiber with a periodicity
structural models of AFs to gain a deeper understanding of ~ 500 nm and an angle of approximately 10°. Dobb et al.
of the characteristics of engineered fibers and to establish a provided a plausible explanation for this phenomenon. The
correlation between their mechanical properties and molecu- fiber sheath initially forms as the fiber passes through the
lar structure. The majority of these models are focused on coagulation bath during the spinning process. However, the
PPTA. Dobb [72] developed a radial wrinkle layer structure core of the fiber relaxes when the spinning stress attenuates.
Fig. 4 a Photograph of PPTA fibers. Structure model (b), micro- Stress–strain curves of several industrial fibers. [80], Copyright 2017.
structure model (c) [73, 74], fibrillar structure model (d) [78], and Reproduced with permission from China Railway Publishing House.
unit cell structure (e) [79] of PPTA fibers. [73], Copyright 1977. i Specific modulus and specific strength of several high-performance
Reproduced with permission from John Wiley & Sons, Inc. [74], fibers. [80], Copyright 2017. Reproduced with permission from
Copyright 1983. Reproduced with permission from John Wiley & China Railway Publishing House. j Limiting oxygen index of sev-
Sons, Inc. [78], Copyright 1983. Reproduced with permission from eral high-performance fibers. [81], Copyright 2018. Reproduced with
John Wiley & Sons, Inc. [79], Copyright 1973. Reproduced with permission from National Defense Industry Press. k Tensile strength
permission from John Wiley & Sons, Inc. Photograph (f) and unit of Kevlar 49 under only atomic oxygen exposure and simultaneous
cell structure (g) [80] of PMIA fibers. [80], Copyright 2017. Repro- exposures of atomic oxygen and UV radiation. [82], Copyright 2006.
duced with permission from China Railway Publishing House. h Reproduced with permission from Elsevier Ltd
13
This results in the formation of periodic wrinkles during The densities of the different types of AFs differ. For
the crystallization phase [76]. Yang [77] thoroughly stud- example, the densities of m-AF, p-AF, and PBO fiber
ied the wrinkles inside the fiber by a spectrophotometric are ~ 1.38 g/cm 3 [84], 1.43–1.47 g/cm 3 [85, 86], and
analysis of the strain birefringence of Kevlar and Kevlar-49 1.54–1.56 g/cm3 [87–89], respectively. Moreover, the dif-
as well as direct imaging by optical microscopy. This work ferences in the densities of the AFs are strongly related to
demonstrated that wrinkles can be diminished substantially the crystallinity of the polymer. For example, the density of
by increasing the axial loading during the spinning pro- high-crystallinity Kevlar-149 is 1.47 g/cm3, whereas low-
cess, thereby improving the mechanical performance of the crystallinity Kevlar-29 has a density of 1.44 g/cm3 [90, 91].
fiber. Panar et al. [78] proposed a fibrillar structure model Unlike other high-performance fibers with higher densi-
to correlate the microstructure and performance, as shown ties, such as 2.56 g/cm3 glass fiber [92, 93] and 1.7635 g/
in Fig. 4d. In their model, the fibrillar structure comprises cm3 carbon fiber for Toray T300, AF exhibits significantly
fibril bundles with a cross-sectional diameter of approxi- low densities. This makes it a key fibrous material in aero-
mately 600 nm. These fibrils, which are parallel to the fiber space applications [94].
axis, are effectively bridged by bundles. This contributes The molecular weight of a polymer is the most fundamen-
to the high modulus and strength of the PPTA fibers. This tal structural parameter that directly affects its mechanical
could be attributed to the cross-linked structure and effective and processing properties. In general, the molecular weights
strength of the fibrils. of commercial AFs are larger than 20,000. This significantly
Figure 4e shows the unit cells of PPTA fibers hypoth- contributes to their remarkable mechanical properties [95].
esized by Northolt [79]. Northolt proposed this type of unit Figure 4h shows the stress–strain curves of several industrial
cell model of PPTA fibers based on a monoclinic unit cell products [80]. The breaking strength of Kevlar is 24.86 cN/
with the following parameters a = 7.87 Å, b = 5.18 Å, c (fiber dtex. This is five times that of steel wires and over two times
axis) = 12.9 Å, and γ = 90° [79]. The figure shows that the that of Dacron 68 Polyester, DuPont 728 nylon, and glass
amide bonds of the molecular chain are arranged along the fibers. In addition to their high tensile strength, AFs have
fiber axis, whereas hydrogen bonds are formed between the a high modulus. As illustrated by the specific modulus and
molecular chains in the horizontal plane. The main chain of specific strength data of several high-performance AFs in
the PPTA fibers is primarily composed of rod-like molecules Fig. 4i [81], the largest value (PBO-HM fibers) is 537 cN/
with predominantly benzene rings. Owing to the conjugated dtex. This is two, four, and nine times that of steel wires,
benzene ring, the molecular chain is rigid and difficult to Dacron 68 Polyester, and DuPont 728 nylon, respectively.
rotate. This facilitates the formation of liquid crystals. As Although the fracture elongation is reduced, the modulus
illustrated in Fig. 4d, the rigid molecular chains in the of Kevlar-149 can attain ~ 1,000 cN/dtex [96–98]. These
liquid–crystal state form a parallel structure as the liquid remarkable mechanical properties of AFs are a result of
concentration increases, and the internal molecular chains their large number of rigid crystallizing units, which facili-
appears to be highly organized. tate the formation of liquid crystals with high orientation
Figures 4f shows a photograph of the PMIA fibers. and crystallinity [72]. For example, PBO and Kevlar fibers
Because it is a high-performance fiber with mechanical can have a crystallinity degree close to 100% and degree
properties inferior to those of the PPTA fibers, few research- of orientation higher than 0.99 [99]. This results in high
ers have studied its micromolecular structure. Thus, only moduli of ~ 130 GPa for Kevlar-49 and ~ 270 GPa for PBO-
the unit cell was studied. Its structure is shown in Fig. 4g. HM. In addition, a few studies indicated that the mechanical
The unit cell of PMIA fiber is triclinic with a = 5.27 Å, properties of AFs can be improved further by adjusting the
b = 5.25 Å, c = 11.30 Å; α = 111.5°, β = 111.4°, γ = 88.0°, processing parameters of the synthesis procedure, spinning
and Z = 1[83]. The hydrogen bonds in the unit cell are in two process, and post-processing treatments [33, 100]. For exam-
planes. Owing to the strong effect of the hydrogen bonds, the ple, Picken et al. [101] demonstrated that the initial modulus
chemical structure of PMIA fibers is exceptionally stable. of PPTA fibers can be influenced significantly by factors
Thus, these display remarkable heat resistance, flame resist- such as the concentration of the polymeric solutions, size of
ance, and chemical corrosion resistance. the air gap, and temperature of the coagulation bath. Allen
et al. [102] manipulated parameters including the solution
concentration, coagulation, heat treatment, and spin stretch
Properties of Aramid Fibers factor to synthesize PPTA fibers with tensile strengths rang-
ing from 0.2 to 4.2 GPa and tensile moduli ranging from 10
Since their invention, various unique properties of AFs have to 160 GPa. Furthermore, certain AF products can serve
been investigated. In this subsection, we review the char- as raw materials for producing the corresponding mechani-
acteristics of multiple AF species, including their density, cally improved products. Kevlar-49 has a tensile strength 1.5
molecular weight, and mechanical strength. times that of Kevlar-29. It is formed using Kevlar-29 using
13
the hot-drawing method. Similarly, Kevlar-49 can be trans- have a negligible effect on the strength of AFs, although
formed into Kevlar-149, which has a higher tensile strength strong acids and bases at high concentrations can damage
[33]. A likely reason is that the rod-like fibers are more ori- fibers [112, 113]. Additionally, Nomex fibers are indigestible
ented along the fiber axis during the hot-drawing process, by insects, and bacteria have a minimal effect on their prop-
thereby enabling the hydrogen atoms on the amide group to erties. It is noteworthy that water at temperatures above the
form more hydrogen bonds with the carbonyl groups on the boiling point can degrade the properties of Kevlar and other
other molecular chain and form hydrogen bond crosslinks AFs [114, 115]. A potential explanation for this phenomenon
between the molecular chains. is that moisture can disrupt hydrogen bonding and reduce
The AFs exhibit exceptionally high degradation tempera- the skin–core bonding strength. This ultimately results in
tures. This is owing to the higher bond dissociation energies destabilization of the AF structure.
of the C–C bonds and C–N bonds in aromatic polyamides. Because AF contains a large number of amide bonds,
These are up to 20% higher than those in aliphatic polyam- its internal molecular chain can be destroyed after mois-
ides. The related temperatures of the different AFs have also ture absorption. Moreover, the amide bonds are vulnerable
been reported. It has been determined that the properties of to hydrolysis, which results in variations in their proper-
AFs can be sustained effectively for a prolonged period at ties [116]. In particular, during marine transportation,
temperatures above 150 °C. The m-AFs have a glass tran- owing to the large amount of moisture and salt in the air,
sition temperature of 270 °C, decomposition temperature the water-absorbing aramid is damaged further by sea salt.
of ~ 450 °C [103–105], and strength retention rate of 90% This severely deteriorates the mechanical properties of the
after 20,000 h in an environment of 200 °C. The glass transi- fiber. Therefore, it is necessary to investigate the hygro-
tion temperature of p-aramid is 345 °C. The decomposition scopic properties of aramids. The index used to measure
temperature can attain 550 °C [33, 98, 106] because of the the hygroscopic performance of the fiber is the moisture
conjugation of the amide and benzene ring, which makes the regain. However, the moisture regain of the fiber differ under
molecular segment more rigid. Furthermore, PBO displays different temperatures and humidities. Therefore, standard
a higher thermal decomposition temperature than p-AFs moisture regains (ISO139:2005, Textiles-Standard Atmos-
by approximately 100 °C [107]. Specifically, the thermal pheres for Conditioning and Testing) are used. The moisture
decomposition temperature of PBO in air is approximately regains of different specifications of AFs are different: those
650 °C. This surpasses that of the p-AFs. In addition, intro- of Nomex, Kevlar-29, Kevlar-49, Kevlar-149, PBO are 4.5%,
ducing flexible groups such as -O- into the main polymer 7.0%, 3.5–4.5%, 1–3%, and 0.6–2% [98, 117–119], respec-
chain (e.g., Tenjin Technora) can cause a decrease in thermal tively. Saijo [120] used small-angle X-ray scattering (SAXS)
stability owing to the more flexible chains [28, 108]. The to demonstrate that the moisture absorbed by the AFs was
limiting oxygen index (LOI) of several high-performance mainly in the micropores of the fibers. However, the mois-
fibers are shown in Fig. 4j [81]. It can be observed that AFs ture retention of a polymer is related to its molecular struc-
without flexible groups exhibit elevated levels of LOI and ture. Auerbach [121] compared the hygroscopic behaviors of
tend to undergo self-extinguishing upon being removed nylon-66 and Kevlar-29. He observed that Kevlar-29 absorbs
from the flame, rather than sustaining continuous burning. a H2O molecule for every two amide bonds, whereas nylon-
Additionally, it should be noted that the PMIA fibers do not 66 absorbs a H 2O molecule for every amide bond. Mooney
fail in flames because their melting points are higher than [122] observed that AFs exhibit a distinct hysteresis-type
their decomposition temperatures. In contrast, the surface behavior and that the hygroscopicity of an AF is directly
of the PMIA fiber is carbonized at 400 °C to form a thermal related to its crystalline structure.
insulation layer. It effectively impedes the transfer of exter-
nal heat into the interior of the fiber. Therefore, one of the Drawback of Aramid Fibers
applications of PMIA fibers is in high-temperature-resistant
materials such as firefighting clothing. Although AFs display remarkable performance capabilities,
Molecular chain structure of AFs contains numerous their applications present multiple challenges. Their overall
benzene rings and carbonyl groups. These benzene rings properties have not been utilized fully in the corresponding
and carbonyl groups in the AFs can further form stronger composite materials. The reasons for these limitations can
conjugation effect and steric hindrance effect. Thus, the fiber be categorized into four aspects. One such constraint is the
surface has fewer active functional groups and is chemically limited axial stretchability of the fiber, which attains only
inert [109–111]. The inert chemical surface of AFs greatly 75–80% of the theoretical modulus. This is owing to the non-
affects the interfacial affinity between aramid fiber and resin parallel orientation of the rod-like molecular chains within
matrix, and then affects its excellent comprehensive proper- the AFs, which have an orientation range of 9°–12° [123].
ties in composite materials. The AFs are insoluble in most Another constraint originates from the unique mechanical
solvents. Most organic solvents and aqueous salt solutions properties of AFs, which are generated by the numerous
13
hydrogen bonds between the polar amide groups located on approaches have been employed to modify fiber surfaces
adjacent chains perpendicular to the fiber axis. Although for introducing reactive groups and/or increasing the sur-
these hydrogen bonds are essential for amide group stabil- face roughness to enhance the interfacial properties. Among
ity, these are weaker than the covalent bonds in the fiber these techniques, physical and chemical surface-modifica-
direction. This results in a low shear modulus, the absence tion methods have been the primary focus of recent studies.
of transverse properties, and a low compressive strength
[33, 124]. The transverse strength of the fiber is approxi- Physical Modification
mately 20% of its longitudinal strength [125]. Additionally,
DeTeresa [126] observed that Kevlar-49 fibers lost 10% of Physical modification is a technique used to improve the
their tensile strength after a 3% axial compressive strain was properties of fibers through physical methods. Thereby, free
applied. Third, AFs contain a substantial number of benzene radical reaction centers are formed on the fiber surface, and
rings and carbonyl groups. These generate conjugation and polar groups are introduced to enhance fiber wettability and
steric hindrance effects. The presence of these features ren- roughness. The main physical modification methods include
ders the fiber surface deficient in active groups and results in ultrasonic impregnation modification [138, 139], plasma
a low surface free-energy (39.8 mJ/m2). This makes the sur- treatment [140], high-energy ray modification [141, 142],
face deficient in reactive functional groups and chemically and supercritical fluid modification [143].
inert [127–129]. In addition, the low wettability of the fiber Ultrasonic impregnation modification involves the utiliza-
surface coupled with its smoothness further contributes to tion of the cavitation effect produced by ultrasonic waves.
the weak interfacial bonding between AF and other materi- It strongly impacts the fiber. This effect is generated under
als. This results in low interlaminar shear strength, compres- the energy stimulation caused by the rupture of the cavita-
sive strength, and fatigue resistance in aramid-based com- tion bubble. Thus, fibrosis of the fiber surface is augmented,
posites. Fourth, AFs have a large number of amide groups thereby increasing the surface roughness [144, 145]. Liu
with highly oriented and crystalline molecular chains that [139, 146] observed that the surface oxygenated polar
break down after a short period of UV irradiation [130, 131]. groups, surface tension, specific surface area, and surface
Exposure to UV light causes irreversible reactions such as aperture of Armos-II fibers increased after ultrasonic treat-
oxidation, degradation, and crosslinking [132]. Such expo- ment. The interfacial shear strength (IFSS) of aramid/epoxy
sure has been demonstrated to contribute to an increase composites also increased. Moreover, Liu observed that
in the surface roughness and elastic modulus [2] as well under ultrasonic processing with an amplitude of 30 μm and
as the attenuation of physical and mechanical properties. a frequency of 20 kHz, the properties of Armos-II fibers and
These ultimately reduce the lifespan of the material [133]. their resin composites were optimal. Ultrasonic modification
Additionally, as shown in Fig. 4k, Ghosh observed a further can improve the fiber surface properties of AFs. However,
reduction in the tensile strength of Kevlar-49 upon expo- it can also destroy the weak bonds between aramid sheets,
sure to atomic oxygen and UV radiation [82]. This drawback thereby resulting in a dramatic decrease in their mechanical
severely restricts the advancement of AFs in long-term out- properties [147–149].
door settings, particularly in severe aerospace environments. Plasma treatment can improve the wettability of the fiber
surfaces by introducing polar oxygen-containing groups
[150–152]. Xi et al. [19] modified aramid (III) using an air
Functionalization of Aramid Fibers dielectric barrier discharge (DBD) plasma at atmospheric
pressure. The results showed that when the power was 31.11
With the further expansion of applications in industrial and W/cm3 and processing time was 21.6 s, the proportion of
cutting-edge strategic materials, various studies have been oxygenated polar groups increased from 15.99 to 27.15%,
conducted to overcome the inherent defects of AFs, includ- and the fiber wetting length attained 17–18 cm. Gu [140]
ing a low surface activity (interface properties) and poor and Wang [110] observed significant surface wettability and
UV resistance, described in “Drawback of Aramid Fibers”. adhesion enhancement between AFs and the matrix after
Therefore, in this section, we review the significant advances subjecting Kevlar-29 to argon plasma treatment. However,
that have been made in surface functionalization of AFs. this treatment requires the use of a vacuum environment. In
addition, if the processing time is prolonged, it would have
Surface Modification to Enhance the Interface detrimental effects on the strength of the fibers owing to the
Properties strong activity of free radicals. Moreover, the high-energy
plasma concurrently compromises the structural integrity of
Previous studies aimed to optimize the surface properties the fibers in the process of energy transfer [153]. Hence, the
of AFs by surface treatments to enhance their interfacial treatment of AFs with plasma is not conducive for industrial
compatibility with other materials [134–137]. Various production.
13
High-energy-ray modification refers to utilizing high- ray modification technology is not mature and is still in the
energy rays such as UV, high-energy electron beams, X-rays, scientific research stage. High-energy radiation has a sig-
and γ rays to treat AFs to enhance the wettability and adhe- nificant impact on the crystallization performance of AFs. It
sion between fibers and other substrates. This improves the significantly reduces the fracture strength and elongation at
physical and mechanical properties of composite materials break of the fibers [159, 160]. The premise of AF modifica-
[154]. Liu et al. [125, 155] studied the application of 60Co tion is to minimize its impact on the mechanical properties.
as the γ-ray irradiation source to improve domestic aramid Therefore, high-energy ray modification is not considered
fiber-12 (DAF12) surfaces in the presence of epoxy chlo- the primary option for AFs modification.
ropropane and diethanolamine medium (Fig. 5a). After the Supercritical carbon dioxide (Sc-CO2) is a highly poten-
treatment, an AF/epoxy composite was obtained by com- tial substance for synthesizing nano/micromaterials. It has
positing it with epoxy resin. The results indicated that the been used in various industrial fields because of its advanta-
γ-ray irradiation treatment caused an increase in the sur- geous aspects including the abundant resources, low cost,
face energy of the fiber. The IFSS value of the composite environmental safety, non-toxicity, non-flammability, and
was improved by 45.17% after a 400 kGy-dose irradiation. tunable processing conditions [164–167]. At the near-critical
Jang et al. [142, 156] used UV/ozone irradiation to photo- point (critical temperature Tc = 304.13 K, critical pressure
oxidize meta-aramid films and fabrics. High-energy UV irra- Pc = 7.3773 MPa) [168], the physical properties of Sc-CO2
diation excitation and ozone oxidation generated carbonyl undergo dramatic variations that can be utilized to modify
and hydroxyl groups on the surface of m-aramid films and AFs. As reported by Jing et al. [169], the treatment of meta-
fabrics. This increased the oxygen content and improved the aramid fabrics using Sc-CO2 in a binary system with 1-butyl-
wettability. The results showed that the modified films and 3-methylimidazolium hexafluorophosphate ( [BMIM][PF6])
fabrics exhibited higher affinities for cationic dyes. High- resulted in a highly effective modification. This is evidenced
energy ray modification does not require the use of catalysts by the reduction in the water contact angle from 124.5° to
and initiators, can be performed at room temperature, and is 83.0°. This was attributed to the creation of [PF6]- at the
a simple process [133, 157, 158]. However, the high-energy fiber surfaces and to an increase in the surface roughness.
Fig. 5 a Surface modification of domestic AF-12 with γ ray irradia- Chemical grafting of PBIA fibers with silane coupling agents to
tion improves the surface of the in the medium of epoxy chloropro- enhance the interfacial interaction with rubber, bismaleimide, and
pane and diethanolamine. [125], Copyright 2014. Reproduced with epoxy resin. [162], Copyright 2018. Reproduced with permission
permission from Elsevier Ltd. b Graphene oxide-modified Kevlar from Elsevier Ltd. d Constructing a new skin for AFs to improve its
K-29 for reinforcing epoxy resin matrixes. [161], Copyright 2021. composite interfacial properties. [163], Copyright 2021. Reproduced
Reproduced with permission from American Chemical Society. c with permission from Elsevier Ltd
13
Another study by Kong et al. [170, 171] demonstrated that aqueous NaOH solution, washed with deionized water, and
the use of Sc-CO2 can improve the surface activities of para- immersed in an aqueous solution of HCl to obtain carboxyl
AFs and aramid pulp. This is followed by the growth of ZnO and carbonyl groups on the fiber surface. Jia [185] treated
nanoparticles on the fiber surfaces. This Sc-CO2-induced PPTA fibers with a KMnO4 solution and obtained the opti-
procedure followed by the nondestructive coordination mal treatment conditions through orthogonal experiments:
of ZnO AFs showed significantly enhanced IFSS and UV a temperature of 30 °C, concentration of 20%, and time of
resistance. Thereby, it overcame the two inherent drawbacks 20 min. After treatment under these conditions, the modified
of AFs. Moreover, the modified fibers exhibited superior fiber/resin composite showed 49.9% higher interfacial bond-
mechanical and thermal performances. Although the Sc-CO2 ing strength than that of the untreated fiber/resin composite.
treatment process is a green and environmentally friendly Ling [186, 187] modified Kevlar fibers with KMnO4 under
method, it has a negligible adverse influence on the physi- acidic conditions. He observed that a long-term treatment
cal properties of AFs [172]. However, this process needs to with high temperature and low concentration could improve
be conducted under high-pressure conditions, which require the surface roughness of the fiber while ensuring its strength.
more sophisticated equipment. Therefore, a gentler treatment Direct fluorination is a neoteric surface treatment method
process was investigated in this study. that is extensively used in polymer materials owing to its
To summarize, physical modification provides certain exceptionally high electronegativity and chemical activity.
notable advantages such as a high efficiency and simple At room temperature, no initiation process is required at
operation. However, these approaches require complex and practically appreciable rates because of the exothermic char-
sophisticated instruments, which incur substantial finan- acteristic of this reaction [188–190]. Mukherjee et al. [11]
cial costs. Incorrect operation and equipment aging can observed that fluorination significantly increased the surface
straightforwardly cause electronic and radiation contami- roughness of AFs and enhanced their bonding capability
nation. Moreover, the physical modification method requires with resins. This, in turn, improved the IFSS of the com-
exceptionally high process parameters. Additionally, exces- posites. Liu et al. [191–193] conducted a series of studies
sive metrology can compromise the performance of the fib- on fluorine-modified PBIA fibers. The results were in agree-
ers, thus contradicting the potential application of AFs as ment, including an increased number of active groups on the
high-performance materials. fiber surface, an increase in the IFSS and pull-out strength,
and reinforcement in the adhesive strength of the fiber-epoxy
Chemical Modification composite. The formation of active groups is mainly derived
from the destruction of crystallization regions, which signifi-
Chemical modification refers to the chemical reaction of cantly degrades the mechanical properties.
AFs, etching, alteration of the molecular structure of the Chemical grafting refers to the connection of active or
fiber surface, and introduction of polar groups. These compatible molecules to the functional groups of the AF
increase the activation energy and improve the interfacial molecular chains using a chemical reagent. It has been
properties of the fiber surface [173, 174]. Many methods are widely studied to improve the surface adhesion of inert
available for chemically modifying the AF surface according fibers such as AFs [194], carbon fibers [195, 196], car-
to the modification mechanism: surface etching [175, 176], bon nanotube fibers [197], ultra-high molecular weight
chemical grafting [177, 178], complexation modification polyethylene (UHMWPE) fibers [198, 199], and polyim-
[179], etc. ide fibers [200]. Tian et al. [161] (Fig. 5b) applied dopa-
Surface etching refers to the use of chemical reagents to mine (DA) to Kevlar K-29 fibers. They then chemically
destroy chemical bonds and crystalline states in the structure grafted carboxylated graphene oxide (CGO) or aminated
of the AF macromolecular chain. This increases the rough- graphene oxide (AGO) onto the fibers to improve their
ness and improves the polarity of the fiber surface [180]. The surface energy by utilizing the super adhesion and physi-
earliest chemical etching involved the modification of AFs cal adsorption of the polydopamine (PDA) layer. Both the
using phosphoric acid [15, 136], sulfuric acid [181], acetic modification methods improved the tensile strength of the
anhydride [182], etc. Chemical etching is a common modifi- monofilaments and IFSS of the modified fiber/epoxy resin
cation method. The reagents used to achieve different etching composite. Moreover, AGO-modified fibers exhibit higher
effects are becoming increasingly diverse. Zhu [183] treated surface energies and interface bonding strengths because
Kevlar-49 fibers with an ethanol solution of NaOH to break of the introduction of multiple amino active groups in
the amide bonds on the fiber surface. This was followed AGO, which form stable covalent bonds with epoxy groups
by reflux to obtain fibers containing amino and carboxyl [201]. Wang et al. [202] polymerized a poly(catechol-
groups. This enhanced the surface activity of Kevlar-49 fib- polyamine) (PCPA) coating on PPTA fiber surfaces and
ers. Ma et al. [184] modified benzimidazole-containing AFs grafted the silane coupling agent γ-(glycidyloxypropy
using a similar strategy. The fibers were hydrolyzed in an ltrimethoxysilane) (GPTMS) onto the PCPA layer. The
13
results showed that compared with untreated AFs (extrac- Other Modification Methods
tion force = 33 ± 3 N, and IFSS = 2.1 ± 0.2 MPa), the inter-
face adhesion between the modified AFs and rubber matrix In addition to physical and chemical modifications, modifi-
obtained by this method resulted in an improvement in cation methods such as coating methods [171, 211, 212] and
the extraction force (60.5 ± 5 N) and IFSS (3.9 ± 0.3 MPa) nanostructures [213, 214] have also been used to improve
[137]. Chen et al. [162] (Fig. 5c) grafted allyl groups as the surface energy of AFs.
pendent groups onto the macromolecular chains of PBIA The coating method involves the application of a resin
fibers through a reaction between the NH groups of benzi- or low-molecular-weight substances with the same polar
midazole and bromopropylene. Subsequently, they intro- groups compatible with the surface of AFs. This enhances
duced a high density of N H2 and C=C groups onto the their adhesion to other materials. Nasser et al. [13] described
surfaces of the fibers by grafting silane coupling agents. a dip-coating strategy in which ANFs bind to fibers through
The modified fibers showed an attractive chemical bond- physisorption and hydrogen bonding. This increases the
ing capability with rubber, bismaleimide, and epoxy resin IFSS by 70.27% and reduces the beam shear strength by
without destroying the mechanical structure of the fiber. 25.6%. Cheng et al. [163] constructed a new skin synthesized
Chemical grafting significantly increased the surface activ- from TPC, PDA, and 2-(4-aminophenyl)-1H-benzimidazole-
ity of AFs. However, most grafting reagents are organic, 5-amine (PABZ) on the old skin of AFs. This resulted in
whereby this damage the fibers and pollute the environ- a substantial increase in the interfacial shear stability, as
ment. Therefore, the identification of environment-friendly shown in Fig. 5d. The addition of 3 wt% functionalized CNT
grafting reagents has become a research hotspot. resulted in an IFSS value of 59.65 MPa. This was 75.3%
Complexation modification involves the use of metal inor- higher than that of the original fiber. However, the thickness
ganic salts to interact with carbonyl or amino groups on the of the coating is difficult to control, and its operability and
surface of AFs. This results in a coordination reaction that repeatability are low [153]. In addition, it is difficult for AFs
destroys the hydrogen bonds between the molecular chains, to stably bond with the coating. This results in the low ser-
thereby decreasing the crystallinity and roughening the sur- viceability of the fiber-enhanced composites owing to their
face [203, 204]. As additives that increase the solubility in exceptionally low surface activity [215].
aramid spinning, LiCl and C aCl2 have been demonstrated to Nanomaterials have been demonstrated to improve the
improve the surface activity of AFs [205–207]. Zhang et al. mechanical stability of fiber composites by enhancing the
[206] treated TH6107 AFs with a C aCl2 ethanol solution. mechanical interlocking between the fibers and matrix.
The 5 wt% CaCl2-treated AFs showed the best overall per- Efforts have been undertaken to treat AFs using different
formance: the interlaminar shear strength (ILSS) improved nanomaterials such as carbon nanotubes [216], TiO2 [25],
significantly, and the tensile strength of the composites SiO2 [217], and ZnO [218]. For example, Zhang et al. [219]
increased by 48.7%. Liu [208, 209] modified PBIA fibers seeded ZnO nanoparticles (NPs) on Rusar fibers and then
with Fe3+ via metal–ligand coordination. Liu reported that grew ZnO nanowires (NWs) on the seed layer with the assis-
the introduction of Fe3+ ions improved the surface polar- tance of poly L-3,4-dihydroxyphenylalanine (PDOPA). This
ity of the fibers. Further grafting with polyethyleneimine improved the adhesion and secondary functionalization. The
(PEI) also demonstrated that F e3+ coordination successfully fiber obtained exhibited an increased IFSS of 37.8%, which
improved the surface activity of the fibers. Li [210] demon- is a remarkable improvement.
strated that a similar effect could be produced using Cu2+ in
complex-modified PBIA fibers. Complexation is a recently Surface Modification to Improve the Anti‑UV
developed method for chemical modification. This method is Properties
simple to operate and can effectively improve the roughness
of the AFs. However, prolonged processing times or high Currently, surface modification and the addition of
solution concentrations degrade the mechanical properties UV-shielding agents during spinning are the two main
of the fibers. Moreover, the material compound on the fiber approaches to improving the anti-UV properties of AFs.
surface should be compatible with the metal complex layer. However, most UV-shielding agents are in the form of nan-
Chemical modification has the advantages of convenience oparticles. The anomalous diffusion and agglomeration of
of operation, high efficiency, noticeable effects, and long nanoparticles in polymer solutions largely restrict the related
duration. However, inappropriate treatment conditions such research and application of UV-shielding agents during ara-
as an excessively high solution concentration, long treatment mid spinning [220]. Surface modification involves grafting
time, or excessively high treatment temperature can cause or coating UV-resistant agents onto the surfaces of the AFs
irreparable damage to the fibers. Therefore, further work is [221]. UV-resistant coatings can be divided into two cat-
required to enhance the surface activity of AFs via chemical egories: organic and inorganic. Organic UV-resistant agents
modification to optimize the reaction conditions. have good compatibility with fiber polymers. However, these
13
can decompose straightforwardly after long UV exposure. Kevlar-49 fibers. The procedure involved alternating the
This reduces their UV shielding performance. In addition, treatment of the fibers, which had previously been treated
organic UV-resistant coatings have problems such as an with an H3PO4 solution, with SiO2 and MgAlFe layered dou-
insufficient heat resistance, a high toxicity, intense skin ble hydroxide (LDH), followed by washing with deionized
irritation, a peculiar smell, and a low washing resistance water and repeated drying in a vacuum oven. The final fib-
[222–224]. Therefore, nontoxic and remarkable adhesive ers treated with three self-assembly cycles clearly showed
organic UV-resistant coatings such as dopamine are gener- improved UV resistance compared with the pristine fibers.
ally used to improve the anti-UV properties of AFs. Cheng After 168 h of UV irradiation, the three self-assembly cycle
et al. [225] conducted a sequential etching process on Kev- fibers retained their tensile properties with a retention rate
lar-29 fibers using NaOH and HCl solutions, as described in of 91–95%. This was approximately 29–14% higher than
“Chemical Modification”. This was followed by the graft- that of the pristine fibers. In another study, Zhang [232]
ing of dopamine onto the fiber surfaces. The obtained fibers synthesized nano-SiO2 on the surface of p-AFs in a Sc-CO2
exhibited good UV absorption characteristics. After expo- atmosphere to improve their UV resistance. The resulting
sure to UV radiation for 168 h, the treated fibers showed AFs were treated at a supercritical pressure of 14 MPa.
an increase in tensile strength and elongation at break of These demonstrated a remarkable UV resistance, with a mar-
21.82% and 20.72%, respectively, compared with the bare ginal decrease in tensile strength, elongation at break, and
fibers. Li et al. [226] used certain doses of UV irradiation tensile modulus after 216 h of UV radiation. Specifically,
to pretreat Kevlar-29 surfaces for DA grafting. The DA- the treated fibers retained 91.5%, 98%, and 95.5% of their
modified fibers showed strength retention and elongation tensile strength, elongation at break, and tensile modulus,
at break that were approximately 20% higher than those respectively, whereas the pristine AFs retained 73%, 91%,
of the untreated fibers after exposure to UV radiation for and 85%, respectively. Overall, these observations indicate
168 h. This method of coating AFs exhibited superior UV iO2 synthesized by Zhou and Zhang can effectively
that the S
resistance. enhance the UV resistance of AFs.
Inorganic UV-resistant coatings that are generally In addition to the above methods for inorganic UV-
employed include GO [227], SiO2 [14, 228], and metal resistant coatings, metal oxides such as T iO2 [25, 233, 234],
oxides [15, 229]. These coatings exhibit desirable features Al2O3 [229], ZnO [235], and CeO2 (Ce0.8Ca0.2O1.8) [236]
such as a good light reflection or refraction capability, non- have been favored because of their good light absorption.
toxicity, non-irritation, broad-spectrum performance, and The sol–gel strategy was the earliest method used for
high chemical and thermal stability. Therefore, these have the anti-UV modification of AFs. Liu et al. [237] synthe-
been receiving increasing attention in recent years. How- sized TiO2 on the surfaces of Kevlar-129 and PBO using
ever, owing to the absence of chemical bonds between the the sol–gel method. Patterson et al. [238] synthesized ZnO
inorganic UV-shielding coatings and AFs, the coatings fall nanoparticles on Kevlar KM2 fabrics using the sol–gel
off. This results in a loss of UV protection. Thus, the cur- method. Both these methods have significantly improved the
rent research consistently prioritizes the rapidity of inor- anti-UV properties. However, coatings synthesized using the
ganic UV-resistant coatings. Zhu et al. [227] synthesized sol–gel method do not adhere effectively to the fiber surface.
PDA directly on the surface of Kevlar-49. This was followed Moreover, a long-term use may cause a decrease in the anti-
by coating with GO through the exceptionally strong adhe- UV effect.
sion of PDA. The results showed that the tensile-strength Because of the detrimental effects of UV radiation on
retention rate of the fiber with the best UV resistance was metal oxide coatings, there is a pressing need to develop
93.4% after exposure to 168 h of UV radiation. Yu et al. coatings with long-lasting UV resistance. To address this
[230] developed cost-effective and straightforward strate- issue, Sun [239] utilized Sc-CO2 to synthesize TiO2 nano-
gies for enhancing the UV resistance of PBO fibers. This particles on the surfaces and interfaces of aramid III fibers.
method involves enclosing the fibers in a reduced GO-MOF This yielded UV-resistant AFs. Similarly, Zhang et al. [170]
(RGO-UIO-66) hybrid layer using size-limited hydrother- synthesized ZnO on p-AFs in Sc-CO2 and produced ZnO-
mal reduction, static adsorption, and thermally assisted coated fibers with significantly improved anti-UV proper-
shrinkage. After 288 h of UV irradiation, the tensile ties (Fig. 6a). Importantly, both the methods resulted in the
strength retention rate of the improved fibers increased by formation of C–O–Ti or C–O–Zn coordination bonds at the
128% compared with that of the pristine PBO fibers, which fiber/fiber interface. This indicated that the binding of the
exhibited a retention rate of 32%. Overall, both the studies fibers and coatings and the service resistance were improved
successfully addressed the challenge of enhancing the UV significantly. In another study, Wang et al. [175] constructed
resistance of AFs through the application of GO, although surface-modified Kevlar-49 fibers by pretreating these with
these used different approaches. Zhou [231] employed the an alkali and HCl aqueous solution before grafting TiO2
LBL self-assembly method to generate a coating layer on nanoparticles onto the fiber surface using a low-temperature
13
Fig. 6 a Enhancing the interfacial interaction of p-aramid with ZnO 2018. Reproduced with permission from Elsevier Ltd. d Synthesis
after Sc-CO2 treatment to improve the UV resistance. [170], Copy- of TiO2 film by ALD on PMIA fibers to enhance the UV resistance.
right 2020. Reproduced with permission from Elsevier Ltd. b Syn- [241], Copyright 2022. Reproduced with permission from Elsevier
thesis of T iO2 NPs on Kevlar-49 with the hydrothermal method to Ltd. e Synthesis of -Al2O3–TiO2 bilayer films by ALD on PMIA fib-
enhance the UV resistance. [175], Copyright 2016. Reproduced with ers to enhance the UV resistance. [242], Copyright 2021. Reproduced
permission from Elsevier Ltd. c Chemical Grafting of Kevlar-49 with with permission from John Wiley & Sons Inc
PDA@tBN@CeO2 to enhance the UV resistance. [240], Copyright
hydrothermal method. The resulting fibers also exhibited an photocatalytic activity and grafted it onto pretreated
improved UV resistance (Fig. 6b). Kevlar-49 fibers. The C e 0.8Ca 0.2O 1.8 UV absorber dem-
Metal-oxide-based UV-resistant coatings such as TiO2 onstrated lower photocatalytic activity than the T iO2 and
and ZnO have remarkable UV-shielding capacity owing to ZnO absorbers and lower oxidation catalytic activity than
their elevated photocatalytic activity. Therefore, these have CeO2. After 168 h of UV irradiation, the modified fibers
been investigated extensively. However, these coatings can retained 94.5% of their tenacity. Alternatively, Gu et al.
produce strong oxidizing substances including superoxide [240] prepared a C eO 2-based UV absorber with a dou-
radicals (•O2−) and hydroxyl free radicals (•OH), upon ble-shell-core structure with low catalytic activity, which
absorption of UV rays [243, 244]. Such oxidizing substances was then grafted onto Kevlar-49 fibers. The preparation
can penetrate the fiber surfaces and catalyze degradation and anti-UV performance are shown in Fig. 6c. The fig-
and thereby, weaken the polymer structures. This, in turn, ure shows that the UV-blocking effect of this absorber,
affects the mechanical properties and service life of the fib- combined with the lower photocatalytic activity, signifi-
ers [245–247]. Therefore, an effective metal oxide UV coat- cantly enhanced the UV resistance of the modified fibers.
ing with weak or no catalytic properties is required. After UV irradiation for 168 h, the modified fibers retained
To develop high-performance UV-resistant materials 1.62 times the fracture retention energy compared with
with a low photocatalytic activity, Gu et al. evaluated the pristine fibers. Both the studies provided evidence that
two approaches. Gu et al. [183] proposed the synthesis grafting absorbers with low catalytic activity onto AFs can
of a Ca-doped CeO2 absorber ( Ce0.8Ca 0.2O 1.8) with low effectively improve their UV resistance while minimizing
13
the loss of mechanical properties damaged by oxidizing Al2O3 and A l2O3/PMIA interfaces. An incident angle of UV
substances. light larger than a certain critical value results in further
The aforementioned strategies for improving the anti-UV reduction in the proportion of UV rays irradiated on the
properties of AFs have a common feature: these require an surface of the PMIA fibers. This enhances their UV resist-
improvement of the surface inertness of the fibers before the ance of the PMIA fibers. The ALD method can significantly
application of UV-resistant coatings. However, pretreatment improve the UV resistance of AFs and reduce the damage
with AFs, such as etching, high-energy ray irradiation, or to the fiber by TiO2 photocatalytic activity. However, the
grafting, can destroy the molecular chain structure on the method is expensive, and the precursor is hazardous. This
fiber surfaces and reduce the strength of the fibers. Thus, hinders large-scale production.
it is necessary to adopt a method that does not destroy the
mechanical properties of the AFs and achieves effective UV
resistance. Atomic layer deposition (ALD) is a vapor-phase Applications of Aramid Fibers and Aramid
deposition process that uses a surface-controlled self-limit- Nanofibers
ing reactors mechanism [248, 249]. This technology displays
numerous advantages such as a high efficiency, low pollu- As a high-performance fiber with ultrahigh strength, body
tion, precise and simple thickness control, and remarkable armor made of Kevlar fibers produced by DuPont is known
conformability to sophisticated surfaces [250–256]. ALD worldwide. This fosters AFs’ reputation as organic fibers
does not require pretreatment when used on AFs. Moreover, with remarkable performance. First, Kevlar fiber was used
its low reaction temperature does not damage their molecu- to replace steel wire to make belt plies. Subsequently, it was
lar structure. These make it a potential technology for con- used in the field of protective anti-ballistic composites. Until
structing functional coatings. Our group [241] used modi- recently, AF and its composites were widely used in aero-
fied ALD (mALD) (specifically, multiple pulsed infiltration space, ballistic protection, automotive, sporting goods, fire
(MPI) technology [257]) to deposit a TiO2 layer on PMIA rescue, and other fields [5, 95, 259–261]. Because of their
fiber surfaces. With prolonged exposure to the precursor tita- advantages such as the remarkable mechanical properties,
nium (IV) isopropoxide (TIP), the interior of the fibers was light weight, high-temperature resistance, flame retardancy,
penetrated successfully, and the amide groups at the fiber chemical stability, and insulation, AFs have been investi-
interface were broken down. This formed an organic–inor- gated by scholars in various new material fields, as shown
ganic hybrid structure [258] that could effectively enhance in Fig. 7. Among these, ANFs have received more attention
the laundry stability and surface luster of the PMIA fabrics. because of their unique 1D nanoscale structure, high aspect
Additionally, similar to LBL, amorphous TiO2 can absorb ratio, ultra-thinness, transparency, and remarkable specific
UV light to a certain extent. However, it exhibits a low pho- surface area. In this section, we summarize the applications
tocatalytic activity. From Fig. 6d, it is evident that the PMIA of the AF/ANF-based composites in daily life.
fibers coated with 1000 ALD TiO2 cycles exhibit an effective
retention of UV resistance. Furthermore, even after 360 min Applications of Aramid Fibers
of exposure to extreme UV radiation and high temperature at
4260 W/m2 above 200 °C, the ALD-modified PMIA fibers Since their invention, AFs have been used as reinforcing
exhibited an initial tenacity retention rate of 54.08%. To fur- and flame-retardant materials. p-AFs such as Kevlar, Terlon,
ther reduce the damage caused by the photocatalytic action Twaron, and Taparan display exceptionally high strengths
of TiO2, we deposited a double-layer ultrathin Al2O3-TiO2 and moduli as well as exceptional thermal, cold, and chemi-
coating onto the PMIA fibers using the same mALD (MPI) cal stabilities. Therefore, p-AFs are typically used directly in
method [242] (Fig. 6e). The tenacity of the ALD-coated AFs various industrial, aerospace, military, and civilian applica-
decreased by approximately 0.85% after 90 min of extreme tions after a simple conventional weaving. M-AFs such as
UV radiation and high temperatures at 4260 W/m2 above Nomex, Conex, and Tametar exhibit remarkable flame retar-
200 °C, which corresponds to approximately 17,500 days dancy and good textile properties. However, their mechani-
of continuous exposure to sunlight. The Al2O3 layer in the cal properties are inferior to those of high-performance fib-
inner part of the coating functioned as a free-radical passiva- ers. Thus, these are commonly used in fireproof clothing,
tion layer, which effectively blocked the secondary damage high-temperature gas filters, rubber belts, and hoses.
of free radicals caused by the absorption of UV light in the In addition to these conventional commercial applica-
outer TiO2 layer. This resulted in a remarkable UV resist- tions, AFs have many other application prospects. Gonzalez
ance (as shown in the bottom half of Fig. 6e). Additionally, et al. [262] reported an immersion rotary jet-spinning (iRJS)
because the refractive index of Al2O3 is higher than that of approach for preparing para-aramid fiber sheets (pAFS),
the PMIA fiber but smaller than that of amorphous T iO2, as shown on the left side of Fig. 8a. Here, high centrifugal
part of the UV light underwent total reflection at the T iO2/ forces are applied to extrude polymer dopes to form jets. The
13
Fig. 7 The potential application fields of AFs and ANFs
diameter of the fiber could be adjusted by controlling the spin- protection factor (UPF) of InOF-1 applied to aramid fabrics is
ning parameters. The efficacy of pAFS was quantified using an considerably lower than that of cotton and polyester fabrics.
experimental setup at the US Army Combat Capabilities Devel- Therefore, the use of InOF-1-coated aramid fabrics can help
opment Command Soldier Center. As shown on the right side protect the skin of outdoor workers from UV radiation.
of Fig. 8a, the ballistic performance of the pAFS was similar The increasing demand for lighter automotive heat-dissi-
to that of Twaron. However, both exhibited a remarkable ther- pating materials coupled with the rapid development of elec-
mal insulation effect. By adopting this methodology, an anti- tronic products has resulted in a surge in research on high
ballistic material with both thermal and mechanical protection heat-dissipation materials [271–274]. AFs have attracted
can be achieved. This presents the potential for development. considerable attention as potential heat-dissipating materials
UV rays can generate reactive oxygen species in the human owing to their high strength and high-temperature resistance
skin, thereby causing oxidative damage and the potential [275]. However, the thermal conductivity of AFs is inef-
development of skin cancer [268–270]. Thus, it is essential fective because of the deficiency of free electrons in their
for outdoor workers to protect their skin from UV radiation. molecular structures. As a result, the heat transfer in AFs
Utilizing fabrics made from anti-UV textiles is a potential relies primarily on lattice vibration, i.e., the transfer of pho-
approach to accomplishing this objective. Li et al. [263] fab- nons, which is not sufficiently efficient [276]. Therefore, the
ricated anti-UV radiation fabrics using InOF-1 as the MOFs thermal conductivity of the AF-based composites displays
and hot-pressed aramid fabrics in a single solid phase. The potential. As shown in Fig. 8c through a wet-forming pro-
transmission of UV radiation significantly decreased after the cess, Xie et al. [264] successfully introduced ZnO NWs that
application of InOF-1 to the aramid fabrics. Moreover, the UV were hydrothermally synthesized into an aramid (Kevlar)
13
Fig. 8 The potential fields of AFs. a p-AF sheets for bulletproof. lar textile for intelligent protective clothing. [265], Copyright 2020.
[262], Copyright 2020. Reproduced with permission from Elsevier Reproduced with permission from American Chemical Society. e
Ltd. b Anti-UV radiation textiles. [263], Copyright 2019. Reproduced m-AF paper for EMI shielding in the extreme environments. [266],
with permission from John Wiley & Sons Inc. c Schematic illustra- Copyright 2020. Reproduced with permission from Elsevier Ltd. f
tion for preparation of paper-based thermally conductive materials. Electrothermal/Photothermal conversion aramid spun-laced nonwo-
[264], Copyright 2018. Reproduced with permission from Springer ven fabric. [267], Copyright 2021. Reproduced with permission from
Science Business Media. d Laser writing of Janus graphene/Kev- Elsevier Ltd
paper-based thermally conductive material. The modified under microwave irradiation. Hazarika demonstrated that the
aramid paper exhibited a significant increase in thermal con- electrical conductivity of the modified fabric was signifi-
ductivity from 0.0867 to 0.1985 W/m K (by 129%) while cantly improved and presented a novel strategy for enhanc-
maintaining a high mechanical strength. ing the sensing performance. Wang et al. [265] developed
With the development of smart wearable textiles, tex- a novel strategy for directly writing laser-induced graphene
tiles with protective properties have received attention. (LIG) onto Kevlar textiles in ambient air. They successfully
Kevlar fibers are essential components of protective cloth- demonstrated the application of the as-prepared textiles in
ing owing to their remarkable mechanical properties [277, smart protective clothing (Fig. 8d). It is noteworthy that
278]. Considerable efforts have been undertaken in this field. the patterns of Kevlar textiles can be adjusted using sim-
Polypyrrole (PPy) is prominent for its simple synthesis, pol- ple computer-controlled laser writing. It is noteworthy that
lution-free characteristic, and high conductivity [279–281]. the patterns of Kevlar textiles can be adjusted using simple
Significant efforts have been undertaken to develop AFs computer-controlled laser writing. Furthermore, they used
by the in situ synthesis of PPy [282–284]. Hazarika et al. this textile to construct a Zn–air battery that exhibited a high
[285] synthesized PPy in situ on surface-treated woven open-circuit voltage of 1.37 V in conjunction with a remark-
Kevlar fibers and coated the surface with GO. Finally, they able flexibility. Notably, in addition to providing the typi-
synthesized Fe-nanoparticle-decorated CNT on the surface cal protective function of the textile, the protective clothing
13
based on this textile is equipped with a sensitive gas detec- ANFs resulted in smaller nanofibers, more transparent and
tion mechanism and displays a remarkable cycle stability. smoother surfaces on the prepared films, and higher conveni-
Electromagnetic interference (EMI) shielding materials ence and efficiency of the preparation process [301, 302].
are paramount in advanced societies, particularly in areas As a light-weight, transparent, ultra-thin, high-strength,
related to national defense, military applications, enter- high-toughness, and high-chemical-stability films [303–309],
prises, and even confidential state information [285–288]. ANFs have been widely studied in the fields of reinforcement
Owing to the remarkable high/low-temperature stability [23, 310], adsorption [311, 312], flexible sensor [313, 314],
and chemical stability of AFs, scientists have focused on filtration [315–317], EMI [318–320], and (particularly) lith-
their application in EMI shielding [267, 289, 290]. Figure 8e ium-ion battery (LIB) separators [321–323]. Xia et al. [324]
shows the results of the electroless silver plating conducted manufactured cellulose/ANFs films using waste cotton textiles
by Zhou et al. [266] on m-AF paper treated with plasma. The and ANFs. As shown in Fig. 9a, the tensile strength and elon-
resulting fiber paper exhibited remarkable high/low-temper- gation of the composite film increased by 63.4% and 154%,
ature and solvent stabilities in conjunction with remarkable respectively, compared with those of the cellulose film to
flexibility and EMI shielding performance. attain 54.4 MPa and 15.8%, respectively. Yang et al. [325]
In cold environments, maintaining thermal comfort and a proposed an aramid-coating-on-aramid method to prepare a
normal body temperature is vital, and textiles that can convert heterocyclic aramid (HA)/heterocyclic aramid (PANF) aero-
electrothermal and photothermal energy are vitally important gel skin–core composite film. They followed a methodol-
[291, 292]. Wang et al. [293] formed an interlaced conduc- ogy similar to that described above [298], except that they
tive network on surface-modified aramid-spunlaced nonwo- added 2-(4-aminophenyl)-5-aminobenzimidazole (APBZ) to
ven fabrics with MXene using a spray–drying technique. As the PPD. The solution was then applied to the surface of the
shown in Fig. 8f, the modified fabrics demonstrated remark- PANF aerogel film, washed with deionized water, and dried.
able electrothermal/photothermal conversion properties while This yielded an HA/PANF aerogel membrane. Owing to the
maintaining good flexibility and breathability. This is attrib- interlocking structure between HA and the PANF aerogel at
utable to the nonwoven structure of the fabric. This method the interface, as well as the superior strength and toughness
can be used to develop intelligent wearable electric heaters. of the HA film, the mechanical properties of the compos-
ite membrane improved significantly. Specifically, the ten-
Applications of Aramid Nanofibers sile strength increased from 0.7 to 11.4 MPa, the modulus
increased from 34.0 to 624 MPa, and the fracture toughness
In general, AFs have diameters ranging from a few microns to increased from 1.0 × 105 to 3.4 × 106 kJ/m3.
marginally more than ten microns [294]. Reducing the diam- Flexible electrodes are an important area of research
eter of the fibers to the nanoscale allows for a more uniform because of their potential use in wearable electronics and
dispersion on other substrates, and the nanoscale fibers may other applications. Among these, ANFs have become popu-
generate other properties [295]. Therefore, ANFs were devel- lar because of their remarkable mechanical properties and
oped because of the comprehensive performance of AFs. flexibility. Efforts have been undertaken to develop flexible
ANFs were first synthesized by Kotov et al. in 2011 [296]. electrodes for this purpose. Kwon et al. [305] utilized the
This involved the use of Kevlar fibers and KOH in dimethyl LBL self-assembly technique to prepare ANF/graphene elec-
sulfoxide (DMSO) with magnetic stirring for a week at room trodes. Specifically, they treated silicon substrates with pira-
temperature to form a dark red solution. This resulted in ANF nha solution plasma and [poly(diallyldimethylammonium
dispersion [297]. However, a crucial drawback of this method chloride)] (PDDA) solution in succession. The substrates
is that the strength of the nanofibers decreases during dehydro- were subsequently immersed in a GO dispersion and an
genation in the presence of NaOH. To address this issue, Tuo at ANF/DMSO dispersion sequentially, and finally rinsed with
Tsinghua University developed a new approach for efficiently water. The flexibility of the ANFs and electrical conductivity
synthesizing ANFs [298]. CaCl2 and methoxy polyethylene of GO enabled the prepared electrodes to exhibit remarkable
glycol (mPEG) were dissolved in NMP at 100 °C in a uniquely bending resistance and electrical properties, as illustrated in
designed N2 atmosphere. These were then cooled to 0 °C in Fig. 9b. This method of LBL self-assembly to achieve con-
an ice water bath. PPD was then dissolved in the reaction sys- ductivity for fabricating flexible electrodes displays potential
tem at 0 °C while being stirred, and a certain amount of TPC for future applications.
was added. This was followed by an acceleration of stirring for The development of lightweight and miniaturized flex-
polycondensation at temperatures below 70 °C. To disperse the ible sensors is of high significance for convenient monitor-
PPTA gel, excess NMP was introduced under strong shear. Sub- ing. Therefore, ANFs can be applied to wearable sensors.
sequently, the dispersion was combined with deionized water Based on the piezoresistive pressure sensor mechanism,
under identical conditions to obtain ANFs [299, 300]. Com- Chen et al. [330] designed and fabricated an ANF-based
pared with the previous method, Tuo's approach to synthesizing pressure sensor. ANF-reinforced bacterial-cellulose
13
Fig. 9 The potential fields of ANFs. a Preparation of transparent batteries. [327], Copyright 2021. Reproduced with permission from
cellulose/ ANFs films with improved mechanical properties. [324], Elsevier Ltd. e High flux organic solvent nanofiltration membrane
Copyright 2021. Reproduced with permission from Elsevier Ltd. b from Kevlar ANFs. [328], Copyright 2018. Reproduced with per-
Robust and flexible ANF/graphene LBL electrodes. [305], Copyright mission from Royal Society of Chemistry. f MXene/ ANFs for EMI
2020. Reproduced with permission from Elsevier Ltd. c Aramid- shielding paper. [329], Copyright 2022. Reproduced with permission
nanofibers-based flexible sensor. [326], Copyright 2021. Reproduced from American Chemical Society
with permission from Elsevier Ltd. d Z-PMIA separator of the Li–S
nanocomposite membranes were prepared using a vacuum- sensor capable of tension, microhumidity, and pressure
filtration self-assembly process. A pressure sensor was sensing. This sensor exhibited high micro-pressure sens-
prepared by modifying a membrane with Ag NWs. This ing, remarkable mechanical durability, high response and
hybrid device provided remarkable long-term stability and recovery rates, and the capability to detect humidity in
exhibited good sensing properties and suitable antibacte- a noncontact manner through the deformation caused by
rial activity owing to the presence of Ag NWs. Further- the hygroscopic expansion of the microstructure. Moreo-
more, as shown in Fig. 9c, Wu et al. [326] used an inkjet ver, the flexibility of inkjet printing enables the design of
printing and buckling strategy to fabricate a wearable various patterns. This makes this novel sensor fabrication
13
method a potential candidate for emerging portable elec- Compared with AFs in the field of EMI shielding, ANFs
tronic devices. are favored because of their better dispersion and uniform-
The invention of LIBs by Whittingham [331, 332], ity [318]. Huang et al. [346] proposed the incorporation of
Goodenough [333, 334], and Yoshino [335] was a signifi- trace amounts of ANFs into a liquid metal to construct a
cant development in energy storage technology. However, supporting framework that yields a self-standing film made
the advancement of LIBs has been impeded by the uncon- of liquid metal. The film consists of high-conductivity liq-
trollable dendrite formation on Li electrodes during the uid–metal networks, exhibits a remarkable conductivity of
charge–discharge cycling. These problems have induced 7752 S/cm, and an exceptionally high degree of EMI shield-
substantial investigations into the development of safer ing. Wang et al. [329] designed high-strength, flexible, and
Li batteries [336–338]. A feasible solution was obtained multifunctional EMI shielding materials that combine ANFs
through a comprehensive study of ANFs, which display and MXenes. In their research, a DMSO solution of MXene
solid and ultrathin properties that make these preferable was obtained through a series of treatments and mixed with
for inhibiting dendrite growth [339–341]. Tung et al. [342] a DMSO solution of ANFs to create a black MXene/ANF
demonstrated that using the LBL self-assembly method composite paper via a blade coating process. The as-pre-
to assemble poly(ethylene oxide) (PEO) and ANFs lay- pared paper exhibited exceptional mechanical properties.
ers on glass slides effectively prevents the formation of Because of the presence of MXene, it exhibited good elec-
hard copper dendrites under extreme discharge conditions. trical conductivity, thereby yielding a high electromagnetic
Liu et al. [327] proposed an approach for the in-situ for- shielding effect (see Fig. 9f).
mation of the zeolitic imidazolate framework ZIF-L(Co)
on m-ANFs to prepare battery separators. As shown in
Fig. 9d, owing to the unique characteristics of ANFs and Outlooks
ZIF-L(Co), the separator exhibited a high mechanical
strength and remarkable thermal stability, and effectively Although considerable achievements in fundamental
suppressed the shuttling of polysulfides and growth of lith- research and advanced applications have been made in
ium dendrites. Additionally, it showed a remarkable cycle recent years, significant challenges and obstacles remain
stability. That is, the capacity fade per cycle was 0.033%. that need to be addressed in the development of advanced
Nanofiltration has been widely used in the chemical, aramid fibrous materials and their composites. (1) The theo-
pharmaceutical, petrochemical, sewage treatment, and retical strength of AFs has not been achieved. (2) The inert
food industries [343]. Therefore, the development of new chemical surface and poor UV resistance limit their appli-
nanofiltration membranes with high separation and solvent cation in extreme environments. Conventional modification
resistance capabilities is a new direction and challenging methods destroy the original properties of the fibers even
[344]. Ji et al. [345] developed an asymmetric membrane when the target properties of the modified fibers improve
that concentrated strongly acidic and basic solutions. Ji marginally. New methods such as plasma-enhanced chemi-
cast a DMSO solution of ANFs onto a polyvinylidene fluo- cal vapor deposition (PECVD) and ALD are hindered by
ride (PVDF) membrane to obtain an ANF-modified PVDF their incapability to be scaled up and the high costs. (3)
membrane. Aided by the presence of ANFs, the modified Although AF-based composites have been studied exten-
membrane has stronger acid and alkali resistance, and a sively and certain achievements have been made, the focus
certain concentration of acids and alkalis, which display has been on improving their mechanical properties. How-
a significant potential for wastewater treatment. Li et al. ever, the functional applications of these composites remain
[328] reported a high-flux organic solvent nanofiltration largely unknown. (4) Most solvents used for preparing AFs
membrane composed of Kevlar ANFs. The preparation and ANFs are toxic, and the preparation process is time- and
process is shown in Fig. 9e. ANFs were non-covalently energy-consuming. ANFs industry is even in its infancy due
bound to polyethyleneimine (PEI) and processed further to it cannot be mass-produced.
into ANF/PEI organic solvent nanofiltration membranes Based on the above challenges, it is necessary to develop
via non-solvent-induced phase separation and post-treat- a green, efficient, simple, and inexpensive synthetic method
ment. The experimental results showed that the permeabil- by identifying low-toxicity or even nontoxic solvents and
ity of the membrane increased by over four times. Moreo- new catalysts for polymerization. The evaluation of mon-
ver, it had strong permeability to organic solvents such omer synthesis and processes that yield AFs with higher
as tetrahydrofuran and acetone. The membranes exhibited longitudinal strength, transverse strength, or degree of
good stability in organic solvents. This method for fabri- polymerization, as well as improvements in the spinning
cating membranes with high chemical stability and perme- process would also be crucial. Additionally, a more univer-
ability provides a new direction for developing nanofiltra- sal approach is required to improve the defects in AFs and
tion membranes using high-performance organic solvents. further expand their application in various fields. To develop
13
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13
340. Tung SO, Fisher SL, Kotov NA, Thompson LT. Nanoporous aramid Zihui Liang is a Lecturer in
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mun. 2018;9:4193. for Advanced Textile Processing
341. He LY, Qiu T, Xie CJ, Tuo XL. A phase separation method toward and Clean Production at Wuhan
PPTA-polypropylene nanocomposite separator for safe lithium ion Textile University. He obtained
batteries. J Appl Polym Sci. 2018;135:46697. his Ph.D. degree from Hubei
342. Tung SO, Ho S, Yang M, Zhang RL, Kotov NA. A dendrite-sup- University in 2020. His research
pressing composite ion conductor from aramid nanofibres. Nat focuses on fiber functionaliza-
Commun. 2015;6:6152. tion, smart textiles, and wearable
343. Vandezande P, Gevers LEM, Vankelecom IFJ. Solvent resistant flexible electronics.
nanofiltration: separating on a molecular level. Chem Soc Rev.
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Zhou XJ, Liu DP, Wyman I. Fabrication of aramid-coated asym- Yuxin Luo is currently a master
metric PVDF membranes towards acidic and alkaline solutions student at Wuhan Textile Univer-
concentration via direct contact membrane distillation. Appl Surf sity. His research focuses on high
Sci. 2021;562: 150185. performance color carbon fiber.
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2021;426: 131288.
Publisher's Note Springer Nature remains neutral with regard to

jurisdictional claims in published maps and institutional affiliations.
Springer Nature or its licensor (e.g. a society or other partner) holds

exclusive rights to this article under a publishing agreement with the
author(s) or other rightsholder(s); author self-archiving of the accepted
manuscript version of this article is solely governed by the terms of
such publishing agreement and applicable law. Yu Zhang is currently studying
for her master’s degree at Wuhan
Textile University. Her currently
Annan He is currently a master research focuses on the func-
student in State Key Laboratory tional fiber materials.
of New Textile Materials and
Advanced Processing Technolo-
gies at Wuhan Textile University.
His research focuses on the func-
tional fiber materials and
devices.
Mengqi Wang is currently a mas-

ter student in State Key Labora-
tory of New Textile Materials
Tonghe Xing is currently a master and Advanced Processing Tech-
student in State Key Laboratory nologies at Wuhan Textile Uni-
of New Textile Materials and versity. His research focuses on
Advanced Processing Technolo- the structural color fibers.
gies at Wuhan Textile University.
His research focuses on the func-
tional modification of carbon fib-
ers and silk.
13
Zhiyu Huang received his mas- Hongmei Zuo is a Lecturer in

ter’s degree from Wuhan Textile School of Textile and Garment at
University in 2022. He is cur- Anhui Polytechnic University.
rently a Ph.D. student in the She obtained her Ph.D. degree
School of Textiles and Clothing from Beihang University in
at Qingdao University. His 2021. Her research focuses on
research focuses on the high- textile reinforced composites and
value recycling of waste cotton surface modification of fiber
textiles, such as the preparation materials.
of multifunctional cellulose
aerogel fibers.
Jie Bai is a senior engineer in Wenshuo Zhang received her

textile engineering. She received M.S. degree in Chemical Engi-
her master’s degree from the neering from the Illinois Institute
Beijing Institute of Fashion of Technology in 2015 and her
Technology in 2014. Her Ph.D. degree in Mechanical
research focuses on functional Engineering from the University
fiber materials. of Illinois at Chicago in 2019.
Her research focuses on
advanced functional nanofibers,
nonwovens, and heat and mass
transfer through porous media.
Liuyan Wu is an undergraduate Fengxiang Chen is an Associate

student at Wuhan Textile Univer- Professor in State Key Labora-
sity. She is now studying in Prof. tory of New Textile Materials
Xu’s team. and Advanced Processing Tech-
nologies at Wuhan Textile Uni-
versity. He received his Ph.D.
degree at Hubei University in
2017. His research focuses on
functional fiber materials and
devices.
Zhicheng Shi is currently a mas- Weilin Xu is an academician of

ter student in State Key Labora- the Chinese Academy of Engi-
tory of New Textile Materials neering and the President of
and Advanced Processing Tech- Wuhan Textile University,
nologies at Wuhan Textile Uni- China. He received the National
versity. His research direction is Science Fund for Distinguished
advanced functional materials. Young Scholars award in 2013.
He is the First Prize Winner of
the National Science and Tech-
nology Progress in 2009. His
research focuses on textile mate-
rials, textile processing technol-
ogy, dyeing and finishing, bio-
medical textiles and natural fiber
materials.
13
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Advanced Aramid Fibrous Materials: Fundamentals, Advances, and Beyond

Article in Advanced Fiber Materials · October 2023

Tonghe Xing Zihui Liang

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Advanced Aramid Fibrous Materials: Fundamentals, Advances,

Received: 16 May 2023 / Accepted: 6 September 2023

Keywords Aramid fiber · Surface functionalization · Application · Challenges and outlooks

Introduction vehicle industries, individual protection, leisure sports,

Fig. 2 Synthesis mechanism of the a m-aramid, b p-aramid, and c PBO (Zylon)

Fig. 7 The potential application fields of AFs and ANFs

Publisher's Note Springer Nature remains neutral with regard to

Springer Nature or its licensor (e.g. a society or other partner) holds

Mengqi Wang is currently a mas-

Zhiyu Huang received his mas- Hongmei Zuo is a Lecturer in

Jie Bai is a senior engineer in Wenshuo Zhang received her

Liuyan Wu is an undergraduate Fengxiang Chen is an Associate

Zhicheng Shi is currently a mas- Weilin Xu is an academician of

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