polymers

Review
Review
Progressof
Progress ofPolymer
Polymer Application
Application in
inCoated
CoatedProppant
Proppantand
and
Ultra-Low
Ultra-LowDensity
Density Proppant
Proppant
Tao Chen
Tao Chen, ,Jie
JieGao
Gao*,*Yuan
, Yuan Zhao
Zhao, , Tian Liang,
Tian Liang, Guowen Guowen
Hu andHu and Xiaobing
Xiaobing Han * Han *

Hubei Key Laboratory of Radiation Chemistry and Functional Materials, School of Nuclear Technology and
Hubei Key Laboratory of Radiation Chemistry and Functional Materials, School of Nuclear Technology and
Chemistry & Biology, Hubei University of Science and Technology, Xianning 437100, China;
Chemistry & Biology, Hubei University of Science and Technology, Xianning 437100, China
taochen518@163.com (T.C.); zhyf308@hbust.edu.cn (Y.Z.); new.tony.leung.3@gmail.com (T.L.);
* Correspondence: gaojie2019@hbust.edu.cn (J.G.); hanxiaobing@hbust.edu.cn (X.H.)
hgwpublic@163.com (G.H.)
* Correspondence: gaojie2019@hbust.edu.cn (J.G.); hanxiaobing@hbust.edu.cn (X.H.)
Abstract: Design, synthesis and application of low-density proppant (LDP) are of great significance
Citation: Chen, T.; Gao, J.; Zhao, Y.;
Abstract:
for Design,
efficient synthesis
and clean and application
exploitation of low-density
of low permeability proppant
oil and (LDP)
gas. On the are of of
basis great significance
a brief introduction
Liang, T.; Hu, G.; Han, X. Progress of forhydraulic
of efficient and clean exploitation
fracturing of low permeability
and the application oil and gas.
of traditional On the basis
proppants, this of a briefsystematically
review introduc-
Polymer Application in Coated tion of hydraulic
summarized fracturing
the polymer and the application
application of LDP,
progress in traditional proppants,
including coated this
sand,review
coated systematically
ceramics, coated
Proppant and Ultra-Low Density summarized the polymer application progress in LDP, including coated
nutshells, especially for polymer composites based ultra-low density proppant (ULDP).sand, coated ceramics,
Finally, the
Proppant. Polymers 2022, 14, x. coated nutshells, especially for polymer composites based ultra-low
existing problems and future development direction are also prospected. density proppant (ULDP). Fi-
https://doi.org/10.3390/xxxxx nally, the existing problems and future development direction are also prospected.
Academic Editor: Yung-Sheng Yen Keywords: LDP; polymer; sand; ceramics; nutshell; ULDP; fabrication; property
Keywords: LDP; polymer; sand; ceramics; nutshell; ULDP; fabrication; property
Received: 15 November 2022
Accepted: 14 December 2022
Published: date
1. Introduction
Publisher’s Note: MDPI stays neu- 1. Introduction
tral with regard to jurisdictional
As one of the most important technology for the exploitation of oil and gas, hydraulic
As one of the most important technology for the exploitation of oil and gas, hydraulic
claims in published maps and institu- fracturing has been widely used in the exploitation of unconventional low permeability
fracturing has been widely used in the exploitation of unconventional low permeability
tional affiliations. reservoir, and secondary exploitation of old oil and gas wells (Figure 1) [1]. Hydraulic frac-
reservoir, and secondary exploitation of old oil and gas wells (Figure 1) [1]. Hydraulic
turing can stimulate hydrocarbon production by creating a network of highly conductivity
Citation: Chen, T.; Gao, J.; Zhao, Y.; fracturing can stimulate hydrocarbon production by creating a network of highly conduc-
fractures surrounding a wellbore. In the hydraulic fracturing, proppant is brought into
Liang, T.; Hu, G.; Han, X. Progress of tivity fractures surrounding a wellbore. In the hydraulic fracturing, proppant is brought
Copyright:
Polymer © 2022inby
Application the authors.
Coated
the fractures generated by hydraulic fracturing with fracturing fluid, therefore effective
into the fractures generated by hydraulic fracturing with fracturing fluid, therefore effec-
Submitted
Proppant andfor possibleDensity
Ultra-Low open access conductivity and and
tive conductivity highhigh
output of oil
output of or
oilgas cancan
or gas be obtained
be obtained[2].[2Among the
]. Among materials
the materialsused
publication
Proppant. under2022,
Polymers the terms and con-
14, 5534. in
used in the hydraulic fracturing, proppant was considered to be the key materialstotoenhance
the hydraulic fracturing, proppant was considered to be the key materials en-
ditions of the Creative Commons At-
https://doi.org/10.3390/ the exploitation
hance efficiency
the exploitation of oil and
efficiency of oilgas,
andespecially for the
gas, especially forold
thewells and low
old wells and permeability
low per-
tribution (CC BY) license (https://cre- reservoir
polym14245534 meability[3].
reservoir [3].
ativecommons.org/licenses/by/4.0/).
Academic Editor: Yung-Sheng Yen

Received: 15 November 2022

Accepted: 14 December 2022
Published: 17 December 2022

Publisher’s Note: MDPI stays neutral

with regard to jurisdictional claims in
published maps and institutional affil-
iations.

Copyright: © 2022 by the authors.

Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and Figure 1.
Figure 1. Schematic
Schematicof
ofthe
thehydraulic
hydraulicfracturing process
fracturing [1].[1].
process
conditions of the Creative Commons
Attribution (CC BY) license (https:// Proppant is a solid particle with certain sphericity and roundness, strength, corrosion
creativecommons.org/licenses/by/ resistance and stability, which can prevent the reclosing of fractures generated by hydraulic
4.0/). fracturing, maintain the smooth flow of oil and gas, and improve the productivity [4,5].
Polymers 2022, 14, x. https://doi.org/10.3390/xxxxx www.mdpi.com/journal/polymers

Polymers 2022, 14, 5534. https://doi.org/10.3390/polym14245534 https://www.mdpi.com/journal/polymers

 Polymers 2022, 14, x FOR PEER REVIEW 2 of 15

Polymers 2022, 14, 5534 Proppant is a solid particle with certain sphericity and roundness, strength, corrosion 2 of 14
resistance and stability, which can prevent the reclosing of fractures generated by hydrau-
lic fracturing, maintain the smooth flow of oil and gas, and improve the productivity [4,5].
In the hydraulic fracturing process, the shape, strength, acid solubility and turbidity of
In the hydraulic fracturing process, the shape, strength, acid solubility and turbidity of
the proppant can influence the integrity of the newly created fractures, thus determined
the proppant can influence the integrity of the newly created fractures, thus determined
the efficiency of oil and gas flow out of the well [6]. The sphericity and roundness are very
the efficiency of oil and gas flow out of the well [6]. The sphericity and roundness are
important because it can influence the strength of the proppant. The sphericity is the de-
very important because it can influence the strength of the proppant. The sphericity is
gree of the proppant close to the sphere, and the roundness refers to the relative sharpness
the degree of the proppant close to the sphere, and the roundness refers to the relative
of proppant edges and corners. The angular and pointed proppant tends to break easily,
sharpness of proppant edges and corners. The angular and pointed proppant tends to
whereas the well-rounded proppant will be mechanically stable. The proppant with high
break easily, whereas the well-rounded proppant will be mechanically stable. The proppant
sphericity and roundness can provide high conductivity, because larger passages can be
with high sphericity and roundness can provide high conductivity, because larger passages
formed for this kind of proppant. The ability to withstand compressive loading is also
can be formed for this kind of proppant. The ability to withstand compressive loading is
necessary for proppant. The proppant mustn’t break into fines and block the fractures,
also
which necessary
will down for the
proppant.
productionThe proppant
rate, thus mustn’t breakshould
the proppant into fines and
with lowblock the fractures,
crushing rate.
which
In addition, the proppant must endure harsh environment such as acid mixture pumpedrate.
will down the production rate, thus the proppant should with low crushing
In addition,
into wells tothe proppant
generated must
crack, endure
thus harsh
the low acidenvironment
solubility and such
lowasturbidity
acid mixture
is alsopumped
very
into wells to generated
important for the proppant. crack, thus the low acid solubility and low turbidity is also very
important
Since for
the the proppant.
natural sand, glass bead and nutshell has been used as proppants in the
Since the natural
hydraulic fracturing, new sand,andglass bead
efficient and nutshell
proppants have has
beenbeen used as
developed proppants
rapidly in the
[7]. After
hydraulic fracturing, new and efficient proppants have been developed
1970s, due to the excellent performance in oil exploitation, synthetic ceramics proppants rapidly [7]. After
1970s, due to the excellent performance in oil exploitation, synthetic
sintered with bauxite as the main materials was rapid developed and promoted. In order ceramics proppants
sintered
to further with bauxite
improve theascomprehensive
the main materials was rapid
properties, developed
polymer coatedand
sandpromoted.
and coated In ce-
order
to further improve the comprehensive properties, polymer coated sand
ramic proppant were developed after 1980s [8]. However, traditional natural sand and and coated ceramic
proppant
synthetic were
ceramicsdeveloped after 1980s
is not suitable [8].eco-friendly
for the However, traditional
hydraulic natural sand
fracturing, and synthetic
because they
ceramics
are settled quickly in low-viscosity fracturing liquid (Figure 2) [9]. In addition, theare
is not suitable for the eco-friendly hydraulic fracturing, because they settled
inertia
quickly
of these in low-viscosity
high fracturing
density proppants liquid
makes them(Figure
hard to2) turn
[9]. In addition,
from the inertia
the wellbore of these
to perfora-
high
tionsdensity
[10]. proppants makes them hard to turn from the wellbore to perforations [10].

Figure 2. Prop effect

Figure 2. effect of
of (a)
(a) traditional
traditionalproppant
proppantand
and(b)
(b)low-density
low-density proppant
proppant [9].[9].

The
The oil and gas
oil and gas production
productionisishighly
highlycorrelated
correlatedwith
with thethe propped
propped length
length andand
area,area,
and
and the fractureconductivity
the fracture conductivityofof hydraulic
hydraulic fracturing.
fracturing. As reported
As reported in thein the literature
literature [11], 3D[11],
3D fracturing
fracturing modelmodel
shows shows that ULDP
that ULDP cover and
cover higher higher andfracture
longer longerareas
fracture
withareas with a
a smaller
smaller propped width. The ULDP can improve the propped length
propped width. The ULDP can improve the propped length and area in low permeability and area in low
permeability shale reservoirs, while mainly improve the propped area in
shale reservoirs, while mainly improve the propped area in high permeability shale res- high permeability
shale reservoirs.
ervoirs. On the
On the other other
hand, thehand, the conductivity
fracture fracture conductivity
was highly was highly dependent
dependent on the prop-on the
proppant
pant size,size,
flowflow
back,back,
and and
finesfines generation
generation [6]. [6]. Generally,
Generally, largelarge proppant
proppant size,size,
lowlowflowflow
back
back and
and low fines generation
generationcancanprovide
providehigher
higherfracture
fractureconductivity.
conductivity.
As
As the
thetraditional
traditionalhydraulic
hydraulicfracturing
fracturingfluid
fluidpossesses
possessesaalow lowviscosity,
viscosity,which
which has
hasa poor
a
carrying abilityability
poor carrying for high density
for high proppant,
density suchsuch
proppant, as natural sand,
as natural ceramic
sand, andand
ceramic glass bead,
glass
which has high density and high fines generation [12]. In order to improve the carrying
capacity of traditional proppant, it is necessary to increase the flow rate or viscosity of
fracturing fluid. Though these methods can solve the problem of carrying ability to some
extent, yet they will cause new problems such as difficult treatment of fluid flow back and
great damage to reservoirs [13]. Therefore, in order to thoroughly solve the problem of
Polymers 2022, 14, 5534 3 of 14

proppant transport, it is of great significance to develop novel proppant with low density,
or new fracturing technology such as liquid self-propping [14]. According to the difference
of density, proppants can be divided into following categories (Table 1) [15].

Table 1. Proppant classification according to the density.

Proppant Bulk Density (g·cm−3 ) Apparent Density (g·cm−3 )

High density (HDP) >1.8 >3.35
Intermediate density (IDP) 1.65~1.80 3.00~3.35
Low density (LDP) 1.50~16.5 2.60~3.00
Ultra-low density (ULDP) <1.5 <2.6

Till now, there are three main strategies to obtain low density proppant: (1) make
the traditional HDP into hollow or porous structure, so as to reduce the apparent density
of the proppant [5,15]. (2) organic polymer coating for traditional HDP, which can not
only reduce the density to some extent, but also can improve the mechanical strength,
sphericity, hydrophobicity and corrosion resistance [6–8]. (3) develop ULDP with organic
polymer, modification with inorganic filler is always needed to improve the mechanical and
thermal properties [15]. Though the porosity of traditional HDP can significantly reduce the
density, yet the mechanical strength and corrosion resistance will also be affected. Therefore,
increasing the content of low density organic polymer in the proppant, including coated
proppant and polymer composite proppant, became the most important development
direction of high performance LDP. As mentioned above, this review firstly introduced the
HDP based on natural sand and synthetic ceramics, then systematically summarized the
application of polymer in coated sand, coated ceramic, coated nutshell, especially for the
polymer composites based proppant.

2. Traditional High Density Proppant

At present, the most used proppant in hydraulic fracturing is high-density natural sand
and synthetic ceramics, the typical properties of these proppants are listed in Table 2 [6].
Because of its low cost and relative low density, the natural sand was also widely used
in the hydraulic fracturing [7]. However, the natural sand possesses high crushing rate,
high turbidity and low sphericity, which is only suitable for the exploitation of shallow oil
and gas wells with low closing pressure. With the depth and pressure increase of the oil
well, the natural sand can not meet the requirements, high performance synthetic ceramic
proppant came into being. Though high-strength ceramic proppant can be made from
aluminous minerals and other industrial wastes, yet the fabrication of ceramic proppant
needs to be sintered under high temperature, leading to the increase of cost [16,17]. Most
of the ceramic proppant was made with high density bauxite as raw materials, leading to
the high density of traditional ceramic proppant. To enhance the carrying ability for high
density ceramic proppant, the increase of displacement or viscosity for the fracturing fluid
is always needed, while this will bring about the problems of difficult treatment of fluid
flow back and great damage to oil and gas reservoirs [18].

Table 2. Typical properties of natural sand and synthetic ceramic proppant.

Proppant Natural Sand Synthetic Ceramics

Apparent density (g·cm−3 ) 2.5~2.7 3.3~3.6
Crushing rate (%) 36 13.5
Acid solubility (%) 5.5 6.9
Turbidity (FTU) 95 60
Sphericity 0.6 0.8
Roundness 0.6 0.8
Cost low high
 Acid solubility (%) 5.5 6.9
Acid solubility (%) 5.5 6.9
Turbidity (FTU) 95 60
Turbidity (FTU) 95 60
Sphericity 0.6 0.8
Sphericity 0.6 0.8
Roundness 0.6 0.8
Polymers 2022, 14, 5534 Roundness 0.6 0.8 4 of 14
Cost low high
Cost low high
In order to reduce the density of synthetic ceramic proppants, novel ceramic prop-
In order
In ordertotoreduce
reducethe
thedensity
densityofof synthetic
synthetic ceramic
ceramic proppants,
proppants, novel
novel ceramic
ceramic prop-
proppant
pant with hollow or porous structure were developed (Figure 3). Template based method
pant hollow
with with hollow or porous
or porous structure
structure were developed
were developed (Figure(Figure 3). Template
3). Template based based
method method
is the
is the most commonly approach to prepare hollow ceramic proppant, and volatile mate-
is thecommonly
most most commonly
approachapproach to prepare
to prepare hollowhollow
ceramicceramic
proppant,proppant, and volatile
and volatile materialsmate-
are
rials are always used as the templates, which can be volatilized through heating in the
rials areused
always always used
as the as the templates,
templates, which canwhich can be volatilized
be volatilized through
through heating heating
in the in the
process of
process of sintering [19]. With the addition of porogen in the fabrication, porous ceramic
process of
sintering sintering
[19]. [19].
With the With the
addition additioninofthe
of porogen porogen in theporous
fabrication, fabrication,
ceramicporous ceramic
proppant can
proppant can be made with the method similar to hollow ceramic proppant [20]. Though
be made with
proppant can the method
be made similar
with to hollow
the method ceramic
similar proppant
to hollow [20]. Though
ceramic proppant the porosity
[20]. Though of
the porosity of high density ceramic proppant can significantly reduce the density, the
high density ceramic
the porosity of high proppant can significantly
density ceramic proppantreduce the density, the
can significantly mechanical
reduce strength
the density, the
mechanical strength and corrosion resistance will also be affected [15].
and corrosion
mechanical resistance
strength andwill also beresistance
corrosion affected [15].
will also be affected [15].

Figure 3. Schemes of the hollow (a) or porous (b) ceramic proppant.

Figure 3. Schemes
Figure 3. Schemes of
of the
the hollow
hollow (a)
(a) or
or porous
porous (b)
(b)ceramic
ceramicproppant.
proppant.

3. Polymers Used in the Proppant Coating

3. Polymers Used in the Proppant Coating
traditional proppant with organic polymer can not
The coating of traditional not only
only decrease
decrease the
the
The coating of traditional proppant with organic polymer can not only decrease the
density of
density of the
theproppants,
proppants,but butalso
alsocan
canimprove
improvethe
thesphericity
sphericity and
and prevent
prevent thethe flow
flow back
back of
density of the proppants, but also can improve the sphericity and prevent the flow back
of proppant
proppant (Figure
(Figure 4) [7].
4) [7]. In addition,
In addition, thethe polymer
polymer coating
coating cancan serve
serve as aasprotective
a protective layer
layer to
of proppant (Figure 4) [7]. In addition, the polymer coating can serve as a protective layer
improve
to improvethe the
chemical resistance
chemical and and
resistance hydrocarbon affinity,
hydrocarbon providing
affinity, interaction
providing between
interaction be-
to improve the chemical resistance and hydrocarbon affinity, providing interaction be-
proppant to prevent
tween proppant leakage,leakage,
to prevent as well as
aswrapping the breaks
well as wrapping proppant
the after the proppant
breaks proppant after the
tween proppant to prevent leakage, as well as wrapping the breaks proppant after the
broken
proppant[8].broken [8].
proppant broken [8].

Figure 4. Schemes of the coating process

Figure 4. process of
of traditional
traditional proppant.
proppant.
Figure 4. Schemes of the coating process of traditional proppant.
Polymers
Polymers areare obtained
obtained through
through the
the polycondensation
polycondensation or or addition
addition polymerization
polymerization of of
small Polymers areAccording
obtained through the polycondensation or addition polymerization of
small monomers. According to the chemical composition, polymers can be
monomers. to the chemical composition, polymers can be divided
divided into
into
small
organic monomers. According to the chemical composition, polymers can be divided into
organic polymers
polymers and and inorganic
inorganic polymers.
polymers. According
According to to the thermal behavior,
the thermal behavior, thethe organic
organic
organic polymers
polymers and inorganic polymers. According to the thermal behavior, the organic
polymers can be divided into thermosetting polymers and thermoplastic polymers. As
can be divided into thermosetting polymers and thermoplastic polymers. As the
the
polymers can
thermosetting be divided into thermosetting polymers and thermoplastic polymers. Asandthe
thermosetting polymers
polymershavehavemany
manyadvantages
advantages such
suchas easy processing,
as easy highhigh
processing, strength
strength
thermosetting
low polymers have many advantages such as easy processing, high strength
and density, they have
low density, been widely
they have used in
been widely thein
used proppants coating
the proppants [8]. On[8].
coating theOnother
the hand,
other
andthermosetting
the low density, they have also
polymers beenpossess
widelysomeused disadvantages,
in the proppants coating low
including [8]. On the other
resistance to
hand, the thermosetting polymers also possess some disadvantages, including low re-
hand, the
oxygen, thermosetting
ozone and polymers
radiation, as also
well as possess
the low some
thermal disadvantages,
stability. The including
properties low
of re-
the
sistance to oxygen, ozone and radiation, as well as the low thermal stability. The proper-
sistance to oxygen,
polymers ozone andproppant
radiation,coating
as wellare
as listed
the lowin thermal stability. The proper-
ties of the mainly
polymers used in the
mainly used in the proppant coating are Table
listed3in
[12], including
Table epoxy
3 [12], includ-
ties ofphenolic
resin, the polymers
resin, mainly used in the
urea-aldehyde, and proppant
so on. coating
Among are
this listed in Table
polymers, epoxy 3and
[12], includ-
phenolic
ing epoxy resin, phenolic resin, urea-aldehyde, and so on. Among this polymers, epoxy
ing epoxy
resin was theresin,
most phenolic
promisingresin, urea-aldehyde,
candidate, and
due to its so performance
high on. Among this andpolymers,
low cost. epoxy
and phenolic resin was the most promising candidate, due to its high performance and
and phenolic resin was the most promising candidate, due to its high performance and
low cost.
low cost.
Polymers 2022, 14, 5534 5 of 14

Table 3. Properties for the polymers used in the proppant coating.

Curing Temperature Chemical

Polymer ◦C Strength Acid Resistance Heat Resistance Hydrophobic
Resistance
Epoxy resin 66~204 good good very good good good
Phenolic-aldehyde 121~204 good good very good good good
Urea-aldehyde 121~204 good good very good good good
Polyurethane 99~121 good moderate good good moderate
Vinyl resin 100~149 moderate good moderate moderate moderate
Polyester 100~149 moderate moderate moderate moderate moderate
Furan resin 191 bad good moderate moderate good

According to the difference of curing style, the coated proppant can be divided into
precuring proppant and curable proppant [7]. The precuring proppant was made by
traditional heat curing, individual proppant particle with smoother surface can be obtained.
In addition, the compressive strength, acid solubility, sphericity and roundness of the
proppant can be improved. For the curable proppant, the polymer was coated on the
substrate firstly, then injected into the formed fracture, finally cured and formed network
structure under high temperature and pressure in the well. The formed proppant network
can not only prevent flow back, but also can decrease the proppant embedding into the
clay or shale [8].

4. Application of Polymer in Coated Proppant

According to the difference of substrates, the coated proppants can be divided into
coated sand, coated ceramic and coated nutshell. Compared with the original substrates,
the comprehensive performance of the coated proppants was improved, but the cost will
also increase.

4.1. Polymer Coated Natural Sand Proppant

Polymer coated sand proppant has been widely investigated and applied (Figure 5),
representative research work are shown in Table 4. The effect of polymer type on the
comprehensive properties of coated sand was investigated by Zhang and co-workers [21],
including furan resin, resole resin, novolak resin and epoxy resin. Compared with nat-
ural sand, the properties of coated sand are significantly improved. The crushing rate
decreased from 36% to less than 4%, making the coated sand proppant can be used in deep
oil wells. The acid solubility decreased to 0.5%, which can greatly improve the resistance
to strong acid originated from fracture cleaning fluid. The turbidity decreased from 95 to
less than 30, which will reduce the pollution of proppant to oil and soil. The sphericity and
roundness increase from 0.6 to 0.8, which will enhance the conductivity. Carbon nanotube
(CNT) toughened epoxy coated sand was reported by Xia [22], high performance coated
sand proppant was obtained with obvious improved conductivity. Epoxy/phenolic binary
mixture coated sand was reported in our previous work [23], the sphericity and round-
ness of the obtained proppant was further enhanced to 0.85. Multicomponent polymer
(polystyrene, polymethyl methacrylate, epoxy) coated sand was investigated by Krishnan
Polymers 2022, 14, x FOR PEER REVIEW
and co-workers [24,25], ultra-low density proppant with bulk density less than 1.5 g·6cm of−15
3

was obtained, but the improvement of crushing rate and sphericity is not obvious.

Figure5.5.Sand
Figure Sand(a)
(a)and
andcoated
coatedsand
sand(b)
(b)proppant.
proppant.

Table 4. Properties of polymer coated natural sand proppant.

Bulk Density Crushing Rate Acid Solubility Turbidity Sphericity and

Polymer Ref.
(g·cm−3) (%) (%) (FTU) Roundness
Polymers 2022, 14, 5534 6 of 14

Table 4. Properties of polymer coated natural sand proppant.

Bulk Density Crushing Rate Acid Solubility Turbidity Sphericity and

Polymer Ref.
(g·cm−3 ) (%) (%) (FTU) Roundness
Furan resin 1.58 13/69 MPa 0.49 30 0.8
Resole resin 1.57 3.9/69 MPa 0.51 26 0.8
[21]
Novolak resin 1.56 3.8/69 MPa 0.50 28 0.8
Epoxy resin 1.58 1.9/69 MPa 0.18 24 0.8
CNT-Epoxy / 5.21/69 MPa 2.83 24 0.8 [22]
Epoxy/Phenolic / 1.6/52 MPa / / 0.85 [23]
(PS-PMMA-CG)-
1.35 9/69 MPa / / 0.7 [24]
(epoxy-CG)
(PS-PMMA/
1.32 5/82 MPa / / 0.7 [25]
DVB)-(Epoxy-CG)
PFVP The conductivity and flow back control ability was significantly improved [26]
Novolac resin Leaching behavior under high temperature and strong acid was improved [27]
GO-KHS 1.58 20/10 MPa 0.7 55 0.8 [28]

The coating of sand can not only improve the intrinsic characteristics, but also can
address the application problems in oil exploitation. Poly(2-fluorine-4-vinylpyridine)
(PFVP) coated sand was developed for the hydraulic fracturing, the crack conductivity and
flow back control ability of the obtained proppant was significantly improved [26]. To give
a deep insight into the chemical stability of the coated sand, novolac resin coated sand was
fabricated and tested at different conditions [27], results revealed that the leaching behavior
under high temperature (400 ◦ C) and strong acid (pH = 3) was improved. In addition,
the concentration of phenolics in the aqueous leachates are lower than 1 ppm. Recently,
graphene oxide (GO)/silane coupling agent (KHS) coated sand was also reported [28],
though the comprehensive performance was not obviously improved, yet the fabrication
method is relative simple.

4.2. Polymer Coated Synthetic Ceramic Proppant

Polymer coated ceramic proppant has also been widely investigated and applied
Polymers 2022, 14, x FOR PEER REVIEW
(Figure 6), representative research work are shown in Table 5. Deng and co-workers 7 of 15
reported the fabrication of ceramic proppant, which sintered with industrial waste fly ash,
maganese oxide and potassium feldspar [29]. After coated with phenolic/epoxy binary
mixture, the apparent
urea as porogen [32], density decreased
epoxy coated ULDPfrom 3.11
with apparent ·cm−3 , of
to 2.64 gdensity the1.03
crushing
g·cm−3rate
washas
ob-
also
tained for this proppant. Due to its hollow structure, the crushing rate increased to kaolin
reduced from 20.3 to 3.76%. Low-cost ceramic proppant was synthesized with 17.01%
and
at 55ZnO [30], the apparent density further decreased to 2.27 g·cm−3 with epoxy coating.
MPa.

Figure6.6.Ceramic
Figure Ceramic(a)
(a)and
andcoated
coatedceramic
ceramic(b)
(b)proppant.
proppant.

Table
To5.further
Properties of polymer
reduce coated synthetic
the apparent density, ceramic
coated proppant.
porous and hollow ceramic proppant
was developed.
Apparent Phenolic-epoxy
Crushing coated porous
Acid Solubility mullite based
Turbidity ceramicand
Sphericity proppant was re-
Polymer g·cm−3 ,
ported−3by Guo and co-workers [31], the apparent density further decreased to 1.90 Ref.
Density (g·cm ) Rate (%) (%) (FTU) Roundness
the compressive strength, sphericity and roundness of the obtained proppant was also
Phenolic/Epoxy 2.64 3.76/52 MPa / / / [29]
Epoxy 2.27 1.16/69 MPa / / / [30]
Phenolic-Epoxy 1.90 2.81/69 MPa / / >0.9 [31]
Epoxy 1.03 17.01/55 MPa / 1.59 >0.9 [32]
Phenolic / 18/82 MPa 4 / 0.9 [33]
Polymers 2022, 14, 5534 7 of 14

improved. Hollow ceramic proppant was fabricated with silica fume as raw material
and urea as porogen [32], epoxy coated ULDP with apparent density of 1.03 g·cm−3 was
obtained for this proppant. Due to its hollow structure, the crushing rate increased to
17.01% at 55 MPa.

Table 5. Properties of polymer coated synthetic ceramic proppant.

Apparent Crushing Acid Solubility Turbidity Sphericity and

Polymer Ref.
Density (g·cm−3 ) Rate (%) (%) (FTU) Roundness
Phenolic/Epoxy 2.64 3.76/52 MPa / / / [29]
Epoxy 2.27 1.16/69 MPa / / / [30]
Phenolic-Epoxy 1.90 2.81/69 MPa / / >0.9 [31]
Epoxy 1.03 17.01/55 MPa / 1.59 >0.9 [32]
Phenolic / 18/82 MPa 4 / 0.9 [33]
Epoxy / Hydrophobicity, suspension ability and conductivity improved [34]
ULW-1.75 1.75 Average porosity 50%, 56 MPa can be tolerated at 121 ◦ C [35,36]

The influence of curing conditions on the performance of phenolic resin coated ceramic
proppant was deeply investigated by Zhang and co-workers [33]. The obtained results
revealed that high temperature is conducive to forming a coating with excellent barrier
properties, and low temperature is benefit for improving the sphericity and roundness.
As the hydrophobicity of the proppant has an important influence on the recovery effi-
ciency of hydraulic fracturing, which can reduce the adsorption of water and increase
the conductivity of oil and gas, therefore it is necessary to enhance the hydrophobicity of
the proppant [6,8,12]. The practical application of epoxy coated ceramic proppant was
investigated by Fan and co-workers [34], the self-suspension ability of the coated prop-
pant increased by 16 times, the hydrophobicity and conductivity were increased by 83.8%
and 16.71%, respectively. ULW-1.75 is the most popular commercial coated ceramic prop-
pant [35,36], which has an average porosity of 50% and can form a ULDP with apparent
density of 1.75 g·cm−3 . In addition, the closing pressure of 56 MPa can be tolerated at
121 ◦ C.

4.3. Polymer Coated Bio-Based Nutshell Proppant

As the nutshell possesses ultra-low density, relative high strength and low cost, lead-
ing to the widely application since 1960s [37]. In order to give a deep insight into the
performance of raw nutshell used directly in hydraulic fracturing, the comprehensive
properties of coconut shell, palm shell and walnut shell was systematically investigated
by Zoveidavianpoor and co-workers [38] (Table 6). The apparent density of these shells
in the range of 1.14 to 1.33 g·cm−3 , but the crushing rate, acid solubility and turbidity is
relative poor. To address the problem of poor corrosion and heat resistance, especially
Polymers 2022, 14, x FOR PEER REVIEW
the low sphericity and roundness for raw nutshell, coated nutshell proppant came8 into of 15

being (Figure 7). On the basis of their previous work, Zoveidavianpoor investigated the
properties of epoxy coated coconut shell proppant [39]. The crushing rate of the obtained
coated proppant
proppant decreased
decreased fromto
from 2.12 2.12 to 0.16%,
0.16%, the acid
the acid solubility
solubility andand turbidity
turbidity reduced
reduced to
to 1.8
1.8 and 38 respectively, the sphericity and roundness increased from 0.7
and 38 respectively, the sphericity and roundness increased from 0.7 to 0.8. to 0.8.

Figure7.7.Nutshell
Figure Nutshell(a)
(a)and
andcoated
coatednutshell
nutshell(b)
(b)proppant.
proppant.

Table 6. Properties of polymer coated bio-based nutshell proppant.

Apparent Crushing Acid Turbidity Sphericity and

Polymer Ref.
Density (g·cm−3) Rate (%) Solubility (%) (FTU) Roundness
Polymers 2022, 14, 5534 8 of 14

Table 6. Properties of polymer coated bio-based nutshell proppant.

Apparent Crushing Acid Turbidity Sphericity and

Polymer Ref.
Density (g·cm−3 ) Rate (%) Solubility (%) (FTU) Roundness
Coconut shell * 1.22–1.33 2.12/55 MPa 44 184 0.7
Palm shell * 1.16–1.19 4.22/55 MPa 52 190 0.7 [38]
Walnut shell * 1.14–1.25 7.0/55 MPa 47 188 0.7
Epoxy / 0.16/55 MPa 1.8 38 0.8 [39]
Phenolic 1.23 15/60 MPa Conductivity increased from 41.8 to 113.4 µm2 ·cm [40]
Phenolic 1.24 14.8/60 MPa / / 0.86 [41]
Phenolic/Epoxy / No crack under 60 MPa, water adsorption significantly reduced [42,43]
ULW-1.25 1.25 42 MPa can be tolerated at 79 ◦ C [35,36]
ULW-1.25 1.25 Conductivity ability was obviously improved 0.62 [11,44]
* Raw materials of nutshell.

In the investigation of coated nutshell, nutshell particles with 20~40 mesh was always
used. Phenolic resin coated nutshell particles was reported by Li and co-workers [40], the
obtained proppant possesses an apparent density of 1.23 g·cm−3 , the water adsorption
decreased from 30 to 17%, and the conductivity increased from 41.8 to 113.4 µm2 ·cm. Li
and co-workers [41] has also further investigated the coating times on the properties of
coated nutshell, the properties of water adsorption and compression deformation were
improved, the sphericity and roundness increased to 0.86. Coated nutshell with phenolic
resin impregnation and epoxy resin coating was reported by Huang [42,43], no obvious
crack was observed under 60 MPa, and the water adsorption decreased from 30.45 to 6.58%.
ULW-1.25 is the most popular commercial coated nutshell proppant [35,36], after
polymer coating the apparent density increased to 1.25 g·cm−3 , the sphericity and round-
ness increased from 0.5 to 0.62, and the closing pressure of 42 MPa can be tolerated at
79 ◦ C [11,44]. The simulation study shows that at the same injection concentration in
slickwater, the ULW-1.25 creates more propped area and longer propped distance than
natural sand, but the fracture conductivity is lower.

5. Polymer Composites Based Ultra-Low Density Proppant

Since the organic polymer has a density close or even lower than that of water, polymer
composites became the most promising ULDP for clean hydraulic fracturing. About two
decades ago, polymer composite based ULW-1.05 proppant was applied in the hydraulic
fracturing [11,44], which is a heat-treated nanopolymer microsphere with an apparent
density of 1.05 g·cm−3 . The sphericity and roundness of ULW-1.05 is greater than 0.9, the
acid solubility is less than 2%, the glass transition temperature of approximately 145 ◦ C, the
closing pressure of 55 MPa can be tolerated at 130 ◦ C [13]. The disadvantage of ULW-1.05
is that it is prone to deformation compared to traditional fracturing proppants, this can be
ascribed to the intrinsic elasticity of polymer.
As we all know, ultra-low density cross-linked polymer beads with very high spheric-
ity can be obtained with suspension polymerization, and this technology has been widely
used in the industry, such as the scale production of ion exchange resin [45] and chro-
matographic column packing [46]. In addition, the size of the proppant prepared with
suspension polymerization can be facile controlled by the stirring speed and dispersant
concentration [45,46]. This will benefit for the enhancing of conductivity in deep reser-
voirs, where small-size proppants are preferred since they can flow into narrower fractures
(Figure 8) [9].
What’s more, the comprehensive properties of cross-linked polymer composite beads
obtained from suspension polymerization can be improved by further chemical cross-
linking and incorporation with inorganic fillers. Therefore, proppant based on polystyrene
microspheres composite was reported by our group for the first time [47,48]. In the study,
graphite/polystyrene composite microspheres were prepared through suspension polymer-
ization, and the properties for proppant application were investigated, including density,
 of ULW-1.05 is that it is prone to deformation compared to traditional fracturing prop-
pants, this can be ascribed to the intrinsic elasticity of polymer.
As we all know, ultra-low density cross-linked polymer beads with very high sphe-
ricity can be obtained with suspension polymerization, and this technology has been
widely used in the industry, such as the scale production of ion exchange resin [45] and
Polymers 2022, 14, 5534 9 of 14
chromatographic column packing [46]. In addition, the size of the proppant prepared with
suspension polymerization can be facile controlled by the stirring speed and dispersant
concentration [45,46]. This will benefit for the enhancing of conductivity in deep reservoirs,
crushing rate, sphericity
where small-size and heat
proppants resistance.since
are preferred Now, thecan
they ULDP
floworiginated from fractures
into narrower polymer com-
(Fig-
posite based
ure 8) [9]. suspension polymerization has been widely studied and applied (Figure 9).

Figure 8. Hydraulic fracture propped with proppant of (a) large, (b) medium, (c) small size [9].

What’s more, the comprehensive properties of cross-linked polymer composite beads

obtained from suspension polymerization can be improved by further chemical cross-
linking and incorporation with inorganic fillers. Therefore, proppant based on polysty-
rene microspheres composite was reported by our group for the first time [47,48]. In the
study, graphite/polystyrene composite microspheres were prepared through suspension
polymerization, and the properties for proppant application were investigated, including
density, crushing rate, sphericity and heat resistance. Now, the ULDP originated from
polymer composite based suspension polymerization has been widely studied and ap-
plied (Figure 9).
Figure8.8.Hydraulic
Figure Hydraulicfracture
fracturepropped
proppedwith
withproppant
proppantofof(A)
(a) large,
large, (B)
(b) medium,
medium, (C)
(c) small
small size
size [9].
[9].

What’s more, the comprehensive properties of cross-linked polymer composite beads

obtained from suspension polymerization can be improved by further chemical cross-
linking and incorporation with inorganic fillers. Therefore, proppant based on polysty-
rene microspheres composite was reported by our group for the first time [47,48]. In the
study, graphite/polystyrene composite microspheres were prepared through suspension
polymerization, and the properties for proppant application were investigated, including
density, crushing rate, sphericity and heat resistance. Now, the ULDP originated from
polymer composite based suspension polymerization has been widely studied and ap-
plied (Figure 9).
Figure 9. ULDP Figure
based on polymer
9. ULDP composite
based beads.
on polymer composite beads.

5.1. Ultra-Low
5.1. Ultra-Low Density Proppant Density
BasedProppant Based on Polystyrene
on Polystyrene
Since polystyreneSince polystyrene
(PS) has excellent (PS)compressive
has excellentstrength
compressive
and wear strength and wear
resistance, resistance, cross-
cross-
linked PS microspheres have been widely studied and applied in ULDP (Table 7). In order (Table 7). In
linked PS microspheres have been widely studied and applied in ULDP
order to reveal
to reveal the performance the PS
of pure performance
microspheres of directly
pure PSused microspheres
as ULDP, directly used as ULDP, pure
pure PS micro-
PS microspheres
spheres was synthesized through was synthesized
suspension through suspension
polymerization polymerization
using styrene as monomer using styrene as
monomer
and divinylbenzene and divinylbenzene
as cross-linking [49]. Theas cross-linking
obtained pure PS [49]. The obtained
microspheres haspure PS microspheres
an ap-
g·cm −3 , the crushing rate is 3.01% under 69 MPa,
parent densityhas an apparent
as low as 1.03 g·cmdensity as low
−3, the as 1.03
crushing rate is 3.01% under 69 MPa, and the
and the sphericity is greater than 0.9. In
sphericity is greater than 0.9. In order to further improve the comprehensiveorder to further improve the comprehensive
performance
performance
Figure 9. ULDP of pure
based PS
on proppant,
polymer inorganic
composite filler
beads.
of pure PS proppant, inorganic filler filled composites microspheres proppant has beenfilled composites microspheres proppant
has been developed rapidly. In our previous work, graphite/PS composite microspheres
5.1. prepared
was Ultra-Lowthrough
Density Proppant
suspension Based on Polystyrene[47]. Novel ULPD was obtained with a
polymerization
low density of 1.05 g · cm −3 , a crushing rate significantly reduced to 1.3%, a decomposition
Since polystyrene (PS) has excellent compressive strength and wear resistance, cross-
temperature of 5% reached to 325 ◦
linked PS microspheres have beenC.widely
Simultaneously,
studied and SiO 2 /PS composite
applied in ULDP microspheres was
(Table 7). In order
prepared with increased apparent density of 1.07 g · cm −3 , the decomposition temperature
to reveal the performance of pure PS microspheres directly used as ULDP, pure PS micro-
of 5% increased
spheres to 372 ◦ C through
was synthesized [48]. In addition,
suspension PS polymerization
composite withusing incorporation
styrene asofmonomer
low cost
carbon black
and divinylbenzene(CB) was as cross-linking [49]. The obtained pure PS microspheres hasdensity
reported [50], the obtained proppant possesses an apparent an ap-
of 1.08 g · cm −3 . Due to its excellent properties [51,52], graphene incorporated PS composite
parent density as low as 1.03 g·cm−3, the crushing rate is 3.01% under 69 MPa, and the
microspheres was also
sphericity is greater than investigated
0.9. In orderintoour previous
further improve work the[53], the performance
comprehensive of the
performance
obtained proppant is similar to ULW-1.05. Carbon nanotube
of pure PS proppant, inorganic filler filled composites microspheres proppant has beenincorporated PS composite
microspheres was reported by Tasque and co-workers [54], the crushing rate as low as 1.7%
under 138 MPa, and the acid solubility is also very low.
Silica fume (SF)/PS composite microspheres was also investigated in our previous
work [55], the obtained proppant has low acid solubility of 1.75%, and high contact angle
of 124.5◦ . In addition, commercial strong acid PS cation exchange resin has also been
used for the preparation of ULDP [56], which has been cross-linked with heavy metal
cations such as iron ion and barium ion, the apparent density of the obtained proppant
increased to 1.56 g·cm−3 , and the crushing rate decreased to 0.6% at 52 MPa. Based on
the graphite/PS proppant [48], coated ULDP proppant was prepared with coating of
Polymers 2022, 14, 5534 10 of 14

epoxy/phenolic resin [57,58]. The density of the obtained coated proppant increased from
1.05 to 1.08 g·cm−3 , and the acid solubility decreased to 0.11%.

Table 7. Properties of PS based ULDP.

Apparent Sphericity and

Samples Crushing Rate (%) Acid Solubility (%) Ref.
Density (g·cm−3 ) Roundness
PS 1.03 3.01/69 MPa / >0.9 [49]
G/PS 1.05 1.3/69 MPa / 0.94 [47]
SiO2 /PS 1.07 3.0/69 MPa / 0.95 [48]
PolymersCB/PS 1.08
2022, 14, x FOR PEER REVIEW 2.0/69 MPa / >0.9 [50]
11 of 15
Graphene/PS 1.05 0.45/52 MPa / 0.95 [53]
CNT/PS 1.05 1.7/138 MPa 0.9 0.9 [54]
SF/PS 1.05 1.0/52 MPa 1.75 >0.9 [55]
Metal/PS 1.56 Recently, the0.6/52 MPaof inorganic fillers
influence / such as graphite>0.9 [56] (CB)
(G) [61], carbon black
Coated-G/PS 1.08 2.22/69
[62], silica fume (SF) [63]MPa 0.11 on the performance
and fly ash (FA) [64] >0.9of PMMA based
[48,57,58]
ULDP
has been deeply investigated by our group. All of the obtained ULDP has an apparent
density
5.2. less than
Ultra-Low 1.25 Proppant
Density g·cm−3, the crushing
Based rate is no
on Polymethyl more than 3% and the sphericity is
Methacrylate
greater than 0.9, as well as excellent corrosion
Since polymethyl methacrylate (PMMA) has high modulus resistance and low turbidity.
and excellent chemical
As shown in Figure 10, the PMMA composited
resistance, cross-linked PMMA microspheres have also been widely of polar aliphatic chains,and
studied which pos-
applied
sesses good flexibility and strong intermolecular interaction, leading
in ULDP (Table 8). In the investigation of Huang and co-workers [59], silane coupling to the high modulus
and low
agent A151abrasion
(vinyl resistance of PMMA
triethoxysilane) was [65,66].
added in On the
the other hand,ofthe
preparation PS composited
cross-linked PMMA of
nonpolar aromatic
microspheres with chains, which
suspension possesses rigidThe
polymerization. structure
A151 canandnot
weak intermolecular
only covalent linkedinter-
to
action, making the PS has a low modulus and high abrasion resistance
the cross-linked PMMA through the addition polymerization of double bond, but also can [67,68]. In order to
make up for the shortcomings of homopolymer [69–71], ULDP based
further cross-linked with the hydrosis and polycondensation of ethoxy, which can form a on FA incorporated
poly(St-co-MMA)
strong composite
inorganic coating on the microsphere was synthesized
surface. In another andbark
report, pine characterized
(PB) was used (Figure 11)
for the
[72]. In addition, ULDP based on acrylonitrile (AN) and vinyl acetate
preparation of ULDP with low cost [60], the obtained proppant has an apparent density as (VA) copolymer
microsphere
low as 1.02 g·cmhas−3also
, andbeen
onlyreported, the obtained
slight deformation wasproppant
observed has a good
within 5 minself-suspension
under 69 MPa.
ability [9].
Recently, the influence of inorganic fillers such as graphite (G) [61], carbon black
(CB) [62], silica fume (SF) [63] and fly ash (FA) [64] on the performance of PMMA based
Table 8.has
ULDP Properties of PMMA
been deeply based ULDP.by our group. All of the obtained ULDP has an
investigated
apparent density less Rate
than 1.25 g·cm −3 , the crushing rate is no more than 3% and the
Apparent Crushing Acid Solubility Turbidity Sphericity and
Samples sphericity is greater than 0.9, as well as excellent corrosion resistance and low turbidity. Ref.
Density (g·cm−3) (%) (%) (FTU) Roundness
As shown in Figure 10, the PMMA composited of polar aliphatic chains, which pos-
A151/PMMA 1.08 6.3/69 MPa / / >0.9 [59]
sesses good flexibility and strong intermolecular interaction, leading to the high modulus
PB/PMMA 1.02 5 min/69 MPa / /
and low abrasion resistance of PMMA [65,66]. On the other hand, the PS composited of >0.9 [60]
non-
G/PMMA 1.06 3.0/69 MPa 0.08 35 >0.9
polar aromatic chains, which possesses rigid structure and weak intermolecular interaction, [61]
CB/PMMA 1.23
making the PS 2.44/69
has a lowMPamodulus and 0.08high abrasion33 >0.9In order to[62]
resistance [67,68]. make
SF/PMMA 1.16 2.2/69 MPa 2 /
up for the shortcomings of homopolymer [69–71], ULDP based on FA incorporated poly(St- >0.9 [63]
FA/PMMA 1.05
co-MMA) composite 3.0/69 MPa microsphere was 0.02synthesized and 54 characterized >0.9 [64] In
(Figure 11) [72].
FA/P(St-co-MMA) addition, ULDP
1.26 basedMPa
0.95/52 on acrylonitrile/(AN) and vinyl acetate/ (VA) copolymer
>0.9 microsphere
[72]
P(AN-co-VA) has also been reported,
1.04 0.2/52 MPa the obtained <1 proppant has a good / self-suspension
>0.9 ability [9].[9]

Figure 10.
Figure 10. Chemical structure
structure of
of PMMA
PMMA and
and PS.
PS.
Polymers 2022, 14, 5534 11 of 14

Figure 10. Chemical structure of PMMA and PS.

Figure11.
Figure 11.Schemes
Schemesof
ofthe
thesynthetic
syntheticprocess
processof
ofpoly(St-co-MMA)/FA
poly(St-co-MMA)/FA composite
composite proppant
proppant [72].
[72].

Table 8. Properties of PMMA based ULDP.

Apparent Crushing Rate Acid Solubility Turbidity Sphericity and

Samples Ref.
Density (g·cm−3 ) (%) (%) (FTU) Roundness
A151/PMMA 1.08 6.3/69 MPa / / >0.9 [59]
PB/PMMA 1.02 5 min/69 MPa / / >0.9 [60]
G/PMMA 1.06 3.0/69 MPa 0.08 35 >0.9 [61]
CB/PMMA 1.23 2.44/69 MPa 0.08 33 >0.9 [62]
SF/PMMA 1.16 2.2/69 MPa 2 / >0.9 [63]
FA/PMMA 1.05 3.0/69 MPa 0.02 54 >0.9 [64]
FA/P(St-co-MMA) 1.26 0.95/52 MPa / / >0.9 [72]
P(AN-co-VA) 1.04 0.2/52 MPa <1 / >0.9 [9]

6. Conclusions and Future Prospects

Proppant is the key materials for hydraulic fracturing, with the increase of low perme-
ability reservoir and the high requirements of environment protection, the demand for LDP
is growing rapidly, especially for the ULDP. However, the density of traditional natural
sand and synthetic ceramic proppant is too high, and the properties of sphericity, crushing
rate, acid solubility and turbidity is not ideal. Though the coating of high density proppant
can reduce the density to some extent, yet the obtained coated sand and coated ceramic
only can be regarded as LDP.
In order to obtain ULDP, organic matrix based materials was rapidly developed for
its construction, including nutshell and polymer composites. Though the nutshell based
proppant is renewable and cheap, yet the sphericity and compressive strength is very low,
the properties of acid solubility, turbidity and heat resistance is also not ideal. In addition,
the coating of nutshell also has limited effect on improving the performance. Based on
suspension polymerization, ultra-low density (less than 1.25 g·cm−3 ) polymer composite
microsphere with very high sphericity (more than 0.9) can be obtained. In addition, the
compressive strength and heat resistance of polymer composites based proppant can be
improved by chemical cross-linking and inorganic filler incorporation. Therefore, polymer
composite based ULDP will be the most promising candidate.
Now, PS and PMMA composite microsphere based ULDP has been widely investi-
gated. With the development of polymer composites, besides the low density and high
sphericity, polymer composite microsphere with improved crushing rate, acid solubility,
turbidity and heat resistance has also been reported, which has good application prospect
in the field of hydraulic fracturing. However, there are also some problems need to be
addressed in the investigation and application. Firstly, there are few researches about the
practical application performance of this kind of ULDP, especially for the conductivity.
Secondly, the cost of polymer materials is higher than that of sand, ceramic and nutshell.
Polymers 2022, 14, 5534 12 of 14

It is hoped that these problems can be solved in the future research, so the industrial
application of polymer composites base ULDP can be realized.

Author Contributions: Conceptualization, J.G. and T.C.; methodology, X.H.; software, T.L.; inves-
tigation, G.H.; formal analysis, Y.Z.; resources, G.H.; original draft preparation, J.G., T.C. and T.L.;
review and editing, Y.Z. and X.H.; project administration, T.C. All authors have read and agreed to
the published version of the manuscript.
Funding: This work was supported by grants from the National Natural Science Foundation of
China (51903080), Foundation of Hubei Provincial Department of Education (Q20222802, D20212801,
B2021223), Scientific Research Foundation of Hubei University of Science and Technology (BK202003,
2022T03, 2021ZX15, 2022ZX13).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

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