1 1 11 1 1 1 1 1 1 1 1 1 1 1 1 IIIIII IIIII 11 1 1 1 1 1 111 11111 11111 lllll 1 1 111 1 1 1 1 1 1 111 1 1 1 1 1 1 1 1 1 1 1 1 1 11 1 1 1 1 1 1 11 1

US 2 0 2 3 0 0 4 3 7 3 9 A l

o United States

5 Patent Application Publication to) Pub. No.: US 2023/0043739 A1

ZHAO et al. (43) Pub. Date: Feb. 9, 2023

(54) METHOD FOR PREPARING SILANE C04B 16112 (2006.01)

COUPLING AGENT/SILICA/PLANT FIBER C04B 20100 (2006.01)

COMPOSITE C04B 20110 (2006.01)

(52) U.S. Cl.

(71) Applicant: CHANGZHOU INSTITUTE OF CPC . . . . . . . . . . .. . . C04B 26132 ( 2 01 3 . 0 1 ) ; C04B 16102
TECHNOLOGY, Changzhou (CN)
( 2 01 3 . 0 1 ) ; C04B 16112 ( 2 0 1 3 . 0 1 ) ; C04B

2010068 ( 2 0 13 . 0 1 ) ; C04B 2011014 ( 2 0 1 3 . 01 ) ;

(72) Inventors: Li ZHAO, Changzhou (CN); Chenyi
C04B 2011051 ( 2 0 1 3 . 0 1 ) ; C04B 2011074
LIU, Changzhou (CN); Jie LI,
( 2 0 13 . 0 1 ) ; C04B 2lll/00017 ( 2 01 3 . 0 1 )
Changzhou (CN); Xiaoyun CAO,

Changzhou (CN); Xinping GUO, (57) ABSTRACT

Changzhou (CN); Rui ZHU,
A method for preparing a silane coupling agent/silica/plant
Changzhou (CN)
fiber composite includes the following steps: S l : pretreating

(73) Assignee: CHANGZHOU INSTITUTE OF plant fiber; S2: preparing hydrolysate of a silane coupling

TECHNOLOGY, Changzhou (CN) agent; S3: preparing a silane coupling agent/plant fiber

composite; S4: preparing a silica nanoparticle dispersion;

(21) Appl. No.: 17/883,282 and S5: preparing a silane coupling agent/silica nanopar­

ticle/plant fiber composite. Through the covalent interaction

(22) Filed: Aug. 8, 2022 among a silanol group (Si-OH) formed by hydrolysis of

the silane coupling agent, Si-OH of the silica, and a

(30) Foreign Application Priority Data hydroxyl group (-OH) on the surface of the plant fiber, the

present invention enables silica nanoparticles to be grafted

Aug. 6, 2021 (CN) 202110899668.4
on the surface of the plant fiber. Using a hydrophobic film

formed by the silane coupling agent, harmful ions are

Publication Classification
prevented from invading, and the volume stability of the

(51) Int. Cl. fiber is improved. Using the pozzolanic activity of the silica

C04B 26132 (2006.01) nanoparticles, the alkalinity and calcium hydroxide content

C04B 16102 (2006.01) around the fiber are reduced.

Patent Application Publication Feb. 9, 2023 Sheet 1 of 2 US 2023/0043739 Al

FIG. 1

FIG. 2
Patent Application Publication Feb. 9, 2023 Sheet 2 of 2 US 2023/0043739 Al

FIG. 3

�;:::::::,?'

ii!

ll!Jff

FIG. 4
US 2023/0043739 Al Feb.9,2023

METHOD FOR PREPARING SILANE Si-OH of the silica, and a hydroxyl group (-OH) on the

COUPLING AGENT/SILICA/PLANT FIBER surface of the plant fiber, the method enables silica nanopar­

COMPOSITE ticles to be firmly grafted on the surface of the plant fiber.

Using a hydrophobic film formed by the silane coupling

CROSS REFERENCE TO THE RELATED agent, harmful ions are prevented from invading, and the

APPLICATIONS volume stability of the plant fiber is improved. Using the

pozzolanic activity of the silica nanoparticles, the alkalinity

[0001] This application is based upon and claims priority
and calcium hydroxide content around the fiber are reduced,
to Chinese Patent Application No. 2 0 2 1 1 0 8 9 9 6 6 8 . 4 , filed on
a microstructure at the interface between the fiber and a
Aug. 6, 2021, the entire contents of which are incorporated
cement matrix is improved, and the corrosion resistance of
herein by reference.
the plant fiber in the cement matrix and the interfacial

bonding property between the fiber and the matrix are

TECHNICAL FIELD
synergistically improved. The method of the present inven­
[0002] The present invention relates to the technical field tion is simple and easy to operate, and is expected to be
of building materials, and in particular relates to a method
applied in the green building industry on a large scale to
for preparing a silane coupling agent/silica/plant fiber com­ reduce the carbon emission of buildings.
posite.
[0006] The present invention is achieved through the

following technical solutions:

BACKGROUND
[0007] A method for preparing a silane coupling agent/
[0003] Cement-based materials are currently the most silica/plant fiber composite, which includes the following
widely used building materials in the world, but they are
steps:
brittle and prone to cracking. Studies have shown that fiber
[0008] S l: pretreating plant fiber;
has a good inhibitory effect on cracking of cement-based
[0009] S2: preparing hydrolysate of a silane coupling
materials. Steel fiber and artificial synthetic fiber can
agent;
improve the toughness of concrete to a certain extent, but

also increase the cost of concrete. To effectively reduce the [0010] S3: preparing a silane coupling agent/plant fiber

cost of fiber reinforced concrete, researchers start to use composite: fully immersing the pretreated plant fiber in the

cheap, easily available, and widely distributed plant fiber in hydrolysate of the silane coupling agent, fishing the plant

nature to replace the traditional artificial synthetic fiber. The fiber out, and drying the plant fiber in the air to maintain the

activity of the silane coupling agent;

application of plant fiber to cement-based composite mate­

rials can improve toughness, promotes sustainable develop­ [0011] S4: preparing a silica nanoparticle dispersion; and

ment, has ecological effects and is in line with the major [0012] S5: preparing a silane coupling agent/silica nan­
strategy of developing a circular economy.
oparticle/plant fiber composite: spraying the silica nanopar­
[0004] A strong interfacial bonding property between fiber ticle dispersion onto the silane coupling agent/plant fiber
and a cement matrix is a necessary condition for a fiber­
composite, and drying the composite.
modified cement-based composite material to obtain high
[0013] Through the covalent interaction among a silanol
toughness. However, the interfacial bonding property
group (Si-OH) formed by hydrolysis of the silane coupling
between plant fiber and a cement matrix is insufficient, and
agent, Si-OH of the silica, and a hydroxyl group (-OH)
the plant fiber needs to be subjected to surface modification
on the surface of the plant fiber, the method of the present
to improve the interfacial bonding property between the
invention enables silica nanoparticles to be firmly grafted on
plant fiber and the cement matrix. The lack of corrosion
the surface of the plant fiber. Using a hydrophobic film
resistance of plant fiber in a cement-based composite mate­
formed by the silane coupling agent, harmful ions are
rial also limits its application in the field of building mate­
prevented from invading, and the volume stability of the
rials. Calcium hydroxide produced by cement hydration
plant fiber is improved. Using the pozzolanic activity of the
dissolves in water, making a pore solution of cement paste
silica nanoparticles, the alkalinity and calcium hydroxide
alkaline. An alkaline environment may dissolve hemicellu­
content around the fiber are reduced, a microstructure at the
lose and lignin in plant fiber, destroy the structure of the
interface between the fiber and a cement matrix is improved,
fiber, and reduce the strength and toughness of the fiber. In
and the corrosion resistance of the plant fiber in the cement
addition, calcium ions enter the internal pores of plant fiber
matrix and the interfacial bonding property between the fiber
and crystallize, making the fiber "mineralized", gradually
and the matrix are synergistically improved.
lose flexibility, become rigid, and prone to brittle fracture.
[0014] Specifically, the plant fiber may be selected from
Therefore, improving the corrosion resistance of plant fiber
sisal fiber, coir fiber and other plant fiber.
in the cement matrix and improving the interfacial bonding

property between the plant fiber and the cement matrix are [0015] Further, in step S l , the plant fiber is pretreated by

the prerequisites for replacing artificial synthetic fiber with the following steps:

plant fiber to toughen a cement-based composite material. [0016] S l - 1: cutting the plant fiber according to require­

ments of a cement-based composite material to be tough­

SUMMARY ened;

[0005] To solve the problems of insufficient corrosion [0017] S l - 2 : cleaning the surface of the cut plant fiber, that

resistance and interfacial bonding property of plant fiber in is, cleaning off impurities from the surface of the plant fiber

a cement matrix, the present invention provides a method for with clean water; and

preparing a silane coupling agent/silica/plant fiber compos­ [0018] S l - 3 : soaking the cleaned plant fiber in an alkaline

ite. Through the covalent interaction among a silanol group solution, washing the soaked plant fiber to a neutral state,

(Si-OH) formed by hydrolysis of the silane coupling agent, and drying the plant fiber.
US 2023/0043739 Al Feb.9,2023

[0019] Further, in step S1-3, the alkaline solution is an fiber, and sprayed again; the spraying process is repeated 2-5

NaOH or KOH solution with the pH of 13 - 1 4 ; the soaking times until the mass ratio of the plant fiber to the silica

time is 0 . 5 - 1 h; and the drying temperature is 60-80° C. nanoparticles is 1 g:(30-100) mg, wherein the mass of the

[0020] Further, in step S2, the hydrolysate of the silane plant fiber is the mass after pretreatment and drying; and the

coupling agent is prepared by the following steps: plant fiber is dried in a blast drying oven at 11 5 - 1 2 5 ° C. for

[0021] S2-1: dissolving the silane coupling agent in a 1 2 - 1 5 h to ensure formation of stable covalent bonds among

mixed system of absolute ethanol and deionized water, and the plant fiber, the silane coupling agent and the silica

stirring the mixed system evenly to obtain a mixed solution; nanoparticles.

and [0030] Beneficial effects of the present invention:

[0022] S2-2: adding glacial acetic acid to the mixed solu­ [0031] ( 1 ) The present invention uses a two-step method

tion to adjust the pH to an acidic state, and stirring the mixed to modify the plant fiber. The surface of the plant fiber is

solution to obtain the hydrolysate of the silane coupling firstly coated with the silane coupling agent, and then coated

agent. with the silica nanoparticles. If the hydrolysate of the silane

[0023] Further, the silane coupling agent in step S2-1 is coupling agent is compounded with the silica nanoparticles

any one selected from of KH550, KH560, KH570, and at first and then the plant fiber is immersed in the compound

KH792; the volume ratio of the absolute ethanol to the dispersion, the silanol group (Si-OH) formed by hydrolysis

deionized water is (4-10):1; and the concentration of the of the silane coupling agent and the Si-OH of the silica

silane coupling agent in the mixed solution is 0 . 1 - 1 . 0 mol/L. nanoparticles compete with each other when reacting with

[0024] Further, in step S2-2, 10-30 wt % of glacial acetic the hydroxyl group (-OH) on the surface of the plant fiber,

acid is added to the mixed solution to adjust the pH to 4-5, which affects film formation of the silane coupling agent on

and the mixed solution is electromagnetically stirred for the surface of the plant fiber, and greatly reduces the

0.5-2 h to obtain the hydrolysate of the silane coupling hydrophobic effect.

agent. [0032] (2) The present invention uses a natural air-drying

[0025] Further, in step S3, the silane coupling agent/plant method to dry the silane coupling agent/plant fiber compos­

fiber composite is prepared as follows: the pretreated plant ite, and can effectively avoid a condensation reaction of the

fiber is immersed in the hydrolysate of the silane coupling Si-OH group of the silane coupling agent in a high

agent and ultrasonically treated for 0 . 5 - 1 h to make the plant temperature environment, so that the activity of the silane

fiber fully immersed, and then the plant fiber is fished out coupling agent is maintained, and excess water is removed.

and dried in the air, and the bath ratio of the plant fiber [0033] (3) Instead of immersing the silane coupling agent/

immersed in the hydrolysate of the silane coupling agent is plant fiber composite into the silica nanoparticle dispersion,

(30-50): 1. Specifically, the plant fiber may be placed in a the method of the present invention uses a spraying method

ventilated place and dried in the air naturally in a lighted to spray the silica nanoparticle dispersion onto the surface of

environment; and the drying standard is that when the the silane coupling agent/plant fiber composite, so that the

surface is covered with absorbent paper, the absorbent paper silane coupling agent coating the surface of the plant fiber

is not significantly wetted. can be prevented from falling off due to secondary hydro­

[0026] Further, in step S4, the silica nanoparticle disper­ lysis.

sion is prepared as follows: the silica nanoparticles are [0034] (4) The present invention uses relatively high tem­

ultrasonically dispersed in deionized water to obtain the perature ( 11 5 - 1 2 5 ° C.) for drying the silane coupling agent/

silica nanoparticle dispersion. silica nanoparticle/plant fiber composite, so that Si-OH

[0027] Further, the concentration of the silica nanopar­ formed by hydrolysis of the silane coupling agent, Si-OH

ticles is 2-20 mg/mL; and the particle size of the silica on the surface of the silica nanoparticles, and OH on the

nanoparticles is 5 - 1 0 0 nm. surface of the plant fiber undergo a condensation reaction to

[0028] Further, in step S5, the silane coupling agent/silica form firm covalent bonds, and the surface of the plant fiber

nanoparticle/plant fiber composite is prepared as follows: can be stably coated with the silane coupling agent and the

the silane coupling agent/plant fiber composite dried in the silica nanoparticles.

air in step S3 is spread on gauze, a spray bottle is filled with [0035] (5) The silica nanoparticles coating the surface of

the silica nanoparticle dispersion, and the silane coupling the plant fiber have high activity and can undergo a pozzo­

agent/plant fiber composite on the gauze is evenly sprayed lanic reaction with the hydration product calcium hydroxide,

once in a spraying mode, and then evenly sprayed again so that the alkalinity and calcium hydroxide content around

from the back of the gauze; the spraying process is repeated the fiber can be reduced, the erosion of the plant fiber can be

2-5 times until the mass ratio of the plant fiber to the silica reduced, and the resulting calcium silicate hydrate can

nanoparticles is 1 g:(30-100) mg; and the composite is dried improve the interfacial bonding property between the plant

at 11 5 - 1 2 5 ° C. for 1 2 - 1 5 h. fiber and a cement matrix, which can be used for toughening

[0029] Specifically, in step S5, the silane coupling agent/ a cement-based composite material.

silica nanoparticle/plant fiber composite is prepared as fol­ [0036] (6) The silane coupling agent forms a hydrophobic

lows: the silane coupling agent/plant fiber composite dried film on the surface of the plant fiber, which can reduce the

in the air in step S3 is spread on gauze, and the silane hydrophilicity of the plant fiber. On the one hand, the

coupling agent/plant fiber composite on the gauze is evenly adsorption of a pore solution of cement paste can be

sprayed once in a spraying mode using a spray bottle filled reduced, and the corrosion resistance of the plant fiber is

with the silica nanoparticle dispersion, and evenly sprayed improved. On the other hand, the volume stability of the

again from the back of the gauze; in order to increase the plant fiber is improved, a micro structure of a transition zone

amount of the silica nanoparticles coating the surface of the at the interface between the plant fiber and a cement matrix

plant fiber, after being dried in the air at room temperature is optimized, and the interfacial bonding property between

for 30-60 min, the gauze is shaken to change the angle of the the fiber and the matrix is improved.
US 2023/0043739 Al Feb.9,2023

[0037] (7) In the silane coupling agent/silica nanoparticle/ sisal fiber was rinsed repeatedly with clean water to a neutral

plant fiber composite prepared by the present invention, the state, and dried in a blast dryer at 60° C. to complete

synergistic effect of the silane coupling agent and the silica pretreatment of the sisal fiber.

nanoparticles coating the surface of the plant fiber can [0049] S2: Hydrolysate of a silane coupling agent was

improve the corrosion resistance of the plant fiber in the prepared; and the preparation of the hydrolysate of the silane

cement matrix, and improve the bonding property at the coupling agent included the following steps:

interface between the plant fiber and the cement matrix, [0050] S 2 - 1 : a silane coupling agent KH550 was dissolved

which makes the plant fiber have great application prospects in a mixed system of absolute ethanol and deionized water,

in toughening and arresting crack of cement-based materi­ and the mixed system was stirred evenly to obtain a mixed

als. solution, wherein the volume ratio of the absolute ethanol to

the deionized water was 4 : 1 , and the concentration of the

BRIEF DESCRIPTION OF THE DRAWINGS KH550 in the mixed solution was 0.2 mol/L; and

[0051] S2-2: 30 w t % of glacial acetic acid was added to

[0038] To illustrate the technical solutions of the embodi­
the mixed solution to adjust the pH to 4.66, and the mixed
ments of the present invention more clearly, the accompa­
solution was stirred electromagnetically for 1 h to obtain the
nying drawings used in the description of the embodiments
hydrolysate of the silane coupling agent (KH550).
are briefly introduced below. Obviously, the accompanying

drawings in the following description are only some [0052] S3: A silane coupling agent/sisal fiber composite

embodiments of the present invention. For those skilled in was prepared: 6.0 g of the pretreated sisal fiber was

immersed in 200 mL of the hydrolysate of the silane

the art, other drawings can also be obtained from the

accompanying drawings without any creative effort. coupling agent (KH550) and ultrasonically treated for 0.5 h

to fully immerse the sisal fiber; then the sisal fiber was fished
[0039] FIG. 1 is a scanning electron microscope (SEM)

image of sisal fiber subjected to pretreatment in Embodi­ out and put on gauze to drain excess water, and placed in a

ment 1 of the present invention. ventilated place to dry naturally for 24 h to obtain the silane

[0040] FIG. 2 is an SEM image of a silane coupling coupling agent/sisal fiber composite.

agent/silica nanoparticle/sisal fiber composite in Embodi­ [0053] S4: A silica nanoparticle dispersion was prepared:

ment 1 of the present invention. 0.3 g of silica nanoparticles was added to 20 mL of deion­

[0041] FIG. 3 is an SEM image of the silane coupling ized water, first electromagnetically stirred for 0.5 h, and

agent/silica nanoparticle/sisal fiber composite subjected to then ultrasonically vibrated for 30 min at the power of 600

high-speed shearing treatment. W to obtain the silica nanoparticle dispersion; then a 100 mL

[0042] FIG. 4 is an SEM image of the silane coupling spray bottle with a scale was filled with the silica nanopar­

agent/silica nanoparticle/sisal fiber composite subjected to ticle dispersion for performing spraying in the next step,

ultrasonic vibration treatment. wherein the diameter of the silica nanoparticles was 50 nm.

[0054] S 5 : A silane coupling agent/silica nanoparticle/sisal

DETAILED DESCRIPTION OF THE fiber composite was prepared: the silane coupling agent/sisal

EMBODIMENTS fiber composite dried in the air in step S3 was spread on the

gauze, and the silane coupling agent/sisal fiber composite on

[0043] The technical solutions in the embodiments of the
the gauze was evenly sprayed once in a spraying mode using
present invention will be clearly and completely described
the spray bottle filled with the silica nanoparticle dispersion,
below with reference to the accompanying drawings in the
and evenly sprayed again from the back of the gauze; in
embodiments of the present invention. It is obvious that the
order to increase the amount of the silica nanoparticles
described embodiments are only a part of the embodiments
coating the surface of the sisal fiber, after being dried in the
of the present invention and not all of the embodiments. The
air at room temperature for 30 min, the gauze was shaken to
following description of at least one exemplary embodiment
change the angle of the fiber, and sprayed again; the total
is merely illustrative in nature and is in no way intended to
spray volume on the front and back sides every time was 5
limit the present invention and application or uses thereof.
mL, the spraying process was repeated 4 times, 20 mL of the
Based on the embodiments of the present invention, all other
silica nanoparticle dispersion was completely sprayed on the
embodiments obtained by those of ordinary skill in the art
surface of the sisal fiber, and the mass ratio of the sisal fiber
without creative efforts shall fall within the protection scope
to the silica nanoparticles was 1 g/50 mg; after spraying, the
of the present invention.
sisal fiber was dried in a blast drying oven at 120° C. for 1 5

h to obtain the silane coupling agent/silica nanoparticle/sisal

Embodiment 1
fiber composite.

[0044] A method for preparing a silane coupling agent/ [0055] Test:

silica/plant fiber composite (the plant fiber was sisal fiber) [0056] The pretreated sisal fiber in Embodiment 1 was

included the following steps: tested with a scanning electron microscope (SEM), and the

[0045] S l: The sisal fiber was pretreated; and the pretreat­ result was shown in FIG. 1. The silane coupling agent/silica

ment process included the following concrete steps: nanoparticle/sisal fiber composite obtained in Embodiment

[0046] S l - 1 : the sisal fiber was cut into short fiber with the 1 was tested by the SEM, as shown in FIG. 2.

length of 100 mm according to requirements of a cement­ [0057] A high-speed shear test was performed on the

based composite material to be toughened; silane coupling agent/silica nanoparticle/sisal fiber compos­

[0047] S l - 2 : the cut sisal fiber was cleaned off mud, sand ite obtained in Embodiment 1 . The high-speed shear test was

and debris on the surface with clean water, and dried in a to simulate the stress condition of fiber in a stirring pot, and

blast dryer at 60° C.; and the specific method was as follows: two-thirds of water by

[0048] S l - 3 : the cleaned sisal fiber was put in 0 . 1 5 mol/L volume was added to a beaker, the prepared silane coupling

of NaOH solution and soaked for 30 min; and the soaked agent/silica nanoparticle/sisal fiber composite was added, a
US 2023/0043739 Al Feb.9,2023

magneton was added, and high-speed shearing was per­ to fully immerse the coir fiber; then the coir fiber was fished

formed for 10 min. Then the silane coupling agent/silica out and put on gauze to drain excess water, and placed in a

nanoparticle/sisal fiber composite was taken out and dried, ventilated place to dry naturally for 24 h to obtain the silane

and shedding of SiO, particles from the fiber surface was coupling agent/coir fiber composite.

observed under an electron scanning microscope. The [0069] S4: A silica nanoparticle dispersion was prepared:
results were shown in FIG. 3 . It can be seen from FIG. 3 that
0.3 g of silica nanoparticles was added to 30 mL of deion­
the SiO, particles stably coat the surface of the plant fiber. ized water, first electromagnetically stirred for 0.5 h, and
[0058] An ultrasonic vibration test was performed on the then ultrasonically vibrated for 30 min at the power of 600
silane coupling agent/silica nanoparticle/sisal fiber compos­
W to obtain the silica nanoparticle dispersion; then a 100 mL
ite obtained in Embodiment 1. Ultrasonic vibration treat­
spray bottle with a scale was filled with the silica nanopar­
ment is a commonly used dispersion method for nanoma­
ticle dispersion for performing spraying in the next step,
terials, and nanoaggregates are dispersed under the vibration wherein the diameter of the silica nanoparticles was 1 0 nm.
of ultrasonic waves. In the test, whether silica nanoparticles
[0070] S 5 : A silane coupling agent/silica nanoparticle/coir
on the modified fiber surface were stable under the action of
fiber composite was prepared: the silane coupling agent/coir
ultrasonic vibration was verified by an ultrasonic method,
fiber composite dried in the air in step S3 was spread on the
and the specific method was as follows: two-thirds of water
gauze, and the silane coupling agent/coir fiber composite on
by volume was added to a beaker, and the modified fiber was
the gauze was evenly sprayed once in a spraying mode using
added and vibrated in an ultrasonic vibrator at 600 W for 1 0
the spray bottle filled with the silica nanoparticle dispersion,
min. Then the modified fiber was taken out and dried, and
and evenly sprayed again from the back of the gauze; in
shedding of silica particles from the fiber surface was
order to increase the amount of the silica nanoparticles
observed under an electron scanning microscope. The
coating the surface of the coir fiber, after being dried in the
results were shown in FIG. 4. It can be seen from FIG. 4 that
air at room temperature for 60 min, the gauze was shaken to
the silica particles stably coat the surface of the plant fiber.
change the angle of the fiber, and sprayed again; the total
[0059] The method of the present invention focuses on
spray volume on the front and back sides every time was 10
"stable coating", and the above shearing and ultrasonic
mL, the spraying process was repeated 3 times, 30 mL of the
vibration tests are destructive tests performed on the com­
silica nanoparticle dispersion was completely sprayed on the
pounded fiber, because in the practice of concrete produc­
surface of the coir fiber, and the mass ratio of the coir fiber
tion, stirring and friction will both wear and damage the
to the silica nanoparticles was 1 g/75 mg; after spraying, the
coating on the fiber surface.
coir fiber was dried in a blast drying oven at 120° C. for 12

h to obtain the silane coupling agent/silica nanoparticle/coir

Embodiment 2
fiber composite.

[0060] A method for preparing a silane coupling agent/ [0071] Through the covalent interaction among a silanol
silica/plant fiber composite (the plant fiber was coir fiber) group (Si-OH) formed by hydrolysis of the silane coupling
included the following steps:
agent, Si-OH of the silica, and a hydroxyl group (-OH)
[0061] S l: The coir fiber was pretreated; and the pretreat­ on the surface of the plant fiber, the method of the present
ment process included the following concrete steps:
invention enables silica nanoparticles to be mly grafted on
fir

[0062] S 1 - 1: the coir fiber was cut into short fiber with the the surface of the plant fiber. Using a hydrophobic film
length of 50 mm according to requirements of a cement­
formed by the silane coupling agent, harmful ions are
based composite material to be toughened; prevented from invading, and the volume stability of the
[0063] S l - 2 : the cut coir fiber was cleaned off mud, sand plant fiber is improved. Using the pozzolanic activity of the
and debris on the surface with clean water, and dried in a
silica nanoparticles, the alkalinity and calcium hydroxide
blast dryer at 60° C.; and content around the fiber are reduced, a microstructure at the
[0064] S l - 3 : the cleaned coir fiber was placed in 0.2 mol/L
interface between the fiber and a cement matrix is improved,
of NaOH solution and soaked for 30 min; and the soaked and the corrosion resistance of the plant fiber in the cement
coir fiber was rinsed repeatedly with clean water to a neutral matrix and the interfacial bonding property between the fiber
state, and dried in a blast dryer at 60° C. to complete and the matrix are synergistically improved. In the compos­
pretreatment of the coir fiber. ite prepared by the present invention, the synergistic effect
[0065] S2: Hydrolysate of a silane coupling agent was of the silane coupling agent and the silica nanoparticles
prepared; and the preparation of the hydrolysate of the silane coating the surface of the plant fiber can improve the
coupling agent included the following steps: corrosion resistance of the plant fiber in the cement matrix,

[0066] S 2 - 1 : a silane coupling agent KH792 was dissolved and improve the bonding property at the interface between

in a mixed system of absolute ethanol and deionized water, the plant fiber and the cement matrix, which makes the plant

and the mixed system was stirred evenly to obtain a mixed fiber have great application prospects in toughening and

solution, wherein the volume ratio of the absolute ethanol to arresting crack of cement-based materials.

the deionized water was 9:1, and the concentration of the

[0072] The above preferred embodiments of the present
KH792 in the mixed solution was 0 . 1 mol/L; and
invention are merely illustrative of the present invention,
[0067] S2-2: 1 0 w t % of glacial acetic acid was added to
and are not intended to limit the present invention. Any
the mixed solution to adjust the pH to 4.98, and the mixed
obvious changes or variations derived from the technical
solution was stirred electromagnetically for 0.5 h to obtain
solutions of the present invention are still within the pro­
the hydrolysate of the silane coupling agent (KH792).
tection scope of the present invention.
[0068] S3: A silane coupling agent/coir fiber composite
What is claimed is:
was prepared: 4.0 g of the pretreated coir fiber was

immersed in 150 mL of the hydrolysate of the silane 1. A method for preparing a silane coupling agent/silica/

coupling agent (KH792) and ultrasonically treated for 0.5 h plant fiber composite, comprising the following steps:
US 2023/0043739 Al Feb.9,2023

S l : pretreating a plant fiber to obtain a pretreated plant the group consisting of KH550, KH560, KH570, and

fiber; KH792; a volume ratio of the absolute ethanol to the

S2: preparing a hydrolysate of a silane coupling agent; deionized water is (4-10): 1 ; and a concentration of the silane

S3: fully immersing the pretreated plant fiber in the coupling agent in the mixed solution is 0 . 1 - 1. 0 mol/L.

hydrolysate of the silane coupling agent, fishing an 6. The method for preparing the silane coupling agent/

immersed plant fiber out, and drying a resulting plant silica/plant fiber composite according to claim 4, wherein in

step S2-2, 10-30 w t % of the glacial acetic acid is added to

fiber in the air to obtain a silane coupling agent/plant
the mixed solution to adjust the pH of the mixed solution to
fiber composite;

S4: preparing a silica nanoparticle dispersion; and 4-5, and the mixed solution is electromagnetically stirred for

0.5-2 h to obtain the hydrolysate of the silane coupling

S5: spraying the silica nanoparticle dispersion onto the

silane coupling agent/plant fiber composite, and drying agent.

a resulting composite to obtain a silane coupling agent/ 7. The method for preparing the silane coupling agent/

silica nanoparticle/plant fiber composite. silica/plant fiber composite according to claim 1, wherein in

2. The method for preparing the silane coupling agent/ step S3, the silane coupling agent/plant fiber composite is

prepared as follows: the pretreated plant fiber is immersed in

silica/plant fiber composite according to claim 1, wherein in

step S 1 , the plant fiber is pretreated by the following steps: the hydrolysate of the silane coupling agent and ultrasoni­

cally treated for 0 . 5 - 1 h to make the pretreated plant fiber

S l - 1: cutting the plant fiber according to requirements of

a cement-based composite material to be toughened to fully immersed, and then the immersed plant fiber is fished

obtain a cut plant fiber; out and dried in the air, wherein a bath ratio of the pretreated

plant fiber immersed in the hydrolysate of the silane cou­

S l - 2 : cleaning a surface of the cut plant fiber to obtain a

cleaned plant fiber; and pling agent is (30-50): 1 .

8. The method for preparing the silane coupling agent/

Sl-3: soaking the cleaned plant fiber in an alkaline

solution to obtain a soaked plant fiber, washing the silica/plant fiber composite according to claim 1, wherein in

step S4, the silica nanoparticle dispersion is prepared as

soaked plant fiber to a neutral state to obtain a washed

plant fiber, and drying the washed plant fiber to obtain follows: silica nanoparticles are ultrasonically dispersed in

the pretreated plant fiber. deionized water to obtain the silica nanoparticle dispersion.

9. The method for preparing the silane coupling agent/

3. The method for preparing the silane coupling agent/

silica/plant fiber composite according to claim 2, wherein in silica/plant fiber composite according to claim 8, wherein a

concentration of the silica nanoparticles in the silica nan­

step S 1 - 3 , the alkaline solution is an NaOH or KOH solution

with a pH of 1 3 - 1 4 ; a soaking time is 0 . 5 - 1 h; and a drying oparticle dispersion is 2-20 mg/mL; and a particle size of the

temperature is 60-80° C. silica nanoparticles is 5-100 nm.

1 0 . The method for preparing the silane coupling agent/

4. The method for preparing the silane coupling agent/
silica/plant fiber composite according to claim 1, wherein in
silica/plant fiber composite according to claim 1, wherein in
step S5, the silane coupling agent/silica nanoparticle/plant
step S2, the hydrolysate of the silane coupling agent is
fiber composite is prepared as follows: the silane coupling
prepared by the following steps:
agent/plant fiber composite obtained in step S3 is spread on
S2-1: dissolving the silane coupling agent in a mixed
a gauze, a spray bottle is filled with the silica nanoparticle
system of absolute ethanol and deionized water, and
dispersion, and the silane coupling agent/plant fiber com­
stirring a resulting mixed system evenly to obtain a
posite on the gauze is evenly sprayed once in a spraying
mixed solution; and
mode, and then evenly sprayed again from a back of the
S2-2: adding glacial acetic acid to the mixed solution to
gauze; a spraying process is repeated 2-5 times until a mass
adjust a pH of the mixed solution to an acidic state, and
ratio of a plant fiber of the silane coupling agent/plant fiber
stirring the mixed solution to obtain the hydrolysate of
composite to silica nanoparticles from the silica nanoparticle
the silane coupling agent.
dispersion is 1 g:(30-100) mg; and the resulting composite
5. The method for preparing the silane coupling agent/
is dried at 11 5 - 1 2 5 ° C. for 1 2 - 1 5 h.
silica/plant fiber composite according to claim 4, wherein

the silane coupling agent in step S2-1 is one selected from

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