560 Vol.28 No.3 YING Shuni et al: Chemical and Thermal Resistance of Basalt Fiber in Incl...

DOI 10.1007/s11595-013-0731-4

Chemical and Thermal Resistance of Basalt

Fiber in Inclement Environments

YING Shuni, ZHOU Xiaodong*

(State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China)

Abstract: To study the applicability of the basalt fiber through various experimental works in thermal
and chemical environments, glass fiber and carbon fiber were compared and discussed. The tensile strength
testing was used to investigate the corrosive resistance of basalt fiber, meanwhile, surface study by scanning
electron microscopy and microanalysis with complementary X-ray diffraction analysis (SEM/EDS) was
also used to ascertain the durability of basalt fiber. The basalt fiber showed better strength retention than the
glass fiber at relatively high temperature. Its tensile strength increased when exposed at 300 ℃ for several
hours, and still maintain about 70% of the initial strength at 400 ℃, whereas that of the glass fiber decreased
dramatically. The better stability of the basalt fiber was observed in hydrothermal and chemical environment.
The tensile strength of the basalt fiber increased by 20% after the immersion in boiling water and remained well
in acid solution, when it comes to glass fiber, the tensile strength decreased to some extent. Although the alkali
resistance of basalt fiber was poor at the initial stage, it shows better resistance than the glass fiber after long
time treatment.
Key words: basalt fiber; thermal stability; corrosion resistance; mechanical property

1 Introduction while Fe 2O 3 and FeO are only found in the basalt

Fiber reinforced composites enjoy widespread
use in diverse applications such as the construction
of aircraft, automobiles and reinforced concrete.
In common, the typical reinforcement of polymer
composites is glass fiber (ca. 85% of the total amount
of reinforcements). But the disadvantage of alkali
and temperature resistance restricts its advanced
application, in which other high strength and fire
resistant fibers have been used, such as aramid fibers,
graphite fibers and carbon fibers, which are limited in
application for their high price.
As a result of its production from rocks of
basic or medium compositions, the basalt fiber
reveals additional advantage in cost. There are many
similarities between the basalt fiber and the glass
fiber. The main components SiO2 and A12O3 are both
dominant in basalt and E-glass fiber. The E-glass fiber
shows a much higher contribution of CaO and B2O3,
©Wuhan University of Technology and SpringerVerlag Berlin Heidelberg 2013
(Received: June 19, 2011; Accepted: May 9, 2013)
YING Shuni(应淑妮): Ph D; E-mail: shiny595@hotmail.com
* Corresponding author: ZHOU Xiaodong(周晓东): Prof.; Ph D;
E-mail: xdzhou@ecust.edu.cn
fiber[1]. Owing to its similar mechanical performance
to the glass fiber, the basalt fiber had also been
used as a reinforcing material[2-5].A combination of
physicochemical and mechanical properties allows
its use as a kind of reinforcing filler for a broad range
of composites, such as the basalt fiber reinforced
cement and other parts. The basalt fiber has better
high temperature performance, owing to the very wide
operation temperature ranges from 269 to 700 ℃,
and as for the glass fiber, it ranges only from 60 to
500 ℃. Besides, the basalt fiber shows the advantage
of hygroscopicity, incombustibility and heat insulation.
The application of the basalt fiber for a structural
strengthening material, such as flame retardant, heat
insulation materials at fire and aerospace and others
serving in inclement environments, is highly expected.
The corrosion resistance of composites relates
to the matrix, interface and reinforcement. Whether
the basalt fiber as a reinforcement material can appear
better mechanical stability in inclement environments,
especially in high temperature and corrosive solutions
attracts our attention. There are few studies for the
chemical and thermal durability of the basalt fiber[6-8].
Thus the aim of this paper is to study the durability
 Journal of Wuhan University of Technology-Mater. Sci. Ed.
of the basalt fiber in inclement environments. In view
of stability analogy between basalt fiber and E-glass
fiber, several experiments were carried out to examine
water-resistance, acid-resistance, alkali-resistance
and thermal stability of basalt fiber. The results may
provide fundamental information for the application
of the basalt fibers as a strengthening material. The
carbon fiber and the glass fiber were also tested for the
comparison purposes.
2 Experimental
2.1 Materials
Basalt fiber (CBF13-800) was provided by
Mudanjiang Co. Ltd. (China). Glass fiber (E-glass 988)
was generally supplied by Jushi Group Co. Ltd. (China).
Carbon fiber (T-300) was produced by Toray Co. Ltd.
(Japan). The diameter of single fiber was about 13 μm
for both basalt fiber and E-glass fiber, and 8 μm for
carbon fiber. All other reagents were analytical grade
and used as received.
2.2 Fiber treatment
To investigate the thermal stability of basalt fiber,
the tensile strength of basalt fiber was measured after
the fibers were subjected to high temperatures 300,
400, 500 and 600 ℃ in a muffle furnace, respectively
at selected time intervals. Glass fiber and carbon
fiber were treated under the same conditions for the
comparison.
The aim of the second series of experiments is
to investigate the corrosion protection performance
of basalt fiber in water, acid and alkali environments.
Before the treatment, the basalt fiber and glass fiber
were calcined at 300 ℃ for 3 h and 400 ℃ for 2 h in
muffle furnace to remove the additions on the fiber
surface. Then the fibers were immersed in water,
sodium hydroxide and hydrochloric acid respectively
at selected time intervals, followed by washing with
deionized water for several times and dried in air.
The difference of corrosion protection between room
June 2013 561
temperature and high temperature was considered,
and the fiber treatments were performed both at room
temperature and at 100 ℃.
2.3 Tensile testing
After each treatment, the tensile strength of basalt
filament was tested by a single-fiber testing machine
(the Second Spin Machine of Changzhou Co., Ltd.,
YG004A) in accordance with GB/T9997-1988. Using
a 50 CN capacity actuator, tensile load was applied on
the filaments at 20 mm clamp distance under a constant
tensile speed of 2 mm/min. Each value is an average of
25 measurements.
2.4 Surface observation and element analysis
The fiber surfaces were observed after coated
with a gold layer to avoid charging under the electron
beam by a scanning electron microscope (SEM), JEOL,
JSM-6360LV. Furthermore, the distribution of elements
on the fiber surface was determined by EDAX Falcon
EDS X-ray spectrometer attached to the SEM system
mentioned above. For the EDS technique, a relatively
large area was measured in order to obtain an average
composition representative of the entire surface.
3 Results and discussion
3.1 High temperature resistance
Several kinds of fibers(basalt, E-glass and carbon
fiber) were treated at high temperatures for various
time and their tensile strength variations are shown in
Table 1. Before the high temperature treatment,
the strength of the basalt fiber and E-glass fiber
shows similar value, however, that of carbon fiber is
comparatively higher. When the fibers were treated at
300 ℃, the strength variations were not significant in
initial stage, but then showed some differences after
longer time. When the treatment was kept for 4 hours
or more, the strength of basalt fiber increased, whereas
that of carbon fiber maintains and glass fiber slightly
decreased. When the temperature rose to 400 ℃, the
strength reduction in basalt and glass fibers became
562 Vol.28 No.3 YING Shuni et al: Chemical and Thermal Resistance of Basalt Fiber in Incl...
distinctive, while the carbon fiber’s strength still
practically unchanged. However the basalt fiber had
better strength retention than the E-glass fiber. When
the temperature increased to 600 ℃, all the tensile
strength of the fibers decreased gradually. The strength
variation of the fibers confirms that the basalt fiber has
better resistance against high-temperature than E-glass
fiber.
The material characteristics of natural basalt
rocks, which nucleate at high temperature, result
in high thermal stability of basalt fibers. The basalt
rocks, however, do not require but produce a natural
nucleating agent such as Fe 3O 4 during the melting
process. Nucleating agents are necessary to obtain
similar micro-structure, thus bring the advantages over
other fibers. The beginning of crystallization is mainly
determined by iron oxides. When the fiber was heated
below 300 ℃, the fiber structure was reformed around
the nucleating agents, which ensures the thermal
stability of the basalt fiber[9]. However, when the fiber
was deposited at higher temperature, the nicks on the
fiber were formed from the oxygenation of a portion of
metal particles, which declined the tensile strength of
fibers.
3.2 Water-resistance
The mass loss of basalt fiber after immersed
in boiling water is illustrated in Fig.1. The relative
percentage weight was obtained by calculating the total
weight of fibers, and relating the amount of each cation
leached to its total amount presented in the original
fibers. As the basalt fiber has a similar composition to
E-glass fiber, there are similarities in some respects
between the two fibers. When glass fiber is contacting
with water, some alkaline ions enter into the internal
structure of glass fiber, and then exchange some ions in
the glass fiber’s network structure.
The silicon hydroxyl groups (Si-OH) are formed
after the Si-O-M bond on the surface broke down
(Eq.(1)). This process is also called leaching in the
literature [7], which is exacerbated by the quantity
of alkalis presented in the glass structure and the
hydrothermal environment. If the pH value of the
solution exceeds 9, the bonds of Si-O-Si and Si-O-M
(M=Na, K, Fe, Mg) are affected[10]. The process that
the hydroxide ion breaks the Si-O-Si bond is shown in
Eq.(2). The byproduct of the preceding equation, SiO2,
can dissociate another water molecule as shown in
Eq.(3).These actions can be combined and was shown
in Eq.(4). The reaction fiber cracks were generated,
which degrades the fiber strength and can result in a
premature fracture or a rupture of the glass fiber and
basalt fiber.
(1)
(2)
(3)
(4)
Fig.1 shows that basalt fiber can keep 99% of its
original weight after immersing in boiling water for
24 h, which is due to its high resistance to the water.
When water further acted on the fiber, a uniform high-
silica layer was formed on the fiber surface, commonly
known as a protective layer. This film has a certain
level of sturdiness while at the same time has a strong
absorption capacity, thus further fiber destruction is
slowed down.
Fig.2(a) shows the strength reduction of fibers
after treated in water at room temperature. It was
found that the change of both the glass fiber and the
basalt fiber was slight. The literature indicated the
developing accelerated test methods can simulate long-
term behavior of these materials within a practical
time frame in the laboratory[11]. Elevated temperatures
were used to accelerate the reaction with water so that
the long-term performance of the materials could be
extrapolated by the accelerated test results. Fig.2(b)
presents the strength variation of fibers treated in
boiling water. With the continuance of the reaction, the
tensile strength of basalt fiber increases by 20% while
decreases to some extent for glass fibers, indicating
basalt fiber has an excellent hydrothermal stability.
During the reaction, the silica-rich film was formed on
the surface and covers the micro-crack on the fiber. As
a result, the probability of fiber rupture was reduced,
and the strength of the fibers rose.
 Journal of Wuhan University of Technology-Mater. Sci. Ed.
3.3 Acid-resistance
The tensile behavior contrast of basalt and
glass fibers after chemical treatment has been studied
preliminary[12,13]. More experimental data and reaction
mechanism will be discussed in the paper. The
proposed mechanism of corrosion is an ion exchange
reaction in which metal ions on the fiber surface are
replaced by hydrogen ions from the acid. This is
enhanced by complex formation of the leached cation
with the anion in the acid solution. Once exposed to
acid mediums, the fibers containing alkalis (Na+, K+,
Ca2+, Al3+) become prone to chemical attack[14]. Ions
are leached into solution from the fibers by an ion
exchange mechanism as denoted by Eq. (5).
(5)
Fig.1 shows, in 1 mol/L HCl solution, basalt
fibers undergo a fast and then slow weight loss. It is
considered that the initial dissolution rate of ions is
quite large due to the high activity of H+ in the solution,
but as the dissolution preceded, the rate decreases and
eventually reaches equilibrium.
The Fig.3 shows the strength variation of fibers
in 1 mol/L HCl solution at room temperature and
100 ℃. The basalt fiber shows good strength retention
in hydrochloric acid solution at room temperature
and the strength even increased when the fiber
was immersed in the acid solution at 100 ℃ for
6 h, but the strength of glass fiber deeply decreased
June 2013 563
after the treatment both at room temperature and
100 ℃. The reaction process of basalt fiber in the acid
solution can be divided into two stages. The first stage
was attributed to the dissolution of ultrafine particles
created during the sample grinding process, which
resulted in the decline of the fiber strength, and the
amount of major ions release followed the order Fe,
Mg > Si > Al > Ca [15,16].Meanwhile, hydration was
concurrent in the acid solution, the thickness of the film
on the fiber surface increased during the reaction, which
improves the acid resistance and prevent the strength
reduction of the basalt fibers. During the second stage,
the effect of H+ on the fiber became obvious and the
strength of fiber declined gradually.
3.4 Alkali-resistance
The attack of basalt fiber and glass fibers by
alkaline ions (OH), according to Eq.(2), is the process
564 Vol.28 No.3 YING Shuni et al: Chemical and Thermal Resistance of Basalt Fiber in Incl...
of dissolution of silica (SiO2), where the Si-OH forms
gel on the fiber surface while the Si-O dissolves in
solution [7]. Fig.1 indicates that the weight loss of
basalt fibers under alkali condition is larger than that
under acid condition, which was attributing to a large
dissolution of Si-O on the surface of basalt fiber.
Fig.4 shows the tensile strength variation of
glass fiber and basalt fiber immersed in 1 mol/L NaOH
solution at room temperature. The tensile strength of
glass fibers has no detectable change, while there is
some increase in basalt fiber strength. However, the
strength variation of basalt fiber seems much different
when the reactions take place at high temperature.
Fig.5 shows the strength loss of fibers exposed
to different concentration of alkali solutions at 100 ℃.
The corrosion of 1 mol/L NaOH solution is particularly
severe and the strength loss is obvious after 10 h. This
severe degradation is due to the high mobility of OH
ions[17]. The strength decline of the basalt fiber seems
slight after immersed in 2 mol/L NaOH solution, and
the strength even increased after 6 h alkali treatment.
As reaction kinetics study show, the reaction between
the basalt fiber and immersion medium is concentration
and temperature dependant, because the diffusion rate
of ions depends closely on the OH  concentration
and temperature. Fig.4 and Fig.5(a) show the tensile
strength of fibers reacted with 1 mol/L NaOH solution,
which can be considered the forepart of the curve of
Fig.5(b), that reacted with 2 mol/L NaOH solution. The
increase of the concentration leads to an acceleration
in the rate of reaction. The figures show the strength
decrease of basalt fiber at the initial stage is larger than
glass fiber, but the basalt fiber shows better strength
retention after long time treatment. The strength of
basalt fiber remains about 63.4% after treated in 2 mol/
L NaOH solution for 24 h, but only 54.5% for the glass
fiber.
The better alkalis resistance of basalt fiber may
be determined by the composition of the fibers. To
investigate the change of the basalt fiber structure
after alkali corrosion, surface element analysis was
performed using scanning electron microscopy and
microanalysis with complementary X-ray diffraction
analysis (SEM/EDS). Fig.6 shows the content of the
components on original basalt fiber, out layer and inner
layer of fibers after treated in 2 mol/L alkaline solution
at 100 ℃ for 6 h. The element of outer layer appears
to be different from inner layer and original fiber. The
concentrations of sodium, potassium and aluminum
reduced, respectively, due to their leaching by sodium
hydroxide solution. Accordingly, the relative content
of magnesium, iron, calcium and titanium increased
because they could not be dissolved effectively by
alkali solution.
Some researchers have attempted to study the
influences of the addition of various oxides on the
 Journal of Wuhan University of Technology-Mater. Sci. Ed.
chemical durability of silicate glass[1,18-20]. They found
that the addition of some oxides like Na2O, K2O and
Al 2O 3 could reduce their chemical resistance, but
other additions such as MgO, Fe2O3 and FeO could
improve it. When the basalt fiber is exposed in alkaline
solution, the main reaction follows Eq.(2). The four
oxygen atoms around the original bridge were replaced
by -OH, the Si-O skeleton was directly damaged,
and the surface structure desquamate led to the drop
of the fiber strength. Figs.7 shows the SEM images
of the basalt fiber after 1, 6, and 24 h of immersion
in 2 mol/L NaOH solution. At the initial stage, there
is pore structure on the surface of the fibers, which
resulted from the corrosion dissolution. Hydration was
accompanied during the reaction, and magnesium, iron
and calcium are easy to form hydroxide on the glass
surface according to Eq.(1). With the continuation of
the hydration reaction, the hydroxide film was formed,
which repaired the surface defects and prevented
the basalt fiber from the further damage to certain
extent, thus the strength increased when the fiber was
immersed for 6 h. The increase of the fiber strength
could be attributed to the protective film which filled up
the pore on the surface of fiber, which was showed in
morphologies after the immersion for 6 h as showed in
Fig.7(b). However, the protection was faint compared
to the deep destruction of Si-O-Si skeleton. With the
passage of time, reaction products developed and fell
apart (as shown in Fig.7(c)), consequently, strength of
the fibers decreased a sound part.
4 Conclusions
The thermal and chemical stability of basalt
fiber comparing with glass fiber was investigated in
this work. The basalt fiber has an excellent thermal
stability below 300 ℃, and its tensile strength increases
from 1 530.7 to 1 823.1 MPa after 6 h whereas that
of glass fiber decreases. It also shows better strength
retention than glass fiber after calcined at 400 ℃. In
the chemical stability test, elevated temperatures were
used to accelerate the reaction. The tensile strength of
basalt fibers increases by 20% after the immersion in
boiling water, but it decreases to some extent for glass
fibers. The mechanical property of basalt fiber remains
well and even increases obviously when the fiber is
leached in acid solution for 6 h at high temperature,
but that of glass fibers is dramatically decreased in
acid solution both at room temperature and at high
temperature. Although basalt fiber has a poor stability
June 2013 565
compared with glass fiber at the initial stage in alkali
solution, it shows better strength retention after long
time treatment. When the fibers was immersed in alkali
solution for 24 h at high temperature, the strength of
basalt fiber can remain about 63.4% of the crude fiber,
whereas that of glass fiber is only 54.5% of the crude
fiber. Thus, basalt fiber has better thermal and chemical
stability than glass fiber and could be used in inclement
environment.
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