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Author's Accepted Manuscript

Microstructure and mechanical properties of low-


carbon MgO–C refractories bonded by an Fe
nanosheet-modified phenol resin
Guoping Wei, Boquan Zhu, Xiangcheng Li, Zheng
Ma

www.elsevier.com/locate/ceramint

PII: S0272-8842(14)01476-X
DOI: http://dx.doi.org/10.1016/j.ceramint.2014.09.091
Reference: CERI9210

To appear in: Ceramics International

Received date: 29 July 2014


Revised date: 17 September 2014
Accepted date: 17 September 2014

Cite this article as: Guoping Wei, Boquan Zhu, Xiangcheng Li, Zheng Ma,
Microstructure and mechanical properties of low-carbon MgO–C refractories bonded
by an Fe nanosheet-modified phenol resin, Ceramics International, http://dx.doi.org/
10.1016/j.ceramint.2014.09.091

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Microstructure and mechanical properties of low-carbon MgO–C

refractories bonded by an Fe nanosheet-modified phenol resin

Guoping Weia, Boquan Zhua,*, Xiangcheng Lia, Zheng Mab

a
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and

Technology, Wuhan 430081, PR China

b
Zhejiang Zili Company Limited, Shangyu 312300, Zhejiang, PR China


Corresponding author: Tel.: +86 27 68862291; fax: +86 27 68862616.

E-mail address: zbqref@263.net (B. Zhu)

Postal address: The State Key Laboratory of Refractories and Metallurgy, Wuhan University of

Science and Technology, Wuhan 430081, PR China.

Abstract: The effect of adding Fe nanosheets on the microstructure of phenol resin and

low-carbon MgO–C refractories was investigated. The results indicate that well-crystallised

carbon nanotubes (CNTs) of 50–100 nm in diameter and of micrometre scale in length could be

generated at 1000 ℃. The yield of CNTs decreases and the diameter of CNTs increases

significantly as the coking temperature increases. The growth mechanism of vapour–solid (V–S)

is transformed into the vapour–liquid–solid (V–L–S) mechanism at 1200 ℃ for CNTs in

low-carbon MgO–C refractories. The mechanical properties and thermal shock resistance at

1000–1400 ℃ of the specimens with 0.5 wt% Fe nanosheets are greatly improved compared

with specimens without Fe nanosheets. The largest magnitudes in the cold crushing strength

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(CCS), the cold modulus of rupture (CMOR), the hot modulus of rupture (HMOR), and the

residual cold modulus of rupture (CMORst) are 25%, 44%, 24%, and 30%, respectively. The

results are attributed to in situ formation of CNTs and the subsequent generation of bridging and

crack deflection mechanisms in the matrix. However, as the coking temperature increases, the

yield of the CNTs becomes lower and their diameter becomes larger. Thus, the favourable

contribution on the thermal shock resistance decreases gradually.

Keywords: CNTs; Growth mechanism; MgO–C refractories; Mechanical properties

1. Introduction

Graphite, as one of the main components in MgO–C refractories, has the

characteristics of high thermal conductivity, low thermal expansion and low

wettability by molten slag [1]. All of these features give rise to MgO–C refractories

with excellent resistance to both thermal shock and slag corrosion. Therefore, MgO–C

refractories have been widely used as the lining of basic oxygen furnaces (BOF),

electric arc furnaces (EAF), steel ladles, vacuum oxygen decarburisation (VOD)

furnaces and ruhrstahl heraeus (RH) vessels in the steelmaking industry [2–6]. With

the development of energy saving and low-carbon or ultra-low-carbon steelmaking

technologies, carbon content reduction is required for the production of traditional

MgO–C refractories [7–9]. The reason for this requirement is that carbon reduction

can decrease the thermal conductivity and avoid the increase in carbon in molten steel.

However, the reduction of the carbon content usually leads to a dramatic reduction of

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the thermal shock resistance of MgO–C refractories [7,10]. To solve this problem,

many researchers utilise the technology of nanostructures by introducing nano-sized

carbon sources such as carbon black (CB), carbon nanofibres (CNFs), carbon

nanotubes (CNTs) and graphite oxide nanosheets (GONs) in the matrix [11–18].

Through this technology, the thermal shock resistance of MgO–C refractories can be

improved significantly. These nano-sized carbon sources of different morphologies

can not only absorb the elastic strain energy (to reduce the stress on the crack tip) but

can also provide a bridging mechanism in the matrix. As a result, the propagation of

cracks in refractories could be inhibited and the toughness could be improved. For

example, Tamura et al. [11] reported that with the addition of carbon black or hybrid

graphite black, the low-carbon MgO–C refractories possessed better

thermo-mechanical properties than conventional MgO–C refractories (w(C) = 18

wt%). Matsuo et al. [15] found that by adding 0.4 wt% CNFs in the matrix of MgO–C

refractories, the cold modulus of rupture was increased by 2.2 times due to the crack

deflection effect of the CNFs. Zhu et al. [17,18] also found that addition of GONs

could obviously enhance the thermal shock resistance of MgO–C refractory.

Recently, increasing numbers of refractory researchers have realised that to further

improve the thermal shock resistance of low-carbon MgO–C refractories, one of the

key issues is to optimise the structure of pyrolytic carbon derived from the binder

[19–23]. It is well known that due to its good wettability with oxide and graphite,

good thermosetting properties and reduced environmental pollution issues, phenol

resin has been widely applied as a binder for MgO–C refractories [3,24]. However,

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some unfavourable behavior and performance were reported to exist when phenol

resin was carbonised, e.g., the isotropic glassy structure for pyrolytic carbon derived

from phenol resin. This structure can lead to brittleness, and this structure is difficult

to be graphitised, even at 3000 ℃. The refractories bonded with this structure could

exhibit poor oxidation resistance [25]. Furthermore, the brittleness and poor oxidation

resistance of pyrolytic carbon will decrease the strength and thermal shock resistance

of low-carbon MgO–C refractories. To solve this problem, much research has been

performed regarding modifying phenol resin to obtain favourable structure and

properties [22,23,25–27].

In previous work of the authors [28–32], transition metal catalysts were introduced

for modifying phenol resin. The results indicate that catalyst characterisation (such as

the type, content and particle size) and temperature have a significant influence on the

morphology and oxidation resistance of pyrolysis carbon derived from modified

phenol resin. CNTs with an average diameter in the range of 20 to 50 nm and a length

on the nanometre scale could be synthesised in pyrolysis carbon derived from phenol

resin modified by nano-sized metallic Ni, FeNi alloy and Ni(NO3)2·6H2O [28–30].

The graphitisation degree and oxidation resistance of the pyrolysis carbon were found

to be increased significantly [29,31].

To prepare a catalyst with high activity and low cost, commercial Fe powders were

ball milled into Fe nanosheets. The purpose of this paper is to investigate the growth

mechanism of in situ CNTs under the action of Fe nanosheets and their effect on the

mechanical properties and thermal shock resistance of low-carbon MgO–C

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refractories. In addition, the strengthening and toughening mechanisms due to the in

situ formed CNTs are examined.

2. Experimental Procedure

2.1 Preparation and pyrolysis of Fe nanosheet-modified phenol resin

Commercial Fe powders (w(Fe) ≥ 98%) with the dispersant of polyvinyl

pyrrolidone (PVP) were ball milled in ethyl alcohol for 20 h. The weight ratios of the

steel balls, Fe powders and ethyl alcohol were controlled as 10:1:2. The rotation rate

of the steel jar was 350 rpm. After ball milling, the slurry was dried at room

temperature for 48 h and then ground into Fe nanosheets.

Fe nanosheet-modified phenol resin was prepared with thermosetting phenol resin

(the carbon yield at 800 ℃ in Ar atmosphere is 46.0–50.0%, and the viscosity at

25 ℃ is 15.0–19.0 Pa·s) and Fe nanosheets. Next, 1.0 wt% Fe nanosheets were

added into the phenol resin and mixed homogeneously by mechanical stirring. The

mixture then became uniform gel specimens. To study the pyrolysis behaviour of Fe

nanosheet-modified phenol resin, the specimens were cured and coked in a reducing

atmosphere (embedded in the graphite bed). The heat treatment temperatures used

were 600 ℃, 800 ℃, 1000 ℃ and 1200 ℃, and the soaking time at the final heating

temperature was 3 h.

2.2 Preparation of low-carbon MgO–C refractory specimens

Fused magnesia (5–3 mm, 3–1 mm, 1–0 mm and < 88 μm, MgO 97.5 wt%), flake

graphite (< 147 μm, C 94.0 wt%), aluminium powder (< 88 μm, Al 99.5 wt%) and

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nanometre carbon black (~ 50 nm, C 96.19 wt%) were used as raw materials. Fe

nanosheet-modified phenol resin was used as the binder. The detailed compositions

for low-carbon MgO–C refractory specimens are presented in Table 1. To investigate

the effects of the Fe nanosheet contents on the properties of low-carbon MgO–C

refractories, Fe nanosheets of different contents of 0 wt%, 0.2 wt%, 0.5 wt% and 1.0

wt% were added to phenol resin for the preparation of refractory specimens. All raw

materials were mixed homogenously and then pressed into the specimens with the

dimension of 25 mm × 25 mm × 140 mm at the pressure of 160 MPa. The pressed

specimens were cured at 200 ℃ for 24 h and subsequently coked at 1000 ℃,

1200 ℃ and 1400 ℃ for 3 h at each temperature under a reducing atmosphere

(embedded in the graphite bed).

2.3 Testing and characterisation methods

The phase composition and the microstructure characteristics of pyrolysis carbon

derived from Fe nanosheet-modified phenol resin and the coked low-carbon MgO–C

refractory specimens were studied using the techniques of X-ray diffraction (XRD,

X’Pert Pro MPD, Philips, Netherlands), scanning electron microscopy (SEM, Nova

NanoSem 400, FEI Company, USA) equipped with energy dispersive spectroscopy

(EDS, Noran 623M–3SUT, Thermo Electron Corporation, Japan) and high resolution

transmission electron microscopy (HRTEM, JEM–2100 UHR, JEOL Ltd., Japan)

equipped with energy dispersive spectroscopy (EDS, JEM–2100 UHR, JEOL Ltd.,

Japan). Semi-quantitative analysis on the basis of RIR (Reference Intensity Ratio)

value was used to estimate mass fraction of the phase identified by X’Pert HighScore

6
software [33,34].

To understand the effect of carbonisation temperature on the crystal structure

parameters of the pyrolytic carbon, metallic silicon was used as the internal standard

to examine the graphitisation degree of the pyrolytic carbon. The value of 2θ002 was

obtained from the Rietveld refinement of the diffraction peak of the (002) plane [35].

The interlayer spacing (d002) and the mean crystallite size (Lc) were calculated based

on the Bragg and Scherrer equations, respectively [35,36]. The degree of crystallinity

(I) can be calculated based on the following equation [37]:


Ac (1)
I= × 100%
Ac + An

where Ac is the peak area in the (002) region of the crystalline phase and An is the

peak area in the (002) region of an amorphous phase. Once the value of d002 was

determined, the graphitisation degree (G) can be calculated according to the

following equation:
0.3440 − d 002 (2)
G= ×100%
0.3440 − 0.3354

where 0.3440 nm represents the interlayer spacing of turbostratic graphite and 0.3354

nm is the interlayer spacing for perfect hexagonal graphite.

The cold crushing strength (CCS) of the coked specimens was measured according

to ASTM C 773–88 (1999). The cold modulus of rupture (CMOR) of the coked

specimen was measured using the three-point bending test at ambient temperature.

The measurement was equipped with electronic digital control system (EDC 120,

DOLI Company, Germany). The force span was 100 mm, the specimen size was 25

mm × 25 mm × 140 mm and a loading rate was 0.5 mm/min. The

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force-displacement curve of the coked specimens was recorded simultaneously during

the three-point bending test. Also using the three-point bending test method, the hot

modulus of rupture (HMOR) of the specimens was measured in a reducing

atmosphere. The test temperature was 1400 ℃, and the soaking time was 0.5 h. The

thermal shock resistance (in a reducing atmosphere) of the coked specimens was

evaluated with the method of water quenching. The coked specimens were heated at

1100 ℃ for 0.5 h in a reducing atmosphere and then placed into flowing water at

room temperature for 5 min. The specimens were dried, and then the values of their

residual cold modulus of rupture (CMORst) were determined after one thermal shock

cycle. All of the preceding measurements were performed using three specimens from

each composition.

3. Results and Discussion

3.1 Pyrolysis of Fe nanosheet-modified phenol resin

An SEM image of the milled Fe powders is shown in Fig. 1. It is clear that milled

Fe powders adopt a sheet structure of 0.1–5 μm in length and 60 nm in thickness.

XRD patterns of 1.0 wt% Fe nanosheet-modified phenol resin carbonised at

different temperatures are shown in Fig. 2. The results reveal that after carbonisation

at 600 ℃, the diffraction peaks at 30.14º, 35.52º and 62.78º should match with the

(220), (311) and (440) planes of magnetite, respectively. The broadening peak from

15 to 30º (2θ) indicates that pyrolytic carbon is typically amorphous. The presence of

magnetite in the pyrolytic carbon reveals that Fe is oxidised by the H2O released

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during the process of carbonisation (shown in reaction (3)). When the temperature

rises to 800 ℃, there is a sharp and intensive diffraction peak at 26.11º, which should

represent the (002) plane of graphite. The observation of this peak suggests that the

amorphous carbon is gradually transformed into crystalline graphite. In addition, the

diffraction peaks at 42.63º and 77.95º should be associated with the (100) and (110)

planes of graphite, respectively. The diffraction peak at 44.73º should be associated

with the (110) plane of α−Fe. During the process of carbonisation, a large amount of

reducing gases, such as CO, H2 and CH4, will also be generated. Thus, the magnetite

phase will be in situ reduced into metallic Fe following reaction (4), which is

generally considered as the catalyst for the formation of graphitised carbon. The

diffraction peaks at the (002) plane of graphite and diffraction peaks at the (110) plane

of α−Fe become sharper gradually with the rise in the carbonisation temperature.

3 Fe ( s ) + 4 H 2 O ( g ) → Fe3O4 ( s ) + 4 H 2 ( g ) (3)

CO / H 2 / CH 4 (4)
F e3 O 4 ( s ) Fe(s)

The crystal structure parameters of the pyrolytic carbon at different carbonisation

temperatures are presented in Table 2. When the temperature is increased to 800 ℃,

the graphitisation degree of pyrolytic carbon reaches 34.88%. The doping of Fe

nanosheets in the phenol resin is confirmed to reduce the graphitisation temperature

significantly. In addition, as the carbonisation temperature increases to 1000 ℃, both

the mean crystallite size and degree of graphitisation increase remarkably. When the

temperature rises to 1200 ℃, there are no significant changes in the mean crystallite

size and the degree of graphitisation.

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The fractured morphology of the pyrolytic carbon carbonised at 600 ℃, 800 ℃,

1000 ℃ and 1200 ℃ is shown in Fig. 3. The morphology and yield of the resultant

carbon were revealed to be strongly dependent on the carbonisation temperature. A

large quantity of magnetite microspheres with a diameter in the range of 150 to 300

nm are formed at 600 ℃, while no CNTs were found in Fig. 3a. It is shown that these

magnetite microspheres formed from Fe nanosheets distribute homogeneously in the

resin carbon resulting good catalyst ability and avoiding the problem of

agglomeration of nano iron oxide particles in the phenol resin. When the

carbonisation temperature increases to 800 ℃, a few CNTs with diameters in the

range of 50 to 100 nm and lengths on the micrometre scale are generated in Fig. 3b.

At the temperature of 1000 ℃, a large yield of CNTs appears, and there is no

significant change in the diameter (shown in Fig. 3c). Note that the yield of CNTs

decreases and the corresponding diameter increases to the range of 50 to 300 nm at a

carbonisation temperature of 1200 ℃, as shown in Fig. 3d.

HRTEM images and electron diffraction patterns of CNTs derived from Fe

nanosheet-modified phenol resin at 1000 ℃ are shown in Fig. 4. These figures

clearly show that the graphite adopts the typical nanotube structure with a lattice

spacing of 0.34 nm. The nanoparticles of Fe are located at the top of each CNT

(indicated by the arrow in Fig. 4a). The electron diffraction pattern of the CNTs (Fig.

4b) indicates that there are three diffraction rings, which corresponds to the (002),

(100) and (110) planes of graphite. The results of HRTEM analysis are quite

consistent with the results of XRD.

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3.2 Phase composition and microstructure of low-carbon MgO–C refractories with Fe

nanosheets

The effect of Fe nanosheet addition on the phase compositions and microstructure

of low-carbon MgO–C refractories was further investigated. The XRD patterns of

specimens SAF0 without Fe nanosheets and SAF0.5 with nanosheets are shown in

Fig. 5. The coked temperatures used are 1000 ℃, 1200 ℃ and 1400 ℃. For

specimen SAF0, MgAl2O4 spinel phases appear at 1000 ℃ (as shown in Fig. 5a and

Fig. 6a), and the intensity of the peaks (2θ = 31.29º) increases with rising temperature.

At the same time, AlN and Al4C3 phases can be formed at this temperature. At a

coking temperature of 1200 ℃, the peaks of Al4C3 disappear. At 1400 ℃, the

diffraction peaks of MgAl2O4 spinel and AlN become sharper and more intensive,

which suggests better crystallisation. For specimen SAF0.5 shown in Fig. 5b, the

phase constituents at different coked temperatures are all consistent with specimen

SAF0. To understand the phase content of the specimens SAF0.5 and SAF0 coked at

different temperatures, the relative content of phase composition calculated based on

the XRD semi-quantitative analysis is presented in Table 3. The results reveal that the

addition of Fe nanosheets could not affect the relative content of phase composition

obviously.

The SEM images of the fracture surfaces of low-carbon MgO–C refractories

(specimens SAF0 and SAF0.5) coked at different temperatures are shown in Figs. 6

and 8. For specimen SAF0 coked at 1000 ℃, there are a few columnar-shaped AlN,

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whisker-like Al4C3 and octahedral-shaped MgAl2O4 particles (confirmed by the XRD

and EDS analysis) in the matrix, as shown in Fig. 6a and b. It is well known that

metallic Al could transform into AlN, Al4C3 and MgAl2O4 in MgO–C refractories at

1000 ℃ through the vapour–solid (V–S), solid–solid (S–S), or liquid–solid (L–S)

reactions [2,38,39]. At 1200 ℃, the size of the AlN and MgAl2O4 spinel increases

significantly (as shown in Fig. 6c and d). Meanwhile, the phase of Al4C3 disappeared

due to its reaction with N2 from the atmosphere to form the AlN phase. Part of AlN

can be oxidised by CO to form Al2O3, which will further react with MgO to generate

MgAl2O4 spinel [2,38]. Up to 1400 ℃, the size of the AlN and MgAl2O4 spinel

increases continually (as shown in Fig. 6e and f). Interestingly, a large amount of bean

sprout-shaped carbon whiskers with a diameter in the range of 200 to 800 nm and

length in the range of 2 to 4 μm are also formed in the matrix at this stage. A particle

is found at the top of each bean sprout-shaped carbon whisker.

Typical HRTEM images of bean sprout-shaped carbon whiskers generated in the

matrix of low-carbon MgO–C refractories at 1400 ℃ are shown in Fig. 7a and b. Fig.

7 indicates that the bean sprout-shaped carbon whiskers adopt a hollow graphite

structure and that the lattice spacing is 0.34 nm. The results of EDS analyses for the

particle at the top of whiskers suggest that the molar ratio of Mg, Al and O is

approximately 1:2:4 (as shown in Fig. 7c), which is in accord with the stoichiometric

proportions of MgAl2O4 spinel. Thus, it can be concluded that the MgAl2O4 spinel

particle is located at the top, which is in agreement with the results of a previous study

[40]. The reason is that the reaction between MgO and C (Reaction 5) in the MgO–C

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system leads to the high pressure of Mg(g) [6,41,42], which reacts with Al(g) and

CO(g) to form MgAl2O4 spinel and bean sprout-shaped carbon whiskers.

MgO(s) + C(s) = Mg(g) + CO(g) (5)

2Al(g) + Mg(g) + 4CO(g) = MgAl2O4(s) + 4C(s) (6)

The formation process of these carbon whiskers can be described as follows: first,

MgAl2O4 spinel crystal nucleates directly through Reaction 6. Meanwhile, the

resultant carbon from Reaction 6 precipitates out from the surface of the MgAl2O4

spinel particle to form the hollow graphite structure. Next, the size of the MgAl2O4

spinel particle increases gradually as the reaction progress. Additionally, the diameter

of the resultant carbon whiskers precipitating out from the surface of the MgAl2O4

spinel particle increases. Thus, the bean sprout-shaped carbon whiskers are formed.

The specimen SAF0.5 with addition of 0.5 wt% Fe nanosheets has the same

microstructure characteristics (shown in Fig. 8a, b, d, e, g and h) as specimen SAF0

mentioned above. However, there is a great difference in that large quantities of CNTs

with an average diameter in the range of about 50 to 100 nm and micrometre scale in

length are formed and interlocked with each other to form intertextures at 1000 ℃ (as

shown in Fig. 8c). As shown in Fig. 9a, the HRTEM image shows a typical nanotube,

and an Fe nanoparticle is located at the top of the CNT. The experimental results are

in good agreement with the microstructure characteristics of CNTs derived from Fe

nanosheet-modified phenol resin at 1000 ℃ (as shown in Fig. 4a). According to the

results of EDS analyses of the CNT in the HRTEM image (as shown in Fig. 9b), the

surface of CNT contains only the C element, which indicates that CNT do not react

13
with Al to form Al4C3. When the temperature is further increased to 1200 ℃, the

average diameter of the CNTs increases up to 500 nm, but the yield of CNTs

decreases (as shown in Fig. 8f). At 1400 ℃, both the average diameter and the inner

diameter of CNTs are further increased. However, there is no significant change in the

yield (shown in Fig. 8i).

3.3 In situ formation mechanism of CNTs in low-carbon MgO–C refractories

Morphologies of in situ formed CNTs in low-carbon MgO–C refractories at

different temperatures are closely linked to their different formation mechanisms. To

achieve a controllable growth of CNTs, it is important to understand their growth

mechanism. In previous research studies [43,44], based on catalyst location in the

CNTs, two types of growth mechanisms, namely the base growth mechanism and the

tip growth mechanism, have been proposed. According to the state of the catalysts

during the growth of CNTs through chemical vapour deposition (CVD), the growth

mechanisms of V–S and vapour–liquid–solid (V–L–S) have also been established.

To date, most research studies have focused on the growth mechanism of CNTs at

below 1200 ℃ . Little attention has been paid to the growth mechanism at

temperatures above 1200 ℃. Based on our experimental results, a possible growth

model of CNTs, as shown in Fig. 10, could be proposed to describe the growth

process of in situ CNTs in refractories. In this model, the growth of CNTs should be

classified as a tip growth mechanism (as shown in Fig. 4a and Fig. 9a), and their

growth process can be divided into the following four main stages. In the first stage,

Fe nanosheets are oxidised into magnetite particles gradually through the reaction (3)

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(confirmed by Fig. 2 and Fig. 3a), and phenol resin is decomposed to release the gases

CO, H2, CH4 and CO2. Along with the decomposition of phenol resin, the magnetite

particles can be reduced into metallic Fe nanoparticles under the reducing atmosphere

formed by CO, H2 and CH4, and the volatile components of hydrocarbon will be

adsorbed onto the active surface of the Fe nanoparticles. At a certain temperature

range, these absorbed hydrocarbon components will finally be decomposed into the

carbon atoms, as shown in Fig. 10a. The second stage might be the process of the

dissolution of the released carbon in the Fe nanoparticles and the subsequent diffusion

from one crystal face to a certain crystal face, as exhibited in Fig. 10b. The third stage

is the realigning of carbon atoms on a certain catalytic crystal face that leads to the

formation of C–C chemical bonds. During this stage, the CNTs are formed and grow

through the continuous combination of C–C chemical bonds. The growth process of

CNTs will push the catalyst particle forward and keep it at the top of the CNTs, as

illustrated in Fig. 10c. During the last stage, the growth of CNTs is stopped when the

catalyst is completely covered by the released carbon, as shown in Fig. 10d.

It is well known that the state of the catalyst is determined by its melting point,

which has great effects on the growth of CNTs. In this particular case, the melting

point of Fe nanoparticles can be calculated based on the following equation [45]:


2γMT (7)
Δt =
rρQ

where Δt is the reduced temperature of the melting point, γ is the surface tension

(1.862 J/m2 for metallic iron), M is the relative molecular mass (55.8 g/mol for

metallic iron), T is the melting point (1808 K for metallic iron), r is the diameter of

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the particle size (approximately 50 nm for Fe nanoparticles, as shown in Fig. 9a), ρ is

the relative density (7.86 g/cm3 for metallic iron), and Q is the Moore latent heat of

fusion (13.81 kJ/mol for metallic iron) [30]. According to the calculation, the melting

point of the Fe nanoparticles (approximately 1466 ℃) is found to be higher than the

coking temperature of 1400 ℃ in this experiment. Additionally, according to the

equilibrium phase diagram of the Fe–C binary system, the eutectic point of this

system is approximately 1153 ℃. Therefore, the catalyst of the Fe nanoparticles will

remain in the solid state during the formation and growth process of CNTs when the

coking temperature is below 1200 ℃. The growth mechanism of CNTs should follow

a V–S growth mechanism (as shown in Fig. 10 ). However, the Fe nanoparticles will

be changed into a liquid state when the coking temperature is above 1200 ℃. Thus,

the growth mechanism of CNTs should follow a V–L–S growth mechanism. During

the process, the liquid iron nanoparticles may lead to the agglomeration due to their

higher surface energy and excellent fluidity (as shown in Fig. 10ⅱ), which may

increase the diameter of the catalyst. Generally, the size of catalytic particles

determines the diameter of the CNTs in CVD growth. The diameter of CNTs coked at

above 1200 ℃ is larger than that coked at below 1200 ℃.

3.4 Mechanical properties of low-carbon MgO–C refractory specimens

The mechanical properties including CCS, CMOR and HMOR of low-carbon

MgO–C refractories coked at different temperatures (1000 ℃ , 1200 ℃ and

1400 ℃) are presented in Figs. 11–13. The CCS and CMOR of all specimens clearly

decrease simultaneously with increasing temperature from 1000 ℃ to 1200 ℃ and

16
then increase simultaneously with the temperature up to 1400 ℃. For example, the

CCS and CMOR of specimen SAF0 at 1000 ℃ are 67.69 MPa and 7.69 MPa,

respectively. At 1200 ℃, the CCS and CMOR are decreased to the minimum values

of 55.81 MPa and 6.34 MPa, respectively. At 1400 ℃, the CCS and CMOR increase

to 73.81 MPa and 9.47 MPa, respectively. However, the HMOR of all specimens

increases with the temperature increasing from 1000 ℃ to 1200 ℃ and then

decreases with the temperature up to 1400 ℃.

The specimens containing 0.5 wt% Fe nanosheets are found to result in the highest

CCS and CMOR values compared to those of the specimens without Fe nanosheets.

In particular, at 1400 ℃, the CCS increases from 73.81 MPa to 92.42 MPa and the

CMOR increases from 9.47 MPa to 13.66 MPa. The corresponding CCS and CMOR

increases in magnitude reach 25% and 44%, respectively. In addition, the greatest

increase in HMOR for different dopants of Fe nanosheets appears at a temperature of

1000 ℃. The value increases from 8.29 MPa to 10.29 MPa, and the magnitude is

approximately 24%. When the coked temperature increases to 1200 ℃ and 1400 ℃,

there is no obvious change in the HMOR value for the specimen with different doping

amounts of Fe nanosheets.

The force-displacement curves of low-carbon MgO–C refractory specimens coked

at different temperatures (1000 ℃, 1200 ℃ and 1400 ℃) are shown in Fig. 14. It

can be seen that no matter what the coked temperature is, the specimen containing 0.5

wt% Fe nanosheets (SAF0.5) demonstrates greater force and larger displacement.

Thus, in situ CNTs have a positive effect on the fracture toughness of low-carbon

17
MgO-C refractory specimens.

The CMORst of different specimens after one cycle of the thermal shock test is

depicted in Fig. 15. The CMORst of specimens coked at 1000 ℃ is observed to

increase gradually with the increase in the Fe nanosheet content. The specimen

containing 0.5 wt% Fe nanosheets exhibits the largest CMORst value at temperatures

of 1200 ℃ and 1400 ℃. The ratio of the CMORst change (β) is obtained by

Equation (8).
S0.5 − S 0 (8)
β= × 100%
S0

where β is the ratio of the CMORst change, S0.5 is the CMORst of specimen SAF0.5,

and S0 is the CMORst of specimen SAF0.

The effect of the addition of Fe nanosheets on the extent of improvement for the

CMORst as the temperature increases is shown in Fig. 16. At 1000 ℃, the ratio of the

CMORst change (30%) is found to the largest. The corresponding CMORst increases

from 3.21 MPa to 4.18 MPa. The change ratio decreases with increasing temperature.

However, the lowest change ratio remains above 15%.

The improvements in the mechanical properties as well as the thermal shock

resistance are greatly associated with the changes in the microstructures of specimens.

In comparison with specimen SAF0, large quantities of CNTs are generated in the

matrix of specimen SAF0.5 at 1000 ℃, which is able to interlock the MgO grains

firmly (as shown in Fig. 8c). When a stress is applied in specimen SAF0, the crack

initiates at the surface of the specimens and subsequently propagates along the side of

the MgO grain in the matrix until the specimen is completely destroyed (as shown in

18
Fig. 17a). For specimen SAF0.5, when the crack passes along MgO grains, CNTs

could absorb and release the stress at the tip of the crack through bridging and crack

deflection mechanisms (as shown in Fig. 17b) due to their high strength and good

toughness. Thus, specimen SAF0.5 exhibits improved mechanical properties, higher

fracture toughness and better thermal shock resistance compared to the specimen

SAF0. However, as discussed above, with an increase in the coked temperature, the

average diameter of the CNTs will be increased and their volume ratio will be

decreased dramatically (as shown in Fig. 8f and i). Generally, the strength and

toughness of CNTs are determined directly by their diameter (the smaller the diameter

of the CNTs, the higher are the strength and toughness of the CNTs) [36].

Consequently, the effect of the addition of Fe nanosheets on the extent of

improvement for the CMORst decreases gradually as the coking temperature increases.

From the experimental results, compared with the specimen SAF0, the mechanical

properties of strength, thermal shock resistance and fracture toughness of the

specimen SAF0.5 coked at 1200 ℃ and 1400 ℃ have also be improved due to the

bridging and crack deflection mechanisms of CNTs in the matrix (as shown in Fig. 8f

and i). However, there is no obvious change in the hot modulus of rupture value for

the specimen SAF0.5 coked at 1200 ℃ and 1400 ℃, respectively. The reasons for

this result will be studied further.

4. Conclusions

(1) Well-crystallised CNTs with an average diameter in the range of 50 to 100 nm and

19
a length on the micrometre scale could be generated in phenol resin and

low-carbon refractories at 1000 ℃. The yield of CNTs is decreased and the

diameter of CNTs is increased obviously as the coking temperature increases.

(2) The growth mechanisms of in situ CNTs in low-carbon refractories follows the

vapour–solid (V–S) and tip growth mechanisms for temperatures below 1200 ℃;

the mechanisms transform into vapour–liquid–solid (V–L–S) and tip growth

mechanisms at temperatures above 1200 ℃. The later growth mechanisms result

in CNTs of larger diameter than that of the former growth mechanism due to the

agglomeration of the catalyst in the liquid state.

(3) At 1000–1400 ℃, the mechanical properties and thermal shock resistance of

low-carbon refractories with 0.5 wt% Fe nanosheets are greatly improved

compared with specimens without Fe nanosheets, which is attributed to in situ

formation of CNTs and the subsequent introduction of bridging and crack

deflection mechanisms in the matrix. However, as the coking temperature

increases, the yield of CNTs decreases and the diameters of the CNTs increase.

Thus, the favourable contribution of the CNTs on the thermal shock resistance

decreases gradually.

Acknowledgements

The authors acknowledge the financial support from the Natural Science

Foundation of China (No. 51174152), the National Key Basic Research Program of

China (973 Program) (No. 2012CB722702) and the Natural Science Foundation of

20
Hubei Province (No. 201471031379).

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Figure captions

Fig. 1. SEM image of Fe nanosheets.

28
Fig. 2. XRD patterns of pyrolytic carbon derived from 1.0 wt% Fe nanosheet-modified phenol

resin at different temperatures.

29
Fig. 3. SEM images of pyrolytic carbon derived from 1.0 wt% Fe nanosheet-modified phenol resin

at different temperatures. (a) Magnetite microspheres formed at 600 ℃, (b) CNTs generated at

800 ℃, (c) the yield of CNTs increases at 1000 ℃, (d) the yield of CNTs decreases and the

corresponding diameter increases at 1200 ℃.

30
Fig. 4. HRTEM image of (a) CNTs derived from Fe nanosheet-modified phenol resin at 1000 ℃

and the higher magnification image (b) of the square area in Fig. 4a.

31
Fig. 5. XRD patterns of low-carbon MgO–C refractory specimens coked at different temperatures:

(a) specimen SAF0 and (b) specimen SAF0.5.

32
Fig. 6. SEM images of low-carbon MgO–C refractories (SAF0) coked at different temperatures: (a)

–(b) 1000 ℃, (c)–(d) 1200 ℃, and (e)–(g) 1400 ℃.

33
Fig. 7. (a) HRTEM image of bean sprout-shaped carbon whiskers generated in the matrix of

low-carbon MgO–C refractories (SAF0) at 1400 ℃; (b) the higher magnification image of the

square area in Fig. 7a; (c) the EDS analysis of point 1 in Fig. 7a.

34
35
Fig. 8. SEM images of low-carbon MgO–C refractories (SAF0.5) coked at different temperatures:

(a)–(c) 1000 ℃, (d)–(f) 1200 ℃ and (g)–(i) 1400 ℃.

36
Fig. 9. (a) HRTEM image of CNT generated in the matrix of low-carbon MgO–C refractories

(SAF0.5) coked at 1000 ℃; (b) the higher magnification image of the square area in Fig. 9a.

37
(a) decomposition of hydrocarbon components into the carbon atoms on the surface of Fe

nanoparticles; (b) dissolution of the released carbon in the Fe nanoparticles and subsequent

diffusion from one crystal face to a certain crystal face; (c) segregation of the released carbon and

formation of CNTs; (d) the growth of CNTs was stopped when the catalyst particles were

completely covered by the released carbon.

Fig. 10. Schematic diagram of the CNTs growth mechanism: ⅰ) V–S model (at below 1200 ℃);

ⅱ) V–L–S model (at above 1200 ℃).

38
Fig. 11. Cold crushing strength (CCS) of specimens coked at different temperatures.

39
Fig. 12. Cold modulus of rupture (CMOR) of specimens coked at different temperatures.

40
Fig. 13. Hot modulus of rupture (HMOR) of specimens coked at different temperatures.

41
Fig. 14 Force-displacement cures of specimens SAF0 and SAF0.5 coked at different temperatures:

(a) 1000 ℃, (b) 1200 ℃ and (c) 1400 ℃.

42
Fig. 15. Residual cold modulus of rupture (CMORst) after one thermal shock cycle (at 1100 ℃) of

specimens coked at different temperatures.

43
Fig. 16. The relative change ratio of the CMORst for specimens SAF0.5 and SAF0 coked at

different temperatures.

44
Fig. 17. Strength and toughness improvement model of specimens: (a) MgO–C refractories

(SAF0); (b) in situ formation of CNTs in low-carbon MgO–C refractories (SAF0.5).

45
Tables

Table 1 The composition of low-carbon MgO–C refractory specimens.

Ingredient (wt%) SAF0 SAF0.2 SAF0.5 SAF1

Fused magnesia aggregate 73 73 73 73

Fused magnesia powder 22 22 22 22

Flake graphite 2.5 2.5 2.5 2.5

Aluminium powder 2 2 2 2

Nanometre carbon black 0.5 0.5 0.5 0.5

Phenol resin (in addition) 4 4 4 4

Fe nanosheets (in addition) 0 0.2 0.5 1

46
Table 2 Crystal structure parameters of pyrolytic carbon derived from an Fe nanosheet-modified

phenol resin.

Carbonisation temperature/℃ 2θ002/(°) d002/nm LC/nm I/% G/%

600 23.4639 0.3788 - - -

800 26.1130 0.3410 6.86 16.62 34.88

1000 26.3488 0.3380 8.74 24.19 69.77

1200 26.3388 0.3381 8.82 24.19 68.60

47
Table 3 The phase content of the specimens SAF0.5 and SAF0 coked at different temperatures.

Periclase Graphite Spinel AlN Al4C3


Specimen Coked temperature (℃)
wt%

1000 92.66 4.41 1.45 0.37 1.11

SAF0 1200 94.04 3.58 1.96 0.42 -

1400 91.42 4.83 2.67 1.08 -

1000 93.30 3.55 1.58 0.65 0.92

SAF0.5 1200 93.17 4.42 2.06 0.35 -

1400 90.94 4.74 2.70 1.62 -

48