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Porous SiC Ceramics with Controlled Pores by CVI and

Oxidation Consumption Processing
a b
Shoujun Wu & Laifei Cheng
a
College of water resources and architectural engineering, Northwest A&F University,
Yangling Shaanxi, People's Republic of China
b
Science and Technology on Thermostructural Composite Materials Laboratory,
Northwestern Polytechnical University, Xi'an Shaanxi, People's Republic of China
Accepted author version posted online: 24 Aug 2015.

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To cite this article: Shoujun Wu & Laifei Cheng (2015): Porous SiC Ceramics with Controlled Pores by CVI and Oxidation
Consumption Processing, Materials and Manufacturing Processes, DOI: 10.1080/10426914.2015.1037897

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 Porous SiC ceramics with controlled pores by CVI and oxidation consumption
processing

Shoujun Wu1, Laifei Cheng2

1
College of water resources and architectural engineering, Northwest A&F University,
Yangling Shaanxi, People’s Republic of China, 2Science and Technology on
Thermostructural Composite Materials Laboratory, Northwestern Polytechnical
University, Xi’an Shaanxi, People’s Republic of China

Corresponding author: E-mail: shoujun_wu@163.com, wusj@nwsuaf.edu.cn

Downloaded by [University of Nebraska, Lincoln] at 16:47 29 August 2015

Abstract

Preparation of porous SiC ceramics with controlled pores is demonstrated by

oxidation consumption of a chemical vapor infiltration (CVI) C/SiC composite. The

results show that the pores formation can be well monitored by thermogravimetric

analysis during the oxidation. Performing the oxidation at 800 ºC is more favorable for

obtaining porous ceramic by carbon oxidation consumption. The pores in the prepared

SiC porous ceramics are uniform and maintain the same size and shapes with the used

carbon fibers. Effective protections of the carbon fibers during CVI as well as negligible

following oxidation of SiC are reasons for the pores control. The novelty of the present

work is to provide a relative simple method for preparation of porous SiC body with

controlled pores as well as for preparation of complex-shaped porous SiC body.

KEYWORDS: SiC; Ceramics; Porous; Infiltration; Oxidation

INTRODUCTION

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 Porous ceramics have been widely used as filters for exhaust gas or molten-metals,

supports for catalytic materials, insulators for thermal application and refractory materials

[1–3]. More and more attention have been paid to porous ceramics due to they possess

low coefficient of thermal expansion, high thermal resistance, high strength and excellent

mechanical and chemical stability [4–6]. Controlling the microstructure, i.e. the size,

shape, connectivity and distribution of the pores is one of the most effective ways to

improve the permeability of porous ceramics [7]. A lot of attempts have been
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successfully developed to preparation porous ceramics using electrophoretic [8], filament

winding, biomimetic [9], slip casting methods [10], ice/fiber-templated method [11] and

extrusion method [12–14]. The newly developed extrusion method has good applicability

to prepare different porous ceramics, in which the size of pore and porosity can be

controlled by the diameter of the fiber and its content, respectively. However, pores in the

extrusion samples are not straight but bent, even disconnected at the junction of two

fibers. Though by extruding a frozen ceramic/camphene body, porous ceramic with

highly aligned porous structure and porosity can be obtained, pore size control is difficult

[14]. Moreover, due to the covalent nature, SiC ceramics are difficult to sinter at

moderate temperatures. Therefore, preparation of SiC ceramics with controlled pores and

porosity, especially with complex shape is important to meet different application

requirements.

SiC obtained by chemical vapor infiltration (CVI) possess well controlled

microstructure and high purity [15] compared to the products by reactive infiltration of Si

into porous carbon templates. Moreover, the CVI is a widely applicable near-net-shape

2
 process which can simultaneously treat a mass of preforms with various shapes and sizes.

Moreover, the carbon fibers also have different shape and size. Therefore, porous SiC

ceramics with controlled pores and porosity should be prepared by oxidation

consumption of the carbon fiber in CVI C/SiC composites. And it is expected that this

method is favorable to prepare complex-shaped porous SiC ceramics.

In this work, possibility of prepare porous SiC ceramics with controlled pores by
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oxidation consumption of a CVI C/SiC composite was examined.

MATERIALS AND METHODS

Porous SiC ceramic with controlled pores is prepared by oxidation consumption of

carbon fibers of a CVI C/SiC composite. T-300 carbon fiber (Toray, Japan) is braided to

form plate-shaped fiber preform using four-step three dimensional (4-step 3D) braiding

method. The braiding angle is 20°. The size of the palte-shaped fiber perform is about 4.5

mm in thickness, about 200 mm in length (along the fiber direction) and about 160 mm in

width. The silicon carbide matrix is deposited into the fiber preforms by low pressure

chemical vapor infiltration (LPCVI) process using Methyltrichlorosilane (MTS,

CH3SiCl3) as precursor. Hydrogen is used as carrier gas. The mole ratio of H2 to

methyltrchlorosilane (MTS) is 10. The deposition of SiC is performed at 1100 ºC under 5

kPa for 120 h. Argon is used as the dilute gas. The mole ratio of Ar to H2 is 1. The fiber

volume fraction is controlled in the range of 40 - 45 %. Then the prepared CVI C/SiC

composite plate was double-sided ground into a thickness of about 4.0 mm using a

precision surface grinding machine. After that, the ground plate was cut into the samples

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 with a length of about 30.5 mm (along the fiber direction) and width of about 4.2 mm.

Finally they were ground into about 4.0×4.0×30mm3 samples. The density and porosity

of the as-received C/SiC is 1.71 g/cm3 and 15.0 %, respectively, measured by

Archimedes method.

It is generally considered that carbon is apt to oxidation consumed above 400 ºC

[16], while pure SiC starts oxidation above 800 ºC but the oxidation rate is very slow
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below 1000 ºC [17]. To obtain porous body, the as-received C/SiC composite is oxidized

at 600 ºC and 800 ºC. In order to monitor the oxidation consumption process of the

carbon fibers, the oxidation is performed in simulated air using Thermal Analysis System

(METTLER TOLEDO STARe, sensitivity of the thermobalance is 0.0001 mg) with

thermogravimetric analysis (TGA) mode, respectively. Mixture of 78 vol.% Ar and 22

vol.% O2 is used as simulated air. The microstructures of the as-received and the oxidized

samples are observed using a scanning electron microscope (SEM, JEOL JSM-6360).

Archimedes method is applied to measure the open porosity of the samples.

RESULTS AND DISCUSSION

Figure 1 shows the thermogravity results of the CVI C/SiC during oxidation. During

oxidation, the CVI C/SiC shows a significant weight loss at the both temperature. However,

during oxidation at 800 ºC over 200 min, the weight loss maintains the same value and the

TGA curve become a horizontal line. The inflexion on the TGA curve of the 800 ºC

oxidation indicating carbon fibers has been fully consumed and no significant oxidation of

SiC. The TGA curve of the 600 ºC oxidation shows a nearly linear manner, though the final

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 weight loss of it is very close to that of 800 ºC. This TGA results suggests 800 ºC is more

favorable to fully oxidation consumption of the carbon fibers.

Residual porosity always exists in CVI composites. The density and volume fraction

of the CVI composites can be described as follows:

ρcom = ρSiC ×Vm + ρC ×V f (1)

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V f + Vm + V p + Vclo = 1

Where ρcom , ρSiC , ρC refers to density of the composite, SiC matrix and carbon,

respectively. Vm , V f , VP , VC refers to volume fraction of matrix, fiber, open pores and

close pores in the composite.

When the carbon fibers are fully consumed while the SiC matrix is free of oxidation,

the weight loss reaches the maximum. Otherwise, the weight loss should be less than this

condition. The maximum oxidation weight loss can be described:

Wloss ,max = 1 - WSiC (2)

Where Wloss ,max , WSiC refers to the maximum relative weight loss of the composite

and weight fraction of the SiC matrix.

According to equation (1) and (2), it can be gained that the maximum relative

weight loss of the composite is about 43-47%, if the carbon fibers are fully consumed.

Table.1 lists the tested weight loss, porosity, and density of the as-received and oxidized

samples. It shows that the tested open porosity by Archimedes method is nearly the same

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 for the two kinds of the oxidized samples with a value of about 68%. Therefore, it is

supposed that after oxidation at 600 ºC for 900 min, carbon fibers in the composite is also

fully consumed. Therefore, the pores formation can be well monitored by TGA results

and performing the oxidation at 800 ºC is more favorable obtain the SiC porous ceramic

by carbon oxidation consumption.

Figure 2 shows morphologies of the as-received CVI C/SiC composite and the
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obtained porous SiC ceramics. It seems that the carbon fibers are fully consumed for both

kinds of the oxidized samples. Moreover, the pores are uniform and maintain the same

size and shapes with that of the carbon fibers. This means the pores are depended on the

size and shapes of the carbon fibers.

In CVI process, deposition of the solid matrix phase is achieved by transportation of

a vapor phase precursor (MTS involved in the present work) into the porous preform, and

then a combination of gas and surface reactions. It is believed that during CVI SiC

deposition, the carbon fiber preform and fibers itself are free of compress deformation or

resulted rupture compared to extrusion or those method with a press process [11,14].

Compared to reactive Si infiltration process [15], during CVI SiC deposition, the fibers

are also free of reactive damage. Therefore, in the CVI C/SiC composite, not only the

fibers keep the original shape and dimension, but also the fiber preform keeps the as-

received shape and architecture. On the other hand, the SiC matrix is nearly free of

oxidation during this work. Therefore, the pores in the oxidation gained porous body are

uniform and maintain the same size and shapes with the carbon fibers as oxidation of SiC

6
 is negligible. There are various commercial carbon fibers with different size and shape as

well as the structure of the fiber preforms. As a result, it can be concluded that the shape

and size of pores, porosity and porous network structure of porous ceramic by this

method can be well controlled by controlling the carbon fibers contained, volume fraction

and architecture of the carbon fiber preform. Furthermore, the pore size can be modified

by further CVI densification. And this character is very favorable to prepare porous SiC

ceramics with controlled pore size, porosity and porous network structure to meet
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different application requirements. And the novelty of the present work is to provide a

relative simple method for preparation of porous SiC body with controlled pores as well

as for preparation of complex-shaped porous SiC body.

CONCLUSIONS

Preparation of porous SiC ceramics with controlled pores is demonstrated by

oxidation consumption of carbon fibers of a CVI C/SiC composite. The following

conclusions can be drawn,

1. Performing oxidation at 800 ºC is more favorable to obtain the SiC porous

ceramic by oxidation consumption of carbon fibers in CVI C/SiC composites.

2. The pores in the prepared SiC porous ceramic are uniform and maintain the same

size and shapes with the carbon fibers. Characteristics of the pores in the SiC porous

ceramic by the present method are depended on the characteristics of the carbon fibers

and the carbon fibers preform.

ACKNOWLEDGEMENTS

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 The authors gratefully acknowledge the financial support from the fund of the State

Key Laboratory of Solidification Processing in NWPU (SKLSP201304) and from the

Human Resources Foundation of Northwest A&F University (No. Z111021101).

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 TABLE 1. Weight loss, porosity and density of the as-received C/SiC composites and

after oxidation

Weight loss Porosity Density

(%) (%) (g/cm3)

As-received 0 15 1.71

600ºC 200min 14.69 27.6 1.49

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600ºC 900min 45.2 67.5 0.95

800ºC 900min 46.7 68.5 0.92

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FIGURE 1. Thermogravity results of the CVI C/SiC during oxidation.
 FIGURE 2. Morphologies of the as-received CVI C/SiC composite and the obtained

porous SiC ceramic: (a) the as-received CVI C/SiC composite, (b) after oxidation at 600

ºC for 900min, (c) after oxidation at 800 ºC for 900min

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