In Situ Reinforcement of Particulate SiC Porous Samples

with -Si3N4-Nanofibers Synthesized by the CVI Method

Without Catalytic Precursors

S. S. Mendoza-Barraza

Facultad de Ingeniería Civil, Laboratorio de NanoMateriales, Universidad de Colima,

Coquimatlán, Colima, México

Facultad de Ciencias Químicas, Universidad de Colima, Coquimatlán, Colima, México

C. I. VillaVelázquez-Mendoza

Facultad de Ingeniería Civil, Laboratorio de NanoMateriales, Universidad de Colima,

Coquimatlán, Colima, México

M. I. Levy-Padilla

Facultad de Ingeniería Civil, Laboratorio de NanoMateriales, Universidad de Colima,

Coquimatlán, Colima, México

J. L. Rodriguez

Facultad de Ingeniería Civil, Laboratorio de NanoMateriales, Universidad de Colima,

Coquimatlán, Colima, México

V. Ibarra-Galván

Facultad de Ciencias Químicas, Universidad de Colima, Coquimatlán, Colima, México

1
 P. J. Herrera-Franco

Centro de Investigación Científica de Yucatán, Mérida, Yucatán, México

A. Zamudio-Ojeda

CUCEI, Departamento de Física, Universidad de Guadalajara, Guadalajara, Jalisco, México

G. Méndez-Montealvo

CICATA-Querétaro, Instituto Politécnico Nacional, Querétaro, México

M. I. Pech-Canul

CINVESTAV-Saltillo, Ramos Arizpe, Coahuila, México

V. M. Araujo-Monsalvo

Instituto Nacional de Rehabilitación, Laboratorio de Biomecánica, Del. Tlalpan, DF, México

V. M. Domínguez-Hernández

Instituto Nacional de Rehabilitación, Laboratorio de Biomecánica, Del. Tlalpan, DF, México

Address correspondence to C. I. VillaVelázquez-Mendoza, Universidad de Colima, Facultad de

Ingeniería Civil, Laboratorio de NanoMateriales, Carr. Colima-Coquimatlán km 9, Coquimatlán,

Colima, 28400, México. Tel: +52 312 3161167. E-mail: carlos.ivm@gmail.com,

carlos_villavelazquez@ucol.mx

Abstract

The aim of this work is to reinforce particulate porous SiC samples by the in situ synthesis of β-

Si3N4 nanofibers within the porous samples by the chemical vapor infiltration method without

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catalytic metallic precursors. The experiment considered the variation of the reaction time (1, 2, 3

and 4 h) and the N2 flow rate (3, 5, 9 cm3/min); while the inner pressure (10 mbar), the thermal

decomposition of the solid precursor Na2SiF6 (400°C) and the temperature of the SiC sample

(1300°C) remained constant. The mechanical properties of the composites revealed a non-linear

behavior due to the arrangement of the particles during the loading process and to the plastic

properties of the β-Si3N4 nanofibers. The stress and strain energy density magnitudes for different

times had a rising behavior up to 3 h (= 15.65 MPa and u = 2.41 MJ/m3) due to the increasing

diameter (100 to 200 nm) and quantity of β-Si3N4 nanofibers; while, at 4 h were significantly

decreased (= 8.83 MPa and u = 1.44 MJ/m3) based upon the reduction of the β-Si3N4 nanofibers

diameter (30 to 100 nm) and to the presence of a new phase (Si2N2O).

Keywords: ceramic-matrix composites, chemical vapor infiltration, corn-starch consolidation,

silicon nitride nanofibers, strain energy density

1. INTRODUCTION

Porous composite ceramic materials have extensive applications in aerospace, aeronautical

and automotive industries due to their relatively low density and high mechanical and thermal

properties. However, the existing forming methods such as slip casting, injection molding or die

compaction have presented many problems related to the processing. For this reason, an alternative

method to manufacture porous composite ceramic materials is the growth of a new ceramic

compound (-Si3N4 nanofibers) within a particulate SiC porous sample by infiltrating gas

precursors. Nonetheless, like the aforementioned processing methods for dense materials, this one

also, for porous materials faces processing challenges to prepare green samples that could

withstand high temperatures (1300°C) without crumbling. First of all, consolidation, stability and

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porosity of the particulate SiC samples at 1300°C must be assured prior to the gas infiltration

process. Ceramic microparticles are normally consolidated by applying a uniaxial load, which may

cause a size reduction of the particles varying the final properties of the samples. Other widespread

consolidation methods include the freeze casting (Xia, Zeng, and Jiang 2012) or the use of organic

binders, such as foams (Mao, Wang, and Shimai 2008; Chuanuwatanakul et al. 2013) and starches

(Lyckfeldt and Ferreira 1998). Starches have been extensively utilized to consolidate different

particulate ceramic materials, some examples are: cordierite (Alves et al. 1998), alumina (Almeida

et al. 2009; Chandradass et al. 2009; Minatti et al. 2009; Gregorová et al. 2010; Gregorová and

Pabst 2011), carbides (Romano, Velasco, and Torralba 2007) and silicon nitrides (Yao et al. 2012).

Furthermore, the starch-consolidation method is easy and affordable since the slip composed of

water, starch and ceramic particles is poured into a ceramic mold of any shape. Later, the slip is

dried and unmolded to obtain green samples, which are normally sintered at high temperatures to

produce ceramic materials with defined geometries (Chandradass et al. 2009).

Different routes to synthesize - and β-Si3N4 nanofibers can be found in literature, such

as: carbothermal nitridation of silica with carbon black and Si3N4 as seeds with temperatures

over 1600C and pressures above 0.6 MPa (Yang et al. 2005), combustion of Si/Si3N4/NH4F/Al at

1900 °C under a nitrogen pressure of 100 atm. (Chen et al. 2001), sol-gel to produce carbonaceous

silica xerogel which is heated at 1300 °C for 10 h in nitrogen (Wang, Jin, and Guo 2006), sol-gel

using tetraethyl orthosilicate (TEOS) and dextrose as Si and C precursors to produce after 7 days

a transparent gel which is treated at 1350 °C for 3h (Chaudhuri et al. 2008), thermal plasma CVD

of several chlorocarbodisilanes with nitrogen at 1500 °C (Bouyer et al. 2001), or direct nitridation

of various reactive compounds: Fe nanoparticles as catalysts at 1450 °C for 3 h (Huang et al. 2013),

a porous unidirectional Si substrate at 1400°C (Islam, Kim, and Lee 2009), Si powders at several

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temperature steps up to 1380 °C (Hanjun et al. 2008), Si powders at 1400°C for 20 h and post-

sintered at 1800 °C for 30 min (Lee et al. 2007), and a mixture of Si3N4, SiO2 with Si powders

using Co as metal catalyst from 1400 to 1500 °C for 1 or 2 h (Jung et al. 2007). Although these

methods have proved to be very efficient synthesizing different silicon nitride nanofibers (- and

β-Si3N4) on various substrates with different morphologies at high temperatures, it is still necessary

to investigate novel low-energy routes to process efficient composite ceramic materials. For this

reason, using a modified version of the chemical vapor infiltration method (CVI) carried out by

Leal-Cruz and Pech-Canul (2006, 2007) and Flores-García et al. (2012) in which they thermally

decomposed the Na2SiF6 solid precursor to process dense composite ceramic materials (made of

ceramic microparticles with dense silicon nitride species) including Si nanoparticles as catalyst;

the authors, in this work, grow β-Si3N4 nanofibers by the infiltration of silicon fluoride species

with nitrogen in order to produce a net of β-Si3N4 nanofibers within a particulate SiC porous

preform at a relatively low temperature (1300°C) and short times (up to 4 h). Once the silicon

fluoride species infiltrate, a reaction with N2 takes place, nucleating and growing a net of β-Si3N4

nanofibers. This route to process particulate composites presents many advantages since the

temperature (1300 °C) and the reaction times (up to 4 h) are among the lowest found in literature,

which makes it a low-energy method. What is more, the inner pressure during the reaction is just

10 mbar above the atmospheric pressure and no catalytic metallic precursors are needed to grow

the β-Si3N4 nanofibers. The stability and strength of the final porous composite material provided

by the net of β-Si3N4 nanofibers are assessed by the stress-strain diagram and the strain energy

density.

2. MATERIALS AND EXPERIMENTAL METHODS

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 In order to produce SiC porous samples, a mixture of SiC microparticles (200-450 mesh,

= 3.2 g/cm3, Sigma-Aldrich), commercial corn-starch (Maizena) and purified water was prepared

with a total mass and volume of 89.09 g and 60 ml, respectively. The appropriate volume ratio of

the final slip of SiC:starch:water was 55:2:43. This ratio assures the manageability of the paste and

hinders the expansion of SiC sample during the thermal processing. Based on a previous work by

Minatti et al. (2009), in which they applied a 2-stage method and various heating processes to

consolidate alumina particles with potato-starch and sugar; in the current study, a direct method is

proposed to consolidate SiC microparticles with corn-starch. This method consists of mixing the

corn-starch with water in a flask under constant stirring during 20 min increasing the temperature

from room temperature to 85 °C with a heating rate of 3.25 °C/min in order to gelatinize the corn-

starch. Later, SiC microparticles were homogeneously mixed with the corn-starch paste to obtain

a final slip. The slip was poured into 2.5 cm (inner diameter) x 0.9 cm (width) impermeable

alumina molds, and left at room temperature during 24 h. This time is necessary to the samples

might evaporate enough water to shrink and facilitate their extraction from the alumina molds. A

green sample (made of SiC microparticles and corn-starch) is placed at the center of a tube furnace

at 1300 °C, while a Na2SiF6 pellet at 400 °C. This Na2SiF6 pellet was formed compressing Na2SiF6

powders with a pressure of 200 kg/cm2 in an iron ring of 2.5 cm (outer diameter), 1.6 cm (inner

diameter) x 1 cm (width), see Figure 1. In the CVI method the solid precursor Na2SiF6 (Sigma-

Aldrich) was thermally decomposed to produce silicon fluoride species that will finally react at

1300 °C with N2 to synthesize β-Si3N4.

A full factorial experimental design by triplicate was used considering two factors: reaction

time with 4 levels (1, 2, 3, and 4 h) and constant N2 flow rate with 3 levels (3, 5, and 9 cm3/min).

The inner pressure at 10 mbar, the temperature of the precursor at 400°C, and the temperature of
400°C

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the SiC sample at 1300°C, remained constant. In this process, based on a work by Leal-Cruz and

Pech-Canul (2006, 2007) where they studied the thermal decomposition of the Na2SiF6 compound

proposing the following reaction (1)

Na2 SiF6  s   2 NaF  s   SiF4  g  (1)

Subsequently, silicon tetrafluoride (SiF4(g)) might react directly with nitrogen to produce

silicon nitride (Si3N4). Consequently, the Si3N4 is synthesized according to equation (2):

3SiF4  g   2 N2  g   Si3 N4  s   6F2  g  (2)

The Si3N4 is formed in gas phase during infiltration through the interstices of the porous

bodies or onto the surface of the SiC particles, which favorably function as nucleation sites. The

-Si3N4 nanofibers growth depends upon the processing parameters and the magnitude of their

respective levels, most significantly on temperature and time. It is worth mentioning that in this

work only nanofibers were grown within the porosity (theoretical value ~50%) of the particulate

SiC sample, no dense Si3N4 material was synthesized. These β-Si3N4 nanofibers provide stability

and strength to the porous ceramic body. This occurs at a relatively low temperature of 1300°C

and short times (up to 4 h), well below typical β-Si3N4 nanofibers synthesis or sintering

temperatures for SiC microparticles (~1900 °C).

Qualitative and quantitative analyses of SiC, corn-starch powders and SiC/β-Si3N4 samples

were carried out by X-ray diffraction (XRD) using a Phillips X’Pert Pro-PANalytical

diffractometer applying Cu-Kα radiation. All samples were microstructurally characterized by

scanning electron microscopy (SEM) using both a Hitachi-TM3000 and a TESCAN Mira3-LM in

order to reveal and identify the morphology of the β-Si3N4 nanofibers. In order to better understand

the paste formation of the slurries, a rheological analysis was performed to the corn-starch at 5 wt.

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% in water. The pasting profile of the starch dispersion (5 w/v %, db) was measured by running a

rotational test in an Anton Paar GmbH Rheometer, model Physica MCR 101 using parallel plates

that had been sandblasted with a diameter of 20 mm and a gap of 1000 µm at a heating or cooling

rate of 2.5 ºC/min and a shear rate of 50 s1. Additionally, thermal analyses (TG, thermogravimetric

(20 – 1300°C) and DTA, Differential Thermal Analysis (20 – 1000°C)) were carried out to identify

the endothermic and exothermic events of the starch, using a simultaneous TGA/DSC (TA

Instruments, SDT Q600). The compression tests were performed using an electromechanical

Instron Universal Testing Machine, model 4502 (Instron Corporation, Canton, MA, USA), at a

crosshead speed of 1 mm/min, with a maximum displacement of 10 mm and maximum load of 10

kN. The samples were placed on a rigid metal plate. The load was applied through a 66 mm

diameter and 18 mm thick circular steel plate. Load and displacement data were recorded using

the Series IX software (Instron Corporation, Canton, MA, USA).

3. RESULTS AND DISCUSSION

3.1. Starch consolidation method

Gas infiltration into porous samples composed of micro or nanoparticles normally presents

various difficulties related to the formation of the porous sample. In this sense, different

consolidation approaches have been reported in literature, as discussed in the introduction, such as

the application of high mechanical loads, or the use of organic binders. Although the former

approach is an easy and clean method, it commonly modifies the size of the particles. Once the

green sample is formed, it is very difficult to measure the size distribution of the particles. On the

other hand, the latter approach tends to be very efficient not only to consolidate the particles but

also to control the final porosity of the green samples at 1300°C. Besides, three conditions must

8
be achieved prior to the gas infiltration process: consolidation, stability and porosity of the SiC

sample. The first condition is easily achieved by the starch gelatinization at temperatures below

90 °C (Figure 2b and 2c). Nevertheless, because samples must be stable (do not crumble during

the positioning stage in the tube furnace) and porous at 1300 °C, residual starch which decomposes

into amorphous carbon, has to be present within the sample in order to join the particles at this

temperature. Figure 2a shows the X-ray diffractograms of the corn-starch and the silicon carbide

powder. While Figure 2b depicts the rheological analysis of the corn-starch (5 wt. %) in water,

showing that the viscosity increases rapidly from 80 to 90 °C and that the slurry maintains its

viscosity after the cooling process. As seen in Figure 2c, the thermogravimetric analysis (TGA)

with an N2 atmosphere indicates that at 1300 °C less than 5 mass % of the original starch is still

present within the sample but at this temperature it was transformed into amorphous carbon, and

this small quantity is enough to maintain the stability of the green sample and also to release the

space occupied by the starch within the porous sample, see Figure 3b. The starch by-product is no

longer corn-starch (amylopectin and amylose), rather it becomes amorphous carbon at 1300 °C.

3.2. β-Si3N4 growth

Since nitrogen reacts with silicon fluoride species and not with SiC, a net of β-Si3N4

nanofibers is expected to cover the SiC particles providing stability and strength to the final

composite with a minimum increase in weight. In this sense, the β-Si3N4 nanofibers are synthesized

using the CVI method, by which a solid compound is thermally decomposed at 400 °C in order to

produce 3 different products: NaF(s), SiF4(g), and fluorine. Later, SiF4 reacts with N2; nucleation

and growth phenomena begin creating new structures (β-Si3N4) that will randomly grow covering

the SiC microparticles. Figure 3a shows the gelatinized corn-starch mixed with SiC

microparticles. In this stage, it would not be possible to infiltrate the volatile compounds since no

9
interstices are present. In order to release the SiC sample from the corn-starch and also to do the

infiltration, temperature of the SiC sample is set at 1300 °C with a flow of N2. At this temperature,

the starch decomposes leaving residuals of amorphous carbon (ca. 5 mass %) accumulating at the

contact points among SiC particles. This percentage is enough to provide stability to the SiC

sample during the infiltration process at 1300 °C, see Figure 3b. The experimental design

considers 2 factors: 1) reaction time with 4 levels, t = 1, 2, 3, and 4 h; and 2) N2 flow rate with 3

levels, f = 3, 5 and 9 cm3/min. The N2 flow rate levels were randomly chosen in an interval from

1 to 9 cm3/min.

With an N2 flow rate equal to 9 cm3/min, Figures 3b to 3f depict the effect of time (0, 1, 2,

3, and 4 h) on the growth of β-Si3N4 fibers. As seen in Figure 3c which is at t = 1 h very few fibers

are present within the interstices. At t = 2 h (Figure 3d) more fibers appear surrounding the SiC

microparticles. At t = 3 h (Figure 3e), β-Si3N4 fibers are completely covering the SiC

microparticles and all the constituents of the sample. These fibers are well defined and their mean

diameter varies from 100 to 200 nm, see Figures 3c to 3e. In Figure 3f, the β-Si3N4 fibers reduce

their diameter producing interwoven fibers with a cotton-like and finer structure (<100 nm). The

experiment indicates that no β-Si3N4 fibers grow at N2 flow rate of 3 cm2/min, while at 5 cm2/min

few fibers appear. The presence of oxygen traces is attributed to the corn-starch decomposition,

producing Si2N2O nanostructures at 4 h. The synthesis, growth and morphology of this new phase

is a subject of another work (VillaVelázquez-Mendoza et al. 2016).

Figure 4 zooms in the β-Si3N4 nanofibers synthesized by the following processing

parameters: p = 10 mbar, T = 1300 °C and f = 9 cm3/min; Figure 4a, at t = 3h shows fibers with

diameter from 100 to 200 nm and Figure 4b, at t = 4 h shows fibers with diameters < 100 nm.

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 Qualitative and quantitative analyses were performed by XRD in order to identity the

silicon nitride phases. Figure 2d, from a sample at t = 4h, the XRD shows the presence of the

following two phases: 85% -Si3N4, JCPDS 01-076-1415 with hexagonal crystal system and

P63/m space group, while 15% of Si2N2O JCPDS 01-083-2149 with orthorhombic crystal system

and Cmc21 space group.

3.3. Strain energy density

Due to the fact, that these composite materials are porous and that the porosity is not

completely filled by the β-Si3N4 nanofibers, the mean of the stress-strain diagram does not present

a linear elastic behavior, Figure 5e. The general behavior of the material can be divided into three

different regions, as shown in Figure 5e. From the origin, that is, a zero stress and strain, up to a

nearly fully densified material. When the compressive load is applied to the sample, all

microparticles tend to re-organize reducing the space among them. The main microstructural

changes are particles translations and rotations (first region). In the case of long SiC particles,

another failure mechanism that could be presented is buckling, resulting from the premature

nonlinear failure of the SiC particles in the material. This behavior depends on the porous structure.

However, the net of β-Si3N4 nanofibers provide stability to the sample because of their plastic

properties (Xie, Mitomo, and Zhan 2000). Owing to this behavior, the stress and modulus values

increase with strain and the material may be thought of as behaving like a linear-elastic material

with reversible deformation on the stress-strain curve. It is believed that the SiC particles together

with the β-Si3N4 nanofibers, behave as laterally constrained columns, and provide a source of

stored elastic energy (second region). When the applied load is increased, the material starts

behaving like a plastic material with plastic deformations, and breakup of the original anisotropic

particles occurs (third region) (Caddock and Evans 1989).

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 Since the peripheral part of the samples cracks at = 0.55, this value was considered as the

rupture value (see Figures 5a to 5d), although the stresses will increase with the strain disregarding

the level of failure, as shown in Figure 5e. The strain energy density (u) is the strain energy per

unit volume and is equal to the area under the stress-strain diagram. This strain energy () is a

measure of the energy needed to deform the sample, which can be measured at different

deformation stages. In this case, = 0.55 was set since it is the value by which the fracture is

evident. As seen in Figures 5f and 5g, the magnitudes of stress and strain energy density values at

= 0.55 increase with time from 0 to 3 h which is a consequence of the quantity of -Si3N4

nanofibers grown in the samples having diameters between 100 to 200 nm. Even though the

quantity of fibers increases with time, the magnitude of stress and strain energy decreases at 4 h,

this is attributed to the reduction of the fibers diameter (from 30 to 100 nm), and to the presence

of a new phase (Si2N2O). Figure 5g does not show the error values since they were obtained

directly from the mean values of the stress-strain diagrams from Figure 5e. It is worth mentioning

that most of the works found in literature related to the processing of Si3N4-SiC composites consist

in growing dense Si3N4 phases using metallic catalytic precursors in order to fill the porosity of

the samples, and that the improvement of the density and the strength are normally achieved by a

subsequent sintering process. In this work, the objective is to reinforce the SiC particulate samples

by growing a net of β-Si3N4 nanofibers at a relatively low temperature (1300 °C) and short reaction

times (up to 4 h) to provide strength and stability to the SiC particulate samples. Since this novel

approach produces particulate porous composite samples whose constituents are not chemically

bonded, they would present lower strength values than those obtained for dense microstructures

(i.e. 60.2 MPa (Huang et al. 2014) and 614 MPa (Hu et al. 2014) both for bending strength).

However, this method could be considered as a low-energy consumption process, and due to the

12
porosity of the samples (c.a. 50%) along with their thermal and mechanical properties, they might

be used as solar receiver collectors (Ortona et al. 2015).

4. CONCLUSIONS

In this study, the authors have presented how to use appropriately the corn-starch

consolidation method to produce consolidated, stable and porous green samples made of SiC

microparticles for subsequent gas infiltration, in order to manufacture SiC/β-Si3N4-nanofibers

composite materials. First of all, the slip was made with corn-starch (2 v. %) and water (43 v. %)

under constant stirring with a heating rate of 3.25 °C/min from room temperature to 85 °C (around

20 min); and secondly, SiC microparticles (55 v. %) were homogeneously mixed with the corn-

starch paste. Using the chemical vapor infiltration method, the thickest β-Si3N4 nanofibers (ca. 100

- 200 nm) were found at 3 h, while the thinnest (ca. 30 – 100 nm) at 4 h, both at T(SiC) = 1300 °C,

T(Na2SiF6) = 400 °C with an N2 flow rate, p = 10 mbar and f = 9 cm3/min. No catalytic metallic

precursors were needed to grow the β-Si3N4 nanofibers. The stress-strain diagram reveals a non-

linear behavior due to the arrangement of the particles during the loading process and to the plastic

properties of the β-Si3N4 nanofibers, resulting in failure modes such as buckling and at high load

levels, rupture and tearing in the tangential orientation of the samples. The magnitudes of the

stresses and strain energy densities for different times have a rising behavior up to 3 h (= 15.65

MPa and u = 2.41 MJ/m3) due to the increasing quantity of β-Si3N4 nanofibers. Meanwhile, at 4 h

the mechanical properties (= 8.83 MPa and u = 1.44 MJ/m3) are significantly decreased based

upon the reduction of the β-Si3N4 nanofibers diameter (30 to 100 nm) and to the presence of a new

phase (Si2N2O).

Funding

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 This work was financially supported by CONACyT Ciencia Básica 2010-155444.

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Figure 1. CVI reactor. Schematic drawing of the experimental setup with furnace temperature
distribution and samples geometry and position.

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Figure 2. a) XRD patterns of SiC microparticles and corn-starch, b) rheological analysis of corn-
starch (5 wt. %), c) thermogravimetric (TG) and differential thermal analyses (DTA) of corn-
starch, d) quantitative and qualitative analysis by XRD of the β-Si3N4 nanofibers synthesized at
4 h.

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Figure 3. SEM photomicrographs of a) SiC microparticles with gelatinized corn-starch. The
following images depict the SiC/β-Si3N4 composites treated under constant temperature
(T = 1300°C), inner pressure (p = 10 mbar), and N2 flow rate (f = 9 cm3/min), with different
processing time levels: b) microstructure of consolidated, porous and stable SiC green sample at
t = 0 h, c) t = 1 h, d) t = 2 h, e) t = 3 h, and f) t = 4 h.

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Figure 4. β-Si3N4 fibers synthesized within the interstices of the SiC porous sample with the
following processing parameters: temperature, T = 1300 °C; inner pressure, p = 10 mbar; and N2
flow, f = 9 cm3/min, a) time, t = 3 h, and b) t = 4 h.

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Figure 5. Photos of a sample synthesized with t = 3 h during the loading process at 1 mm/min,
with a)  = 0.0, b)  = 0.25, c)  = 0.55, d)  = 0.75. e) Mean stress-strain diagrams of the
composites processed at 1300C for different processing times. Figures f) and g) depict the stress
and strain energy density values at  = 0.55 of the composite ceramic samples subjected to a
uniaxial compressive test. All samples were processed at 1300C, at 5 different times (0, 1, 2, 3,
and 4 h), the deformation rate was set at 1 mm/min.

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