Materials Science and Engineering C 26 (2006) 862 866 www.elsevier.

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Microstructure and fracture-mechanical properties of carbon derived Si3N4 + SiC nanomaterials

M. Kaxiarova a,*, J. Dusza a, M. Hnatko b, P. Sajgalk b
b a Institute of Materials Research, Slovak Academy of Sciences, Watsonova 47, 043 53 Kosice, Slovak Republic Institute of Inorganic Chemistry, Slovak Academy of Sciences, Dubravska cesta 9, 842 36 Bratislava, Slovak Republic

Available online 17 November 2005

Abstract The microstructure and basic mechanical properties, as hardness, fracture toughness, fracture strength and subcritical crack growth at room temperature were investigated and creep behavior at high temperatures was established. The presence of SiC particles refined the microstructure of Si3N4 grains in the Si3N4 + SiC nanocomposite. Higher hardness values resulted from introducing SiC nanoparticles into the material. A lower fracture toughness of the nanocomposite is associated with its finer microstructure; crack bridging mechanisms are not so effective as in the case of monolithic Si3N4. The strength value of the monolithic Si3N4 is higher than the characteristic strength of nanocomposites. Fractographic analysis of the fracture surface revealed that a failure started principally from an internal flaw in the form of cluster of free carbon, and on large SiC grains which degraded strength of the nanocomposite. The creep resistance of nanocomposite is significantly higher when compared to the creep resistance of the monolithic material. Nanocomposite exhibited no creep deformation, creep cracks have not been detected even at a test at 1400 -C and a long loading time, therefore the creep is probably controlled mainly by diffusion. The intergranular SiC nanoparticles hinder the Si3N4 grain growth, interlock the neighboring Si3N4 grains and change the volume fraction, geometry and chemical composition of the grain boundary phase. D 2005 Elsevier B.V. All rights reserved.
Keywords: Mechanical properties; Microstructure; Nanocomposite; Silicon nitride

1. Introduction During last years Si3N4 + SiC nanocomposites have been developed in which nano-sized SiC particles are dispersed in the Si3N4 matrix [1,2]. These particles are usually located either intragranularly, with a size of approximately 30 40 nm, or intergranularly with a size of approximately 150 170 nm [3]. Nanocomposites are developed using different concepts/ processing techniques and characterized as regards their microstructure and room and high temperature mechanical properties [4 9]. Most of the Si3N4 + SiC nanocomposites were prepared by hot pressing and the hindered densification due to the presence of SiC particles was overcome using higher densification temperature in comparison to that for the monolithic Si3N4. In the case of gas pressure sintering the densification problem was solved using relatively large amount of sintering additives, e.g., mixtures of yttria and alumina or

silica. Herrmann et al. [2] prepared Si3N4 + SiC nanocomposites with excellent high temperature properties using gas pressure sintering and sintering with Y2O3 additive. The attraction of silicon nitride ceramic matrix composites incorporated with SiC as a second phase is, however, limited owing to their high cost. During the last years an attempt has been made to substitute amorphous Si C N powder with carbon and SiO2, which would be a cheaper alternative for producing Si3N4 + SiC nanocomposites, with excellent mechanical properties. The aim of the present contribution is to study microstructure and some mechanical properties of Si3N4 + SiC nanocomposites prepared by using SiO2 + C reaction and to compare their properties with the monolithic silicon nitride. 2. Experimental material and methods Two different nanocomposites prepared by carbothermal reduction from the starting mixture listed in Table 1 were studied. Samples were hot-pressed under a specific heating regime, atmosphere and mechanical pressure regime at 1750 -C for 2 h [10]. Beside nanocomposites, a monolithic Si3N4 (a

* Corresponding author. Tel.: +421 55 7922 432; fax: +421 55 7922 408. E-mail address: kasiarova@imrnov.saske.sk (M. Kaxiarova). 0928-4931/$ - see front matter D 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.msec.2005.09.032

M. Kasiarova et al. / Materials Science and Engineering C 26 (2006) 862 866 Table 1 Composition of the starting powders of nanocomposites Sample Composition [wt.%] Si3N4 C1B C2B 93.23 84.13 Y2O3 4.91 4.43 C 0.43 0.43 + 3.62 SiO2 1.43 1.43 + 5.96 Table 2 Values of hardness and fracture toughness of the studied materials Material Si3N4 C1B C2B Hardness [GPa] 14.28 T 0.29 14.46 T 0.15 16.34 T 0.12

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Fracture toughness [MPa m1/2] 4.95 T 0.21 4.54 T 0.07 3.75 T 0.53

commercial reference silicon nitride SL200 [11]) was also used in the investigation. The monolithic silicon nitride was fabricated by CeramTech, Plochingen, Germany. It is a gas pressure sintered silicon nitride with Al2O3 (3 wt.%) and Y2O3 (3 wt.%) additives. Microstructure of the materials was characterized on polished and plasma-etched sections of the bulk materials in scanning electron microscopy (SEM). Hardness was measured on polished cross-sections of bars using standard Vickers indentation at the load of 10 N. For the fracture toughness measurement a sharp notch was introduced according to the VAMAS TWA#3/ ESIS TC6 Round Robin Instruction using a razor blade [12]. In all cases the notch tip radius was less than 10 Am. Thirty specimens with dimensions 3 4 45 mm were tested in four-point bending test. Specimens were ground and polished by 15 Am diamond grinding wheel before testing. Two edges on the tensile surface were rounded with a radius of about 0.15 mm in order to eliminate failure from edges of the specimen. The specimens were broken with a cross-head speed of 0.5 mm/min, test environment was ambient air. The fracture initiating flaws fracture origin were examined using SEM and EDX analysis. Subcritical crack growth was established by constant stressrate flexural testing. Forty specimens were broken in four-point bend test at displacement-control mode with cross-head speeds of 0.05, 0.5 and 5 mm/min. The distance between inner and outer rollers is 20 and 40, respectively. All tests were performed in laboratory air and at room temperature (22 23 -C). From the records of load versus displacement the actual loading rate in N/s was determined and thus the corresponding stress rate was calculated. The SCG parameter N can be determined by linear regression analysis using all strength values over the complete range of individual stress rates. Plotting of the log r log r

diagram yields 1/1 + n as a slope of regression straight line from which the SCG parameter N is obtained. Creep tests of C2B and monolithic silicon nitride were performed in four-point bending using a fixture made of silicon carbide with inner and outer span lengths of 20 and 40 mm, respectively. The measurements were carried out in a creep machine with dead-weight loading system, on air, at temperatures between 1200 -C and 1400 -C, with outer fibre stresses in the range from 50 to 150 MPa. The deflection of sample was recorded continuously during the creep test. From the deflection data, the outer fibre strain was calculated as a function of time, t, by the method of Hollenberg et al. [13] and taken as the creep strain, (. The creep rate was calculated from the slope of the ( versus t curve. 3. Results and discussion 3.1. Microstructure Characteristic microstructures of the experimental materials are illustrated in Fig. 1. Microstructure of each material consists predominantly of elongated homogeneously distributed h-Si3N4 grains with a low aspect ratio. The nanocomposite additionally contains globular nano- and submicron-sized SiC particles, located in the Si3N4 grains intergranularly (average particle size is about 45 nm) or intragranularly between the Si3N4 grains (average particle size approximately 250 nm). On SEM micrographs it was difficult to distinguish between the SiC particles located intergranularly and the grain boundary phase because they are similarly affected by plasma etching. The average Si3N4 grain size (diameter) is in the material C1B 160 nm and in the material marked C2B 140 nm. Grains with diameter larger than 500 nm occur in the microstructure of both studied nanocomposites only occasionally. The volume fraction

Fig. 1. SEM microstructure of plasma etched composite, (a) monolithic Si3N4, (b) nanocomposite C1B, (c) nanocomposite C2B.

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M. Kasiarova et al. / Materials Science and Engineering C 26 (2006) 862 866 Table 3 Dependence of characteristic strength values on stress rate Stress rate [MPa/s] r 0 [MPa] Si3N4 1 10 100 719 870 960 C1B 749 786 823 C2B 649 671 682

Fig. 2. Weibull plot of a carbon derived Si3N4 SiC nanocomposites and monolithic silicon nitride.

of the SiC nanoparticles located inside the grains was 1 vol.% for the material C1B and 3.2 vol.% for C2B. The average diameter of the monolithic Si3N4 grains was 790 nm. From the microstructural investigation it is already clear that a small amount of nanoparticles in the matrix markedly refined the microstructure of Si3N4 grains. 3.2. Hardness and fracture toughness The measured values of hardness and fracture toughness are summarized in Table 2. Higher hardness values of nanocomposites were expected in comparison to monolithic Si3N4, because of the addition of harder SiC inclusions into a softer Si3N4 matrix. Higher volume fraction of SiC particles in C2B than in C1B caused higher hardness values in C2B. The fracture toughness values of both nanocomposites were lower than the fracture toughness of the monolithic Si3N4. This can lead to the conclusion that any nano-phase toughening effect in these materials does not probably exist and the determined value of fracture toughness is valid for fine Si3N4 grains with a low aspect ratio. During cooling of nanocomposites from the sintering temperature the differences in the elastic moduli and in the linear thermal expansion coefficients generally results in the generation of residual stresses in the matrix as well as in the particles. Thermal expansion mismatch in the Si3N4 + SiC nanocomposite caused tensile radial stress at the Si3N4/SiC grain boundaries. The radial residual stresses between the SiC

particles and Si3N4 matrix have tensile character, but the tangential component of the residual stress is compression and in the case of the intergranularly located SiC positively influences the Si3N4/SiC grain boundary strength. Presence of a glassy film on the grain boundaries caused internal stress relaxation and lower residual stresses in Si3N4 + SiC nanocomposite in comparison with Al2O3+ nanoSiC composite [14]. In monolithic Si3N4 with coarser grains and higher aspect ratio pull-out and deflection were present which induced toughening like mechanisms. Such crack bridging mechanisms are not active in the finer microstructure of nanocomposites. 3.3. Strength Weibull distributions of the measured four-point flexure strength values of the investigated nanocomposites and monolithic silicon nitride are in Fig. 2. The two-parameter Weibull statistics gives, for C2B nanocomposite, a characteristic strength of r 0 = 669 MPa and Weibull modulus m = 5.4. The C1B nanocomposite exhibits a higher characteristic strength and Weibull modulus than the nanocomposite C2B; r 0 = 779 MPa and m = 8.7. However, strength characteristics of the reference monolithic Si3N4 have the best strength values from among the studied materials, the value of its characteristic strength is 870 MPa with Weibull modulus of 12.4. In this case the refined microstructure of nanocomposites did not bring a positive effect to strength characteristics. This is caused by the defectiveness of the nanocomposite as revealed by the fractographic analysis. Strength limiting flaws were common technological defects such as large grains, Fig. 3a, powder agglomerates, Fig. 3b, and pores. Defects were most frequently present in C2B material in the form of agglomerates of SiC grains often connected with a porous area and/or in the form of clusters of non-reacted carbon. Their dimensions were in a

Fig. 3. Characteristic defects in nanocomposites, (a) large grains of SiC, (b) cluster of non-reacted carbon.

M. Kasiarova et al. / Materials Science and Engineering C 26 (2006) 862 866 Table 4 Values of slow crack growth parameter N for the studied materials Material Si3N4 C1B C2B N 38 48 62 Table 5 The results of strain exponent n and activation energy Q Material Si3N4 Nanocomposite C2B Activation energy [kJ/mol] 820 480 Stress exponent 2.28 4.21 0.8 1.28

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Creep mechanism Cavitation Diffusion, grain boundary sliding

range from 10 Am to 180 Am with the average defect size of 80 Am. The number of this defects influences the degradation grade of the strength characteristics. In material C1B technological defects are less frequent. Defects were of the same type as in C2B material, their dimensions were from 15 Am to 120 Am with an average size of 52 Am. During flexure test, the middle of the specimens exploded at the moment of failure into many small parts in the studied monolithic system without presence of a visible fracture origin on fracture surfaces. This defectless microstructure results in the best strength characteristics of the monolithic silicon nitride. 3.4. Subcritical crack growth at room temperature The measured values of strength for different loading speeds are summarized in Table 3. It is evident that with increasing stressing rate the strength values increase, because there is less time for subcritical crack growth until fracture occurs. The values of slow crack growth parameter N are in Table 4. The determined N value indicated that the material is not very sensitive to the subcritical crack growth. The resistance of materials to subcritical crack growth depends on the glassy phase which surrounds the Si3N4 grains. The best resistance to subcritical crack growth for nanocomposite C2B is probably connected with the amount of nanoparticles located on the grain boundaries. Firstly, the presence of nanoparticles changed the volume fraction of glassy phase and secondly, the presence of nanoparticles changes the chemistry of intergranular glassy phase. 3.5. Creep behavior Characteristic creep curves obtained in a step-wise loading regime are illustrated in Fig. 4, the label Si3N4-SiC replaced

by C2B exhibits only minimum creep deformation up to 1300 -C. Significant creep deformation was detected above the temperature 1350 -C, only. The creep resistance of the nanocomposite was found to be significantly higher when compared to the creep resistance of the monolithic Si3N4. Based on the shape of the creep curve of Si3N4 it is possible to say that after the primary creep stage a creep crack nucleation takes place in the Si3N4 through cavitation and cavity joining. In the nanocomposite no creep crack has been detected even after very long loading times and the creep is probably controlled by diffusional mechanism. The higher creep resistance of the nanocomposite C2B when compared to the monolithic Si3N4 can be explained by the different additives and by the presence of the SiC nanoparticles on the boundary of Si3N4 grains. The stress exponents and activation energies, together with the results of TEM examination, show that there exist different creep mechanisms in the monolithic silicon nitride and in the nanocomposite; namely cavitation together with grain boundary sliding and solution/precipitation, respectively. The results of strain exponent n and activation energy Q are shown in Table 5. It seems that the intergranularly located SiC nanoparticles are very important. They hinder the grain growth of the Si3N4, changing the shape and chemistry of the grain boundaries and grain boundary phases. 4. Conclusions Monolithic silicon nitride and nanocomposites prepared by carbothermal reduction of SiO2 and carbon have been studied. The following main results were found: A positive influence of the addition of SiC particles on the room temperature strength and fracture toughness was not observed; The presence of SiC inclusions in nanocomposites have a positive influence on the subcritical crack growth of the nanocomposites; A significant influence of the SiC nanoparticles addition has been found on high-temperature properties, especially on the creep resistance of these materials. Acknowledgments This work was supported by the Slovak Grant Agency Project No. 2/4173/04, APVT-51-049702, Centrum of Excellence NANOSMART and Grant SO 51/03R80600/ 03R0603.

Fig. 4. The creep deformation behavior of experimental materials at different temperatures and stresses.

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