Silicon Nitride composites with the addition of CNTs – A review
Tribological Properties of Si3N4+3 wt. % MWCNTs
Awais Qadir
Supervisor: Prof. Dr. Dusza János
120/06/2019Semester Progress Report June - 2019,
Obuda University
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Tribological Properties of Si3N4+3 wt. % MWCNTs
Materials Preparation
α-Si3N4Powder
Mixing with 3 wt%
MWCNTs
HIPing at 1700 ˚C for
3 hours
Mixing with 3 wt%
MWCNTs
HIPing at 1700 ˚C for
3 hours
HIPing at 1700 ˚C for
3 hours
Mixing with 3 wt%
MWCNTs
10 hrs oxidizedα-Si3N4
20 hrs oxidizedα-Si3N4 320/06/2019 Semester Progress Report June - 2019,
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Density of composites
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Un-oxidized
S3N4-3 wt. %
MWCNT
10 hours
oxidized S3N4-
3 wt. %
MWCNT
20 hours
oxidized S3N4-3
wt. % MWCNT
Apparent Density (gm/cm3) 3.161 3.199 3.235
Relative Density (%) 93.4 94.5 95.6
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Tribological Testing
Resprocatory ball-on-plate Technique,
Applied load 13.5 N, Sliding speed 10 mm/s, Sliding
distance 720 m, Dry conditions, Room temperature, Ball
Si3N4
Confocal Microscopic image of WearTrack
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Un-oxidized Si3N4 + 3 wt. % MWCNTs
10 hrs oxidized Si3N4 + 3 wt. % MWCNTs
20 hrs oxidized Si3N4 + 3 wt. % MWCNTs
Coefficient of Friction (COF)
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Depth of Track
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0 500 1000 1500 2000 2500
-40
-30
-20
-10
0
10
20
30
40
59
.90
(m
)
68
.69
(m
)
72
.43
(m
)
De
pth
(m
)
Lenght (mm)
Un-oxidized
10 hrs oxidized
20 hrs oxidized
Wear Volume
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Un-oxidized 10 hrs oxidized 20 hrs oxidized
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
0.40
We
ar
Vo
lum
e: m
m3
Samples
Decrease in wear volume is attributed to the relative density of the material. Higher relative density, lower wear volume
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Silicon Nitride composites with the addition of CNTs – A review
Carbon Nanotubes Si3N4
• Silicon nitride (Si3N4) is classifiedas an advanced structural ceramicwith high melting point, hard andrelatively chemical inert. It hasthree crystallographic structureon room temperature which arenamed as α, β and ϒ.
• cutting tools, bearings, sealingsand gas turbine engines due to itsexceptional flexural strength, highhardness, resistance to oxidationand thermal properties .
• brittleness, low flaw tolerance,limited number of slip systemsand low reliability limit, lowelectrical conductivity itsapplications in several sectors.
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Material Density (g/cm3)
Tensile Strength (GPa)
Stiffness (GPa)
CNTs 1.3 – 2 10 – 60 1000
Wood 0.6 0.008 16
Steel 7.8 0.4 208
Carbon Fiber 1.7 – 2.2 1.7 – 3.3 200 – 960
Epoxy 1.25 0.005 3.5
Processing of Si3N4+CNTs composites
• Efficient milling process enhances the uniform dispersion of CNTs in the matrix and eventually uniform dispersion enhances the relative density of the sintered composites.
• Processing Techniques: Hot Isostatic Pressing (HIP), Hot pressing (HP), Gas pressuresintering (GPS), Spark Plasma Sintering (SPS).
• Sintering Additives: TiO2, Y2O3, Al2O3, MgO, SiO2, AlN, HfO2 and ZrO2
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Microstructure Development
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Influence on Hardness
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-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
0
2
4
6
8
10
12
14
16
18
20
22
[55]
[14]
[44]
[50]
[50] SPS
[57]
[58]
[46]
[45]
[51] Bead milling 2 hrs
[51] Ball milling 24 hrs
Vic
ke
r's H
ard
ne
ss: G
Pa
CNTs Content (wt. %)
Influence on Strength
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0 1 2 3 4 5 6 7
200
300
400
500
600
700
800
900
1000
1100
1200
1300
[13]
[55]
[14]
[15]
[56]
[44] 4 pt. bending
[57]
[12]
[22]
[56]
[58]
[59]
[51]
[60]
Fle
xu
ral S
tre
ng
th: M
Pa
CNTs Content (wt. %)
Influence on Fracture Toughness
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-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
8.5
[55]
[14]
[44]
[50] HIP
[50] SPS
[57]
[58]
[46] SPS for 5 min, 100 MPa gas pressure
[46] SPS for 3 min, 50 MPa gas pressure
[45]
[51] Bead milling 2 hrs
[51] Ball milling 24 hrs
Fra
ctu
re T
ou
gh
ne
ss: M
Pa
.m1
/2
CNTs content (wt. %)
Toughening Mechanism by CNTs
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fracture toughness increases with the
increasing size of the crack
Crack deflection at the CNT/ Si3N4 interface,
crack-bridging by CNTs and CNTs pulling out
on the fracture surface of silicon nitride
composites
Origin of Fracture
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fracture origin is microstructure imperfections
such as pores, inner residual cracks, non-
densified part, clusters of reinforcement
particles and impurities.
Electrical Properties
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0 1 2 3 4 5 6 7 8
1.0x10-8
2.0x10-8
3.0x10-8
4.0x10-8
5.0x10-8
6.0x10-8
7.0x10-8
8.0x10-8
9.0x10-8
10-2
5x10-2
5x10-1
5x100
5x101
5x102
[45] HIP
[97] SPS 1600 C
[97] SPS 1300 C
[100] SPS 1585 C
[12] HIP
[61]
[101] GPS
[101] HIP
[51] bead milling
[51] ball milling
[60] GPS + HIP, bead milling
[60] GPS + HIP, ball milling
[49] SPS at 1600 C
Ele
ctr
ica
l C
on
du
ctivity (
S/m
)
CNTs content (wt. %)
electrical resistivity of monolithic Si3N4 >1014 Ω.cm
at room temp
Major challenges in integrating CNTs in Si3N4
• Uniform dispersion
• Damaging of CNTs
• Oxidation of CNTs
• Clustering of CNTs
• Densification inhibition
• CNTs induce porosities in the composite
• Poor interfacial boding between matrix grainsand CNTs
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Concluding Remarks
• CNTs induce the porosity which is main causeof degradation of mechanical propoerties
• CNTs can cuase of toughening mechanism bycrack bridigng, crack deflection and pulling-out.
• Electrical properties are enhanced with theaddtion of CNTs
• Tribological properties also enhanced with theaddition of CNTs
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Concluding Remarks
• To obtain CNT-reinforced Si3N4 with betterproperties and tailored microstructure, theseissues should be considered: achievinghomogeneous dispersion of CNTs in the Si3N4matrix, to avoid the CNTs agglomeration,entangling, clustering and damaging,interfacial bonding between CNT and Si3N4grains and toughening mechanism (crackbridging, crack deflection and pull-outmechanisms).
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Future Plans
• Oral presentation at 6th international conference “Fractography of Advanced Ceramics” in the Smolenice Castle Congres Center, Smolenice SAS on September 08 - 11, 2019.
• Tribological test under different loads• Electrical Conductivity measurement of monolithic and
CNTs reinforced Si3N4. • Thermal Properties measurement of monolithic and
CNTs reinforced Si3N4.• Writing an article on Tribological properties of Si3N4+3
wt.% MWCNTs. •
20/06/2019 23Semester Progress Report June - 2019,
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List of Publications 2017-2019• A. Qadir, Z. Fogarassy, Z. E. Horváth, K. Balazsi, and
C. Balazsi, “Effect of the oxidization of Si3N4 powder on the microstructural and mechanical properties of hot isostatic pressed silicon nitride,” Ceramics International, vol. 44, no. 12, pp. 14601–14609, Aug. 2018. (Impact Factor 2.986). https://doi.org/10.1016/j.ceramint.2018.05.081
• Awais Qadir; Katalin Balazsi; Csaba Balazsi; Jan Dusza “Processing and properties of S3N4 + MWCNTs composites from oxidized silicon nitride powder”, July 2019 (to be submitted) (Journal with IF).
• Awais Qadir; Pinke Peter; Jan Dusza; “ CNTs reinforced silicon nitride composites - A review, July 2019 (to be submitted) (Journal with IF).
2420/06/2019Semester Progress Report June - 2019,
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https://doi.org/10.1016/j.ceramint.2018.05.081
Participation in Conferences 2017-2019• Junior EuroMat Conference 2018, Budapest
• Fine Ceramics Day 2018, Budapest
• Attended Hungarian Microscopic Conference 2017 in Siofok,
Hungary - Magyar Mikroszkópos Társaság• Poster Presentation in ECerS 2017, 15th
Conference & Exhibition of the European Ceramic Society, 2017
• Poster Presentation International Conference Deformation and Fracture in PM Materials, High Tatras, 2017. Oct.22-25.
• Poster Presentation in Joint ICTP-IAEA Workshop on Fundamentals of Vitrification and Vitreous Materials for Nuclear Waste Immobilization, The Abdus Salam Centre for Theoritical Physics (ICTP), Trieste Italy. Nov. 06 -10, 2017.
• Oral Presentation “17th PhD Students Materials Science Day”,University of Pannon, Veszprem, Hungary, Dec. 4. 2017
• Doctoral Summer School at Károly Róbert University, August 2017
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References• [14] Cs. Balázsi, Wéber, F., Kövér, Z., Shen, Z., Konya, Z., Kasztovszky, Z., ... & Arato “Application of carbon nanotubes to silicon nitride matrix
reinforcements,” Curr. Appl. Phys., vol. 6, no. 2, pp. 124–130, Feb. 2006.• [44] S. Pasupuleti, Peddetti, R., Santhanam, S., Jen, KP, Wing, ZN, Hecht, M., & Halloran, JP “Toughening behavior in a carbon nanotube
reinforced silicon nitride composite,” Mater. Sci. Eng. A, vol. 491, no. 1, pp. 224–229, Sep. 2008.• [45] A. Kovalčíková, Cs. Balázsi, J. Dusza, and O. Tapasztó, “Mechanical properties and electrical conductivity in a carbon nanotube reinforced
silicon nitride composite,” Ceram. Int., vol. 38, no. 1, pp. 527–533, Jan. 2012.• [46] Cs. Balázsi, Shen, Z., Kónya, Z., Kasztovszky, Z., Weber, F., Vertesy, Z., ... & Arato, P. “Processing of carbon nanotube reinforced silicon
nitride composites by spark plasma sintering,” Compos. Sci. Technol., vol. 65, no. 5, pp. 727–733, Apr. 2005.• [47] E. L. Corral, Cesarano III, J., Shyam, A., Lara-Curzio, E., Bell, N., Stuecker, J., ... & Barrera, EV “Engineered Nanostructures for
Multifunctional Single-Walled Carbon Nanotube Reinforced Silicon Nitride Nanocomposites,” J. Am. Ceram. Soc., vol. 91, no. 10, pp. 3129–3137, 2008.
• [48] J. Gonzalez‐Julian, J. Schneider, P. Miranzo, M. I. Osendi, and M. Belmonte, “Enhanced Tribological Performance of Silicon Nitride-Based Materials by Adding Carbon Nanotubes,” J. Am. Ceram. Soc., vol. 94, no. 8, pp. 2542–2548, 2011.
• [49] M. Belmonte, S. M. Vega-Díaz, A. Morelos-Gómez, P. Miranzo, M. I. Osendi, and M. Terrones, “Nitrogen-doped-CNTs/Si3N4 nanocomposites with high electrical conductivity,” J. Eur. Ceram. Soc., vol. 34, no. 5, pp. 1097–1104, May 2014.
• [50] O. Tapasztó, Kun, P., Weber, F., Gergely, G., Balazsi, K., Pfeifer, J., ... & Balazsi, C. “Silicon nitride based nanocomposites produced by two different sintering methods,” Ceram. Int., vol. 37, no. 8, pp. 3457–3461, Dec. 2011.
• [51] M. Matsuoka, J. Tatami, T. Wakihara, K. Komeya, and T. Meguro, “Improvement of strength of carbon nanotube-dispersed Si3N4 ceramics by bead milling and adding lower-temperature sintering aids,” J. Asian Ceram. Soc., vol. 2, no. 3, pp. 199–203, Sep. 2014.
• [52] C. Balázsi, K. Sedláčková, and Z. Czigány, “Structural characterization of Si3N4–carbon nanotube interfaces by transmission electron microscopy,” Compos. Sci. Technol., vol. 68, no. 6, pp. 1596–1599, May 2008.
• [60] S. Yoshio et al., “Dispersion of carbon nanotubes in ethanol by a bead milling process,” Carbon, vol. 49, no. 13, pp. 4131–4137, Nov. 2011.• [61] P. Ge, K. Sun, A. Li, and G. Pingji, “Improving the electrical and microwave absorbing properties of Si3N4 ceramics with carbon nanotube
fibers,” Ceram. Int., vol. 44, no. 3, pp. 2727–2731, Feb. 2018.• [97] E. L. Corral, H. Wang, J. Garay, Z. Munir, and E. V. Barrera, “Effect of single-walled carbon nanotubes on thermal and electrical properties
of silicon nitride processed using spark plasma sintering,” J. Eur. Ceram. Soc., vol. 31, no. 3, pp. 391–400, Mar. 2011.• [100] J. González-Julián, J., Iglesias, Y., Caballero, AC, Belmonte, M., Garzón, L., Ocal, C., ... & Osendi, “Multi-scale electrical response of silicon
nitride/multi-walled carbon nanotubes composites,” Compos. Sci. Technol., vol. 71, no. 1, pp. 60–66, Jan. 2011.• [101] B. Fényi, P. Arató, F. Wéber, N. Hegman, and C. Balázsi, “Electrical Examination of Silicon Nitride – Carbon Composites,” Materials Science
Forum, 2008. [Online]. Available: https://www.scientific.net/MSF.589.203. [Accessed: 15-May-2019].
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Thank You for your attention!Köszönöm a figyelmet!
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