Silicon Nitride composites with the addition of CNTs A...

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


3 hours


3 hours

Mixing with 3 wt%

MWCNTs

10 hrs oxidizedα-Si3N4

20 hrs oxidizedα-Si3N4 320/06/2019 Semester Progress Report June - 2019,

Obuda University

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,

Obuda University

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).


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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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Thank You for your attention!Köszönöm a figyelmet!


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