DEPARTMENT OF MECHANICAL ENGINEERING

NATIONAL UNIVERSITY OF SINGAPORE

China, June 29, 2015

ICNAME 2015June 29 – July 1, 2015, Harbin, China

A/Prof. Manoj Gupta

2

Magnesium as Base Material

Faculty of EngineeringMechanical Engineering

http://earthobservatory.nasa.gov/IOTD/view.php?id=885

Sixth most abundant element in earth’s crust (2% by mass).

Third most dissolved mineral in sea water (1.1kg/m3)

G. Neite, K. Kubota, K. Higashi, and F. Hehmann, “Magnesium-

Based Alloys,” in Materials Science and Technology, Wiley-VCH

Verlag GmbH & Co. KGaA, 2006.

http://www.dreamstime.com/stock-photos-sustainable-earth-looking-

magnifying-glass-globe-looked-lens-sustainability-image30740863

3http://www.google.com.sg/imglanding?q=periodic%20table&imgurl=http://www.corrosionsource.com/handbook/periodic/periodic_table.gif&imgrefurl=http://www.corrosionsource.com/handbook/periodic/

&h=480&w=580&sz=19&tbnid=G4wY8RtD2Q3AMM:&tbnh=111&tbnw=134&prev=/images%3Fq%3Dperiodic%2Btable&usg=__2K1JZaCKxL3ggLvPLXeNiIDZwnY=&ei=tFZ7S5W-

E4q0rAe_k9n1Dw&sa=X&oi=image_result&resnum=4&ct=image&ved=0CBcQ9QEwAw&start=0#tbnid=G4wY8RtD2Q3AMM&start=0

Positives

Melting Point (650 deg C)

Density (1.74 g/cc)

Specific Strength

Damping

Electromagnetic shielding

Negatives

Ductility (5-8%) (!)

Modulus (40-45 GPa) (!)

Wet corrosion (!)

Cost (!)

Can Magnesium Catch up With Aluminum?

4http://www.google.fr/imgres?imgurl=http://cmgroup.net/user_assets/ae685e3d4f0c4366b2eb035f7284782f989a5e1b/_industry_item_large.png&i

mgrefurl=http://cmgroup.net/en/industries/magnesium&h=330&w=500&tbnid=2Kuf1vXL-

hxJqM:&zoom=1&tbnh=118&tbnw=179&usg=__bSFosMwhKJRelwgwL7Wh8xElBr8=&docid=G3eFlGQ88pUJSM

Increase in Mg supply indicates an increase in its use in engineering applications. However, a common researcher may not be aware of it.

5

Magnesium Has Plenty of Room to Catch Up With Aluminum

6

Mg-materials are promising replacements for Al, Ti and Steels.

Mg Based Materials - Comparison

Processing Advantages

Low energy requirement for melting

Excellent castability

Excellent machinability

Can be turned, milled at high speed

High production rate

Improved tool life

The EU Regulation (EC No 443/2009) sets standards to frame the CO2

emissions of new passenger cars. The limit set by the Regulation is 130 g

of CO2/km. From 2020, this level is to be reduced to 95 g of CO2 .

For that, it will be necessary to attain high mileage of ~30 km/l.

Magnesium Provides The Opportunity for Fuel

Efficiency and Reduced CO2 Emission

8

Convair XC-99: High Mg content in airframe.

1947

Why Are We Afraid of Magnesium?

1943

http://www.1st100.com/part2/maggie.htmlhttp://www.air-and-space.com/xc99.htmwww.hydro.comAutouniversum.worldpress.com

1950

~ 20 kg of Mg usage in Beetle cars.

1970

Mg fan blade.

9

BMW N52 engine (2004-2011)

Magnesium alloy for the crankcase shell, with

aluminum inner block.

http://en.wikipedia.org/wiki/BMW_N52

Magnesium alloy for Engine Block (1969-

1978) - PORSCHE.

http://blog.caranddriver.com/flat-sixy-the-evolution-of-

porsche-911-engine-size-technology-and-output-in-the-u-s/

10

Oct 24, 2012 @ 12:49 PM

http://www.worldcarfans.com/112102349720/gm-introduces-magnesium-sheet-metal---promises-to-be-lighter/lowphotos#0

11

12

The relation between vehicle mass and fuel consumption.

Eliezer, D., E. Aghion and F.H. Froes, 1998. Magnesium science and technology, Adv Mat Performance, 5: 201-212.

http://www.tifilms.com/americas/en/sustainability/greenhous

e-gas-emission

Main Reasons Why Magnesium Is Considered

Magnesium in Airplanes

“Through the efforts of Dow [...] the ocean is yielding its magnesium. For the first

time in history man is successfully tapping this inexhaustible benefit of a metal

whose phenomenal lightness gives swiftest wings to the airplane so essential to our

victory drive.

Magnesium will lighten the tasks of man in countless ways as yet undreamed of,

except in the minds of far-seeing engineers and [...] who are already planning the

future.”- 1942 Dow Chemical Ad

14

Posted: Sep 03, 2012 - 2017

Nanotechnology-based Magnesium Materials for Vehicles, Airplanes and Satellites

Materials scientists to develop new magnesium materials for ground boundvehicles, airplanes and satellites in the EU-project EXOMET, which iscoordinated by the European Space Agency (ESA).

27 partners

20 million Euros investment for 5 years.

For that purpose the scientists use nanoparticles, silicon carbide, aluminiumoxide as well as nanocarbon particles.

http://www.nanowerk.com/news2/newsid=26582.php

15

Magnesium, absorbable-drug

eluting stent. Courtesy of

BIOTRONIK, Berlin, Germany.

Screws used to correct mild hallux

valgus [82]: left: titanium screw

(fracture compressing screw, Königsee

Implantate GmbH, Allendorf, Germany),

and right: MAGNEZIX compression

screw. Courtesy of Syntellix AG,

Hannover, Germany

http://www.jle.com/fr/revues/mrh/e-docs/magnesium_based_implants_a_mini_review_303769/article.phtml?tab=images

Magnesium Emerging As Implant Material

http://www.pharmacyonline.com.au/blackmores-bio-

magnesium-tab-x-100/

Effect of Aluminum Addition on the Microhardness and Tensile Strength of AZ31-Al2O3 Magnesium Nanocomposite

Magnesium in Marine -Military Application

1- N. Jeal, “High-Performance Magnesium,”Advanced Materials & Processes, 9 (2005), 65-672- Heidi Maupin1, Eric Nyberg2and SuveenN. Mathaudhu. Magnesium Alloys in Army Applications: Past, Current and Future

Solutions. The Sixth TriennielInternational Fire & Cabin Safety Research Conference, 25-28 October 2010, Atlantic City, NJ.

Magnesium in Marine Application

2.5 liter V6 magnesium alloy engine block

(Photo: US Department of Energy)

19

Processing Techniques

&

Experimental Procedures

Faculty of EngineeringMechanical Engineering

20

Processing

Liquid Metallurgy Route

Matrix

Mg Turnings (99.9% Purity)

Powder Metallurgy Route

Matrix

Mg Powder (96.5% Purity)

Reinforcements

Al2O3

Y2O3

MgO

ZrO2

Processing Techniques

CNT

Ti

Ni

Cu

TiB2

TiN

SiC

TiC

Amorphous

Metastable

Hollow

21

Faculty of EngineeringMechanical Engineering

Argon

Gas

TankResistance Furnace

Ar Ar

Thermocouple

Crucible Lid

Graphite Crucible

Pouring Nozzle

Molten Slurry

Mold

Substrate

750 oC

Motor

Argon-filled Chamber

Stirrer

Disintegrated Melt Deposition (DMD)

22

Mg Nanocomposite Casting

Mg Billet

Extruded Rod

Ingot/Billet /Rod

23

Cast Ingots

Raw cast ingot

Machined ingot

(~35 cm length, ~18kg/ingot)

~ 42 cm length18 cm dia.

24

Powder Metallurgy Route

Reinforcement Mg Powder

Blending

V- Blender rotated at 50 rpm

Planetary Ball Mill

Compaction

Diameter:35 mm

Height: 40 mm

Sintering

Tube Furnace (2 Hrs) /

Microwaves (14 minutes)

Microwave Sintering Setup

• Hybrid heating using microwaves and radiant heat from SiC susceptors.

Microwave Oven

00:00 Controlled atmosphere

chamber

Lid

Powder compact

Insulation

Outer ceramic crucible

Inner ceramic crucible

Dummy Block

Turntable

1 2 3 4 56 7 8 9 0 Microwave susceptor

MaterialsHeating Duration Temperature Atmosphere Energy consumption

(mins) (OC) kWh

Conventional ~170 512 (0.85 Tm) Argon 17

Microwave 14 ( 91%) 640 Air 0.7 (96%)

26

Magnesium Based Nanocomposites

27

Why Nano-Composite Technology?

To improve on limited ductility of magnesium

To improve on modulus of magnesium

To improve on dynamic properties of magnesium

To improve on high temperature stability of magnesium

To improve creep performance of magnesium

To improve on wear resistance of magnesium

To improve on fatigue performance of magnesium

To improve on corrosion resistance of magnesium

To improve the damping capability of magnesium

28

Reinforcement at Nanolength Scale

Faculty of EngineeringMechanical Engineering

29

Reinforcement at Nanolength Scale -LOGIC

Ductility can be reduced by 80% with the addition of micron-size

ceramic particles as reinforcements

High percentage of cracked particles and particle-matrix

interfacial failure

Broken Particles

Voids at Particle

Matrix Interface

Y. El-Saeid Essa, J. Ferna´ndez-Sa´ez, J.L. Pe´rez-Castellanos, Comps Part B: Eng, 34 (2003) 551-560

30

Metal - Ceramic Nano-

Composites

Faculty of EngineeringMechanical Engineering

Mg-Al2O3 System (DMD)DMD – Disintegrated Melt deposition technique + hot extrusion

Material

Reinforcement Vol. Percent

(%)

0.2 Tensile Yield

Strength(MPa)

Ultimate Tensile

Strength(MPa)

Tensile Fracture Strain

(%)

Mg 0 97 ± 2 173 ± 1 7.4 ± 0.2

Mg/0.22Al2O3 0.22 146 ± 5 207 ± 11 8.0 ± 2.3

Mg/0.66Al2O3 0.66 170 ± 4 229 ± 2 12.4 ± 2.1

Mg/1.11Al2O3 1.11 175 ± 3 246 ± 3 14.0 ± 2.4

Al2O3 particle size: 50 nm

Extrusion ratio: 22.5:1

Hassan, S.; Gupta, M., Enhancing physical and mechanical properties of Mg using nanosized Al2O3

particulates as reinforcement. Metallurgical and Materials Transactions A 2005, 36, (8), 2253-2258.

Simultaneous improvement in strength and ductility can be realized.

Mg-B4C System (DMD)

Material

Reinforcement Vol. fraction

(%)

0.2 Tensile Yield

Strength(MPa)

UltimateTensile

Strength(MPa)

Tensile Fracture Strain

(%)

Mg 0 120 ± 9 169 ± 11 06.4 ± 0.7

Mg/1.04B4C 1.04 137 ± 5 215 ± 8 17.4 ± 2.0

Mg/1.74B4C 1.74 160 ± 2 240 ± 5 12.4 ± 1.7

B4C particle size: 50 nm; Extrusion ratio: 22.5:1

S. Sankaranarayanan, R.K. Sabat, S. Jayalakshmi, S. Suwas, M. Gupta, Effect of nanoscale boron carbide particle addition on the

microstructural evolution and mechanical response of pure magnesium. Materials & Design, Volume 56, 2014, Pages 428-436.

Material

Reinforcement Vol. fraction

(%)

0.2 Comp. Yield

Strength(MPa)

Ultimate Comp.

Strength(MPa)

Compressive Fracture Strain

(%)

Mg 0 70 ± 8 234 ± 8 19.2 ± 0.9

Mg/1.04B4C 1.04 102 ± 2 308 ± 9 25.5 ± 1.2

Mg/1.74B4C 1.74 115 ± 4 345 ± 4 21.7 ± 1.1

Mg-BN System (DMD)

Material

Reinforcement Vol. fraction

(%)

0.2 Tensile Yield

Strength(MPa)

UltimateTensile

Strength(MPa)

Tensile Fracture Strain

(%)

Mg 0 120 ± 9 169 ± 11 6.4 ± 0.7

Mg/0.3BN 0.3 133 ± 4 193 ± 7 8.6 ± 0.8

Mg/0.86BN 0.86 154 ± 2 223 ± 2 15.3 ± 0.6

Mg/1.44BN 1.44 178 ± 5 255 ± 3 12.6 ± 1.3

BN particle size: 50 nm; Extrusion ratio: 22.5:1

Material

Reinforcement Vol. fraction

(%)

0.2 Comp. Yield

Strength(MPa)

Ultimate Comp.

Strength(MPa)

Compressive Fracture Strain

(%)

Mg 0 70 ± 8 234 ± 8 19.2 ± 0.9

Mg/0.3BN 0.3 84 ± 9 275 ± 12 18.9 ± 0.7

Mg/0.86BN 0.86 97 ± 3 297 ± 8 17.1 ± 1.5

Mg/1.44BN 1.44 109 ± 4 307 ± 6 17.6 ± 2.0

Fatigue Behavior

34

35

Max

imu

m S

tres

s (M

Pa)

Variation of maximum stress (s max) with fatigue life (Nf) at load ratio (R = -1)

Fatigue Life (Nf)

AZ31/1.0 vol% CNT AZ31

200

100

150

50

104 105 106 107

T.S. Srivatsan, C. Godbole, M. Paramsothy, and M. Gupta, Influence Of Nano-sized Carbon Nanotube Reinforcements On

Tensile Deformation, Cyclic Fatigue and Final Fracture Behavior of a Magnesium Alloy, Journal of Materials Science, Vol. 47,

Issue 8, April 2012, pp. 3621-3638.

Ma

xim

um

Str

es

s (

MP

a) 150

AZ31/1.0 vol% Al2O3

AZ31

T = 250C

R = - 1

100

50

104 105 106 107

Fatigue Life (Nf)

stress (r max ) with fatigue life (Nf) for

2O3 at ratio (R = r mi n/r ma x)

Variation of maximum stress with fatigue life (Nf) for AZ31 and AZ31/1 vol.% Al2O3

at load ratio R = -1

T. S. Srivatsan, C. Godbole, T. Quick, M. Paramsothy and M. Gupta, Mechanical Behavior of a Magnesium Alloy Nanocomposite Under

Conditions of Static Tension and Dynamic Fatigue, Journal of Materials Engineering and Performance, Volume 22, Issue 2 (2013), Page

439-453.

37

Faculty of EngineeringMechanical Engineering

Dynamic Behavior

For applications in vehicles, aircraft and armor to evaluate their resistance to dynamic loads associated with accidental collisions or foreign-object impact .

Split Hopkinson Tensile Bar

Strain rate of 1.2 x 103 s-1

38

AZ31-Al2O3 System

Nanocomposites show:

a. Enhanced yield stress.b. Ultimate Strengthc. Ductility (11% to 33%)

Y. Chen, Y.B. Guo, M. Gupta, V.P.W. Shim, Dynamic tensile response of magnesium nanocomposites and the effect of

nanoparticles, Materials Science and Engineering A, 582, 359-367, 2013.

0

50

100

150

200

250

300

350

400

0 5 10 15 20 25

Tru

e S

tress /M

pa

True Strain %

AZ31-1200/s

AZ31C1.0-1200/s

Az31C1.4-1200/s

AZ31C3.0-1200/s

Tension test Results at Strain Rate ~ 103 s-1

39

Faculty of EngineeringMechanical Engineering

High Temperature Behavior

40

Variation in yield strength and tensile strength as a function of temperature.

Mg-Y2O3 System

A Mallick, KS Tun and M. Gupta, Deformation Behaviour of Mg/Y2O3 Nanocomposite at Elevated Temperatures, MSE A, 551,

222-230, June 2012.

Temp.

(in °C)

Yield Strength (MPa)

Pure Mg Mg / Y2O3

25 132 148

100 84 98

150 58 92

200 47 70

250 41 62

Temperature (°C)

41

Creep Performance

42

MaterialMicrohardness

(Hv)

Compressive Yiel

d Strength

(MPa)

Ultimate Compr

essive Strength

(MPa)

Compressive Frac

ture Strain

(%)

Pure Mg 46 ± 1 76 ± 4 273 ± 9 19.2 ±0.7

Mg-5Sn-2Y93 ± 6

(+100)

105 ± 1

(+38)

402 ± 14

(+47)20.5 ± 1.3

Mg-5Sn-2Y-1.5ZnO114 ± 4

(+148)

121 ± 6

(+59)

432 ± 11

(+58)

27.4 ± 1.9

(+34)

Number in brackets represents percentage improvement in properties when compared to pure Mg.

Composition is in wt. %

Results of Microhardness and Compressive Property Measurements

Processing: DMDHot Extrusion: 20:1 ratio

Sn: Mg2Sn melts at 770 °C and can provide high temperature stability.

Y: Assists in solid solution and precipitation hardening and enhances ductility.ZnO: 90-nm and 99.9% purity.

43Representative compression creep curves for Mg-5Sn-2Y and its nanocomposite.

Dry Sliding Behavior

44

45

The composites exhibit better wear resistance up to 25% compared to its monolithiccounterpart due to their superior hardness and strength.

Under high sliding speed of 10 m/s, thermal softening is observed due to increased frictionalheating. The alloying of calcium and addition of nano alumina particulate reinforcement

appears to be beneficial in improving wear resistance up to 30% and delaying the onset ofthermal softening under severe sliding conditions.

AZ31B/ 1.5Vol.% Al2O3 (DMD – 20.25:1)

M. Shanthi, QB Nguyen and M. Gupta, Sliding Wear Behavior of Calcium Containing AZ31B/Al2O3 Nanocomposites, Wear, 269 (5-6), 473-479, July 2010.

46

Faculty of EngineeringMechanical Engineering

Machining Behavior

47

Recast layer

Microcrack

Sample showing EDM-drilled hole

a. High aspect ratio holes (0.5 mmΦ and 12 mm height) successfully drilled with minimal damages.

b. Abnormal arcing and random spark discharges avoided in nanocomposites when compared to micro-composites. Bands are craters are normally observed in micro-composites.

c. Minimal surface roughness (Ra: 3-8 mm) due to process efficiency and nano-reinforcement. Size of recast layer restricted to 18 mm

K. Ponappa, S. Aravindan, PV Rao, J. Ramkumar and M. Gupta, The Effect of Process Parameters on Machining of Magnesium nano alumina Composites

through EDM, International Journal of Advanced Manufacturing Technology, 46 (9-12), 1035-1042, Feb 2010.

48

Faculty of EngineeringMechanical Engineering

Dry Oxidation

49

Faculty of EngineeringMechanical Engineering

Table 4. Oxidation rate (mpy) of monolithic AZ31B and nanocomposite samplescalculated following Wagner’s model [mpy = 534W / (DAT)] [1] at differenttemperatures [2].

[1] Baboian, R. 1995. ‘Corrosion Tests and Standards, ASTM Manual Series: MNL 20’, ASTM Fredericsburg.[2] Nguyen, Q.B., Gupta, M. and Srivatsan, T.S., 2009. Mater. Sci. Eng. A 500, 233-237.

Time (mins)

At 4500C

AZ31B-1.50Al2O3

AZ31BWeight change

(mg/cm2)

Fig. 3. Influence of temperature on weight change kinetics of AZ31B and AZ31B-1.50 Al2O3 at 450°C [2].

50

Salt Water Corrosion

Faculty of EngineeringMechanical Engineering

51

Faculty of EngineeringMechanical Engineering

Results from polarisation plots using Tafel extrapolation method for AZ31B and AZ31B /1.50vol%Al2O3 (NI) nanocomposite in NaCl solution [1].

[1] Kukreja, M., Balasubramaniam, R., Nguyen, Q.B. and Gupta, M., 2009. Corr. Eng. Sci. Technol. 44(5), 381-383.

Higher salt water corrosion resistance of nanocomposite:

- reduction in the amount of CATHODIC second-phase particles

(Mg17Al12) within the AZ31B metal matrix

Mechanical Properties of Magnesium Composites Containing Amorphous

Reinforcements

Advantages of Metallic Amorphous Reinforcements

Exhibit high strength (~ 1-5 GPa).

Exhibit large elastic strain limit ~ 2%.

Prevents undesirable interface reactions with matrix due to its amorphous

structure.

Compatible matrix/reinforcement interface due to its metallic nature.

Excellent wear resistance.

Excellent corrosion resistance.

9

Mg-Ni60Nb40 System (PM+MWS)

MaterialReinforcement

Vol. fraction(%)

0.2 Compr. Yield Strength

(MPa)

Ultimate Compr. Strength

(MPa)

Compr. Fracture Strain

(%)

Mg 0 70 ± 6 265 ± 8 16.2 ± 0.8

Mg+3Ni60Nb40 3 85 ± 4 283 ± 10 17.4 ± 1.1

Mg+5Ni60Nb40 5 130 ± 11 320 ± 11 18.4 ± 1.3

Mg+10Ni60Nb40 10 90 ± 7 322 ± 10 17.2 ± 1.6

S. Jayalakshmi, Shreyasi Sahu, S. Sankaranarayanan, Sujasha Gupta and M. Gupta. Development of Novel Mg-

Ni60Nb40 Amorphous Particle Reinforced Composites with Enhanced Hardness and Compressive Response, Materials

and Design 53 (2014) 849–855.

Compressive Strength: > 2GPa Crystallization Temp: > 600 deg C

High Elastic Strain Limit: ~ 2% Sintering Temp: 550 deg C

Av. Particle Dia: 10 microns

Crystallite Size: 27Ao

55

Mg-Cenosphere Composites (Foam Composites)

200µm

Microstructure of DMD Processed Mg-based foam composites.

56

CTE (x10-6/C)

Coefficient of thermal expansion of DMD Processed Mg and Mg – Cenospheres Composites.

57

Material Density

(g/cc)

Volume %

Cenosphere

UTS

(MPa)

Hardness (Hv)

Mg 1.7361 ± 0.0004 0 170 ± 8 47 ± 2

Mg-5Ceno 1.6406 ± 0.0048 (6%) 13.24 230 ± 10 98 ± 2

Mg-10Ceno

Mg-15Ceno

1.4905 ± 0.0085 (17%)

1.4203 ± 0.0136 (23%)

26.48

39.72

215 ± 9

180 ± 8

110 ± 6

112 ± 7

Density, Hardness and UTS of DMD Processed Mg and its Composite Foams.

58

Tensile stress – strain curves of DMD processed magnesium and its composite foams.

59

Compressive stress – strain curves of DMD processed Mg and its composite foams.

Use Magnesium Technology in Maritime - IDEAS

Light Weighting of Ships for transportation purposes like for CNG, LNG etc.

Underwater gliders and surveillance or exploration ships.

To improve ship maneuverability.

Reducing carbon signature.

Energy efficiency.

Collision resistance materials for example against icebergs.

CONDITIONS

O Dry and damp conditions.

O Vibration control

O Crash worthiness

61

A. Magnesium based composites can be processed using conventionalprocessing methods requiring no additional infrastructural cost.

B. The addition of nanoparticles, amorphous and hollow reinforcementsto magnesium is capable of simultaneously and significantly increasingmultiple engineering properties of magnesium based materials.

Conclusions

Magnesium Has Arrived.

Think out of box.

Use in Maritime Industries before someone else steals

the show.

Aluminums and plastics can be replaced.

62

ACKNOWLEDGEMENTS

Authors wish to acknowledge National University of Singapore for funding thisresearch through various grants and studentships, Agency for Science,Technology and Research (ASTAR), Temasek Defense Science Institute andMinistry of Education (ongoing) – R 265 000 493 112.

Team Members Over Years Ongoing Gradute StudentsDr N SrikanthDr Syed Fida Hassan Brenda NaiDr Eugene Wong Tan XingheDr Goh Chwee Sim Ganesh MeenashisundaramDr Sharon Nai Sravya TekumallaDr Khin Sandar TunDr Muralidharan Paramsothy Final Year StudentsDr Nguyen Quy Bau Almost 100 of themDr ME AlamDr Meisam Kouhi Habibi Summer InternsDr Sankaranarayanan Seetharaman More than 20.Dr Shanthi Muthusamy

Faculty of EngineeringMechanical Engineering

63

Faculty of EngineeringMechanical Engineering