Alumina Particulate-Epoxy Composite Mechanics via Piezospectroscopy Imad Hanhan, Joseangel Rosas, Any Lai, Erik Durnberg, Ashley Jones, Gregory Freihofer, Seetha Raghavan

Mechanical and Aerospace Engineering, College of Engineering and Computer Science, University of Central Florida, Orlando, FL 32816, USA

INTRODUCTION & MOTIVATION

OBJECTIVES

FUTURE WORK

REFERENCES & ACKNOWLEDGEMENTS

LOAD TRANSFER THEORY

Nanoparticles embedded within a matrix have the capabilityof improving a wide variety of mechanical properties.Alumina-based nanocomposites have the ability to provideintrinsic characteristics of this enhancement through thestress-sensitivity of photo-luminescent emissions.

• Study Al2O3 particulate mechanics with piezospectroscopy.• Establish particle-matrix load transfer characteristics under

varying parameters including volume fraction and strain rate.

PIEZOSPECTROSCOPY

[1] Stevenson, A., Jones, A., and Raghavan, S., “Stress-Sensing Nanomaterial calibrated withPhotostimulated Luminescence Emission” Nano Letters, Vol. 11, pp.3274-3278, 2011.

[2] Clyne T.W., Withers P.J.,1993, An Introduction to Metal Matrix Composites, Cambridge,Great Britain.

[3] Fu S.Y., Feng X.Q., Lauke B., Mai Y.W., “Effects of Particle Size, Particle/Matrix InterfaceAdhesion and Particle Loading on Mechanical Properties of Particulate-PolymerComposites,” Composites, Part B 39, pp.933-961, 2008.

[4] Kim J. and Lee J., “A new Model to Predict Effective Elastic Constants of composites withSpherical Fillers.” Journal of Mechanical Science and Technology 20 (2006) 1891-1897.

[5] Nielsen L.E., “Generalization for the Elastic Moduli of Composite Materials,” Journal ofApplied Physics, Vol. 41 (1970).

[6] Erik Durnberg, Ashley Jones, Joseangel Rosas, George Sunny, and Seetha Raghavan,"Monitoring Strain Rate Effects on Nanocomposites using Piezospectroscopy," 55thAIAA/ASMe/ASCE/AHS/SC Structures, Structural Dynamics, and Materials Conference,January 13-17, 2014

[7] Erik Durnberg, Imad Hanhan, Gregory Freihofer, and Seetha Raghavan, “ExperimentalPiezospectroscopic Measurements To Study Load Transfer in a Single Alumina ParticleEmbedded Within an Epoxy Matrix,” Proceeding of the Society for the Advancementof Material and Process Engineering 2014 conference, 2-5 June 2014, Seattle, WA.

To better understand particulate load transfer, a macro-scaleanalysis of single particle composites, on the millimeter scale,was conducted.

Scan pattern to identify

stress concentrations using

Piezospectroscopy

Damaged zone on an Aerospace structure coated with an alumina

nanocomposite

Alumina Nanocomposite Coating

ISOLATED PARTICLE LOAD TRANSFER RESULTSNANOCOMPOSITE STRAIN RATE EFFECT

RESULTS OF PIEZOSPECTROSCOPIC RESPONSE

Experimental values leadto an R1 PS coefficient of-4.56 ± 0.21 cm-1/Gpa.This indicates that theparticle is sustaining astress ratio of 0.60 [7].

Sample 4 – Particle Stress vs Applied Stress

Deboning

point

67.5 MPa

Fracture

point

Sample Number

R1 PS Coefficient (cm-1/GPa)

R2 PS Coefficient (cm-1/GPa)

1 -4.279 -3.966

2 -4.541 -4.208

3* -3.463 -2.975

4 -4.622 -4.349

5* -1.973 -3.187

6 -4.807 -4.456

All isolated particle results follow the trend above in which theparticle sustains load up to a certain point, and then maintains aconstant peak position. This could be due to the particledeboning from the matrix.

Future work includes the analysis of X-Ray diffraction resultsfrom experiments conducted at the Canadian Light Source X-Ray Synchrotron Facility. X-Ray diffraction was chosen due toits ability to measure stress through the particle, as opposedto photo-luminescence which is a surface measurement.

Photo-luminescence (PL) X-Ray Diffraction (XRD)

These experiments included samples with varying Al2O3

particle sizes to analyze particle size effect and compare tovolume fraction effect.

A manually-actuated load frame wasused to apply force to the epoxy matrix,and a load cell was used to collect forcedata. As a force is held on the matrix,the x-ray synchrotron beam producesXRD rings which are strain sensitive. Thering distortion can be measured andrelated to strain.

There are a number oftheoretical models thathave steered both theunderstanding of loadtransfer between a matrixand a particle, and theeffect of strain rate.

Piezospectroscopy is the method of monitoring the opticalspectrum of a photo-luminescent material and correlatingspectral peak shifts to stress through the PS coefficient. Onceexcited with a laser source, alumina emits an optical spectraconsisting of distinct stress-sensitive peaks, R1 and R2, due toits naturally occurring Chromium ion (Cr3+) impurity. Bymonitoring the resulting spectral peak shifts of R1 and R2,particle stress can be determined.

• All 3 sensitivities look to be similar at low stress and start todiffer during the failure regime.

• Increase in stress transferred to the nanoparticle withincrease in strain rate in the failure regime.

• Normal load transfer mechanics can be seen in the failureregime of the lower strain rates as the material shows asoftening effect, where there can be de-bonding and microcracking taking away stress concentrations on thenanoparticles.

• The higher strain rate shows a hardening effect in the failureregime.

-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0.0

0.1

0 0.02 0.04 0.06 0.08 0.1 0.12

Fre

qu

en

cy S

hif

t (c

m-1)

Uniaxial Compressive Stress (GPa)

Frequency Shift vs. Stress [1]

5% 25% 38%

Our previous work showed that by embedding aluminananoparticles within an epoxy matrix, the piezospectroscopicsensitivity to applied stress on the nanocomposite could betuned with respect to particle volume fraction [1].

Dilute Eshelby

Equations

Ep, νp Em, νm

13𝜎𝑗𝑗

𝜎𝑐

Inputs

f

Stress Ratio Output

Equivalent

composite

properties

model

Em, νm

𝜎𝑐

Theoretical ModelsTheoretical-Experimental Relationship

Compared to pure alumina in perfect axial loading (A) and alumina inperfect hydrostatic loading (C), alumina nanoparticles in compositesexperience mixed loading conditions (B) characterized by their PScoefficients.

Pea

k S

hif

t Δν

Applied

Uniaxial Stress σc

0

1

3𝛱𝑖𝑖

𝛱𝑖𝑖

𝛱𝐶

𝝈𝒄 𝟎 𝟎𝟎 𝟎 𝟎𝟎 𝟎 𝟎

𝝈𝒄 𝟎 𝟎𝟎 𝝈𝒄 𝟎𝟎 𝟎 𝝈𝒄

𝝈𝒂 𝟎 𝟎𝟎 −𝝈𝒃 𝟎𝟎 𝟎 −𝝈𝒃

A)

B)

C)

∆𝑣𝑃 = ∆𝑣𝑁𝐶∆𝑣𝑁𝐶 = ΠNC∆𝜎𝐴∆𝑣𝑃 = ΠP∆𝜎𝐻

ΠP∆𝜎𝐻 = ΠNC∆𝜎𝐴

∆𝜎𝐻∆𝜎𝐴

=ΠNC

ΠP

Stress Ratio in terms of PS coefficient

It is known that

ΠP 𝑅1 = −7.59𝑐𝑚−1

𝐺𝑃𝑎[2]

Varying strain rates resulted in varying load transfer from thematrix into the nanoparticles. As the strain rate (10-2 s-1, 10-3 s-1,and 10-4 s-1 ) increases, the ultimate strength of ananocomposite sample increases [6].

The experimental set up contains aload frame which places the samplein compression, while PL data iscollected by utilizing a laserexcitation source.

Experimental set-up at theCanadian Light Source

Alumina XRD rings

raw image from NEW_pi_m1p14_15s_17855ev1-1.tif

100 200 300 400 500 600 700 800 900

100

200

300

400

500

600

700

800

900

0

10

20

30

40

50

60

* Outlying samples not used in calculations.

0 0.2 0.4 0.6 0.8 10

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

Particle Volume Fraction

Hydro

sta

tic S

tress R

atio

Dilute Eshelby [2]

Non-dilute Eshelby [2]

Haplan 1969 [3]

Mori-Tanaka 1979 [3]

Kim 2006 [4]

R1 experimental

R2 experimental

Nielsen 1970 [5]

Wavenumber (cm-1)

Arb

itra

ry I

nte

nsi

ty

ΔνR1

ΔνR2

Wavenumber vs. Intensity

By conducting a photo-luminescent map of the single particle asthe force is increased on the matrix, it was found that the stressdistribution on the particle is non-uniform, which is notaccounted for by the theoretical models.

This work is supported by the University of Central Florida in house research grant andNational Science Foundation Graduate Research Fellowship under Grant No. DGE-1144246and Grant No. 1130837. Use of the Center for Nanoscale Materials was supported by theU.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, undercontract No. DE-AC02-06CH11357. Undergraduate research efforts were supported by theResearch and Mentoring Program (RAMP).

0 0.02 0.04 0.06 0.08 0.1 0.12 0.14-0.7

-0.6

-0.5

-0.4

-0.3

-0.2

-0.1

0

Uniaxial Compressive Stress (GPa)

Peak

Sh

ift

(cm

-1)

4.5% Volume Fraction - Stress vs. Peak Shift

Low Strain Rate (10-4s-1)

Intermediate Strain Rate (10-3s-1)

High Strain Rate (10-2s-1)