21/12/2005 Depth Sensing Indentation of Polymeric Materials

Rushabh J. Vora, Dr. I. A. Ashcroft and Dr. R. Hague

Presented by: Rushabh J. Vora

Contents
Introduction Objectives Experimental Technique
Study of cure kinetics and time dependent behaviour Investigation of viscoelastic/viscoplastic behaviour and determination of suitable test parameters Finite element Analysis (FEA) and Atomic force microscopy (AFM)

Conclusions

Introduction
Rapid Prototyping (RP) Stereolithography (SL) Ageing and non-uniform mechanical properties. DSI technique. Application to polymers. Sensitivity to stress state and strain rate.

Objectives
Investigation of mechanical properties of an epoxy based SL7580 using DSI technique. Investigation of viscoelastic/viscoplastic behaviour determination of suitable testing parameters and

To investigate curing of the SL resin and relate this to the mechanical properties. To generate comparative mechanical data using standard test methods such as uniaxial compressive, tensile and creep tests and dynamic mechanical thermal analysis (DMTA).

Objectives
Finite element modelling is used to increase understanding of DSI of polymers. AFM is used to study the surface roughness, nonuniformities and indentation impression.

Stereolithography (SL) process

The photopolymer used in the current research is SL7580, which is produced by RenShape Solutions, the tooling unit of Huntsman advanced materials (www.huntsman.com)
SL7000

from 3D system

Sample preparation
Post-processing technique
Group A: - Stereolithography samples cleaned with TPM (Tri-propylene Glycol Monomethyl Ether)

Group B: - Stereolithography samples cleaned with TPM and U.V post cured for 90 minutes.
Group C: - Stereolithography samples treated with Methanol. Group D: - Stereolithography samples treated with Methanol and U.V post-cured for 90 minutes.

DSI Technique
A Nanotest 600 from Micro Materials was used for the DSI tests. Loads ranging from 5 to 100mN were used and loading rate, dwell time and unloading rate were all varied independently.
Experimental set-up for DSI

Study of time-dependent behaviour of SL7580

SL7580 samples treated with methanol and U.V post cured for 90 minutes.
4500

Plastic depth (nm)

4000 3500 3000 2500 2000 1500 1000 500 0 0 5 10 15 20 25

Weeks

Study of time-dependent behaviour of SL7580

5

250

Indentation modulus (GPa)

200

Hardness (MPa)

150

1
100

SL 7580 samples treated with methanol SL 7580 samples treated with methanol and U.V postcured for 90 min 0 0 5 10 15 20 25 30

50 SL 7580 samples treated with methanol SL 7580 samples treated with methanol and U.V postcured for 90 min 0 0 5 10 15 20 25 30

Time (weeks)

Time (weeks)

Study of time-dependent behaviour of SL7580

5

200 180 160 140

Indentation modulus (GPa)

Hardness (GPa)

120 100 80 60 40 20 0 SL 7580 samples treated with T.P.M SL 7580 samples treated with T.P.M and U.V postcured for 90 min 0 5 10 15 20 25

0 SL 7580 samples treated with T.P.M SL 7580 samples treated with T.P.M and U.V postcured for 90 min 0 5 10 15 20 25

Time (weeks)

Time (weeks)

Cure kinetics of SL7580

Differential

Scanning Calorimetry (DSC) tests

14 12 10 8 6 4 2 0 50 100

mW

Heating rates

-2 0 -4 -6

150

200

250

300

350

Temperature (0C)
Dynamic DSC plots at 3, 7, 10 and 15 0C/min

Cure kinetics of SL7580

Dynamic heating runs
H T dH dT dT T0
T

dH dT dT T0 H T
n

T1

3 2.5 2 1.5 1

Isothermal runs nth

dH dt dt 0 H t

0.5 0 0 50 100 150 200

250

order mechanistic model

Temperature (0C)
0 -2 0 50 100 150 200 250

Temperature (0 C)

Ln(K) (1/sec)

d n k (1 ) dt

-4 -6 -8 -10 ln (K) -12

Cure kinetic parameters for SL7580

Standardization chart: Relation between hardness (MPa) and degree of cure.
250 1 0.9 200 150 100
Hardness (MPa)

Hardness (MPa)

0.8 0.7 0.6 0.5 0.4 0.3 0.2

Degree of cure

50 0 0 1 2 3 4 5 6

0.1 0

Degree of cure

d ln( ) ln( k ) n ln(1 ) dt

250

1 0.9 0.8 0.7 0.6 0.5 0.4 0.3

200

Kinetic

constants k = 3.36*10-5 sec-1 n = 2.8

150

100

50

Hardness (MPa) Degree of cure

0.2 0.1 0 25

0 0 5 10 15 20

Time (weeks)

Degree of cure

Time (weeks)

Hardness (MPa)

Cure kinetic parameters for SL7580

Indentation hardness vs. Degree of cure
240

y y 0 ae

bx
Hardness (MPa)

220 200 180 160 140 120 100 80 60 40 0.0 0.2 0.4 0.6 0.8 1.0

Kinetic parameters y0 = -46.55, a = 123.7 and b=0.6503

Degree of cure Degree of cure

Investigation of viscoelastic behaviour of SL7580

25

When no dwell period is applied the

Load (mN)

unloading curve shows a nose or bowing which increases with loading rate. This compromises the application of the standard data analysis methods developed for metals.

20

2 mN/sec 0.5 mN/sec

15

0.1 mN/sec
10

0 0 500 1000 1500 2000 2500 3000

Displacement (nm)
Load-displacement plots at different loading rates and constant unloading rate.

Investigation of viscoelastic behaviour of SL7580

25

The bowing effect also increases with decreasing unloading rate.

Load (mN)

20 15

0.1mN/sec 0.5mN/sec 2mN/sec

10 5

Assumption behaviour incorrect

of

purely

elastic is

during and the

unloading

0 0 500 1000 1500 2000 2500 3000

viscoleastic

Displacement (nm)

behaviour must be accounted for before extracting meaningful

Load-displacement plot at constant loading rate and different unloading rates

mechanical properties.

Investigation of viscoelastic behaviour of SL7580

Loading rate 2mN/sec
25 20

Load (mN)

Unloading rate 0.1mN/sec

300s dwell

Elastic

unloading

can

be

15 10 5
No dwell

180s dwell 60s dwell

achieved by the addition of a suitable dwell period at maximum load prior to unloading.

However, data obtained is still a function of the non-uniform stress state and the test rate.

500

1000

1500

2000

2500

3000

3500

Displacement (nm)
Load-displacement plots with different dwell periods.

Investigation of viscoelastic behaviour of SL7580

It can assumed that if the unloading and reloading curves
20 25

Load (mN)

follow the same path then the initial portion of the unloading curve is elastic.

15 10 5 0 0 400 800

No dwell 60 s dwell

180 s dwell 300s dwell

1200

1600

2000

2400

2800

3200

Displacement (nm)

Multiple load cycles reloaded to same maximum load after different dwell periods

Investigation of viscoelastic behaviour of SL7580

25
Dwell 180sec

20

Load (mN)

15

1 mN/sec

0.1 mN/sec 0.5 mN/sec

10

0 0 500 1000 1500 2000 2500 3000 3500

Displacement (nm)
Multiple load cycles reloaded to same maximum load at different loading rate

Investigation of viscoelastic behaviour of SL7580

Displacement (nm)

Load-displacement plots with different loading rates and fixed unloading rate (0.5 mN/sec).
25

700 600 500 400 300 200 100 0 0 50 100 150 200

2mN/sec

0.5mN/sec 0.1mN/sec

Dwell 180sec

20

Load (mN)

15

2 mN/sec 0.5 mN/sec 0.1 mN/sec

Time (sec)

10

Creep curves for 180s after different loading rates

0 0 500 1000 1500 2000 2500 3000 3500

Displacement (nm)

Investigation of viscoelastic behaviour of SL7580

4000 130

Indentation modulus(MPa)

3500

110 100

3000

90 80 70

2500

2000

Indentation modulus (Mpa) Indentation hardness (Mpa)

60 50 40

1500 0 0.5 1 1.5 2 2.5

Loading rate (mN/sec)

Indentation modulus and hardness at different loading rates.

Indentation hardness(MPa)

120

Atomic force microscopy (AFM) Study

VEECO Dimension 3100 AFM

Atomic force microscopy (AFM) Study

AFM images of Centre and Edge of unpolished sample

Centre

Edge

Investigation of non-uniform mechanical properties

300

Indentation hardness (MPa)

250 200 150 100 50 0 Group C (Centre) Group C (Edge)

300

250

Hardness (MPa)

200

150

-1

Time (Weeks)
100 Group DD (Center) Group (Centre) Group DD (Edge) Group (Centre)

SL samples treated with methanol.

10

50 0 2 4 6 8

Time (Weeks)

SL samples treated with methanol and U. V postcured for 90 min.

Bulk mechanical testing

True stress (MPa)

Tensile

tests

35 30 25 20 15 10 5 0 0 5

100mm/min

10mm/min 1mm/min

0.1mm/min
10 15 20 25 30 35

True stress (MPa)

80 70 60 50 40 30 20 10 0 0 2 4 6 8 10 12 14 16

100mm/min 10mm/min 1mm/min 0.1mm/min

True strain (%)

High

temperature (600C)

True Strain (%)

Room

temperature

Bulk mechanical testing

Compressive

tests
Yield stress (MPa)

100 80 60 40 20 0 Compression Tests Tensile Tests

100

Compressive stress (MPa)

80

60

40

Increasing Test rate

10

12

Test rates (mm/min)

20

0 0 5 10 15 20 25

Comparison between compressive and tensile yield stress at room temperature.

Strain (%)

Compressive stress vs. strain at room temperature.

Bulk mechanical testing

Creep tests

Creep constants B=7.35e-12 m=4.2763

Dorn Tensile creep experimental set up

relation

ss B m

Bulk mechanical testing

DMTA
@
Dynamic Properties vs Temperature
2.0E+09 0.300

Modulus (Pa)

Displacement 0.001, 0.005, 0.01, 0.05, 0.1, 0.15 mm @ Frequencies 1, 2, 5, 10, 100 Hz

1.8E+09 0.250 1.6E+09 1.4E+09 0.200 1.2E+09 1.0E+09 8.0E+08 0.100 6.0E+08 4.0E+08 0.050 2.0E+08 0.0E+00 0.0 20.0 40.0 Temperature (C) 60.0 0.000 80.0 0.150

Tan Delta

Finite element modelling

8

Node Quad Elements

Spherical indenter with 50 m radius

Conical indenter with same area to depth ratio as Berkovich indenter

Finite element modelling

Linear

Mohr-coulomb Material Model

Finite element modelling

Displacments

in X-direction

Compression stresses in X-Direction

Conclusions
The DSI technique has been used to characterise the mechanical behaviour of an epoxy SL resin with respect to time under various environmental and loading conditions.

A kinetic cure model has been applied to the resin and a good correlation between the predicted degree of cure and mechanical properties has been demonstrated.

Viscoelastic/viscoplastic behaviour has been observed in the DSI load-unload plots, which is dependent on loading/ unloading rates and dwell period at maximum load.

FEA can be used to increase understanding of material behaviour under indentation.

Contact
Rushabh J Vora
PhD student Wolfson School of Mechanical and Manufacturing Engineering

Loughborough University
r.vora@lboro.ac.uk