Nanoscale Thermal Analysis

Nanoscale Thermal Analysis
Quantitative Nanoscale Property Mapping

with Automated Transition Temperature Microscopy
Thomas Mueller, Ph.D., Product Line Manager, Bruker Nano Surfaces
thomas.mueller@bruker-nano.com
Agenda
1.
Introduction
a. AFM for polymers
2.
Bruker Nano Thermal Analysis

a. Operating Principle
b. Application Examples
c.
3.
Correlation With Bulk Measurements
Transition Temperature Microscopy

a. Operating Principle
b. Application Examples
c.
4.
2/15/2012
Quantification
Summary & Conclusions

Bruker NanoSurfaces Division
Introduction to AFM:
Tool for Nanoscale Topographic Information
Monolayer of C60H122 alkane, 600nm scan

Atoms on HOPG, 8nm scan
Array of engineered DNA, 2m scan

2/15/2012
What you want to know about polymers

- quantitative nanomechanical properties
PFQNM-Height
PFQNM-Adhesion
PFQNM-Modulus
PeakForce QNM can quantitatively and

unambiguously identify modulus and
adhesion variations. Phase imaging and
multifrequency imaging techniques cannot.
Comparison of the adhesion and phase

images clearly shows that the phase contrast
is primarily due to adhesion, whereas one
might more commonly assume that it reflects
modulus variations
Section plot illustrates ability to measure the

modulus across the polymer layers
Tapping-Height
Tapping-Phase
Multilayered polymer film,

10 m scans
Left: PeakForce QNM
Right: TappingMode
2/15/2012

- electrical properties
High-resolution current mapping on organic photovoltaics

Enabled by PeakForce TUNA and ppm-level environmental control
Current map on PEDOT-P3HT

overlaid on nm-scale
topography.
Achieving highest resolution

in topography and current
(2mm image size, 10nm
height scale, 5pA current
scale)
Very soft samples cannot be

imaged in contact mode
based CAFM.
Only possible with PeakForce

TUNA.
Sample courtesy of Prof. Nguyen, UCSB
2/15/2012

- thermal properties? chemistry?
Topography
Quantitative nanomechanics PFQNM
Nanoscale electrical properties PFTUNA
Thermal properties Tg, Tm
What is it Chemistry
Influence of processing, wear, UV exposure on
component distribution, aggregation etc
6
2/15/2012
Conventional Material Analysis

Quantitative, bulk
Thermal Mechanical Analysis (TMA) setup shown
TMA
Material-specific information, but no spatial resolution
2/15/2012
Bringing Thermal Analysis to the Nanoscale

The Tip
Topography
Phase
Controllable probe
temperatures up to
400C
0.7 mm scan
2/15/2012
Bringing Thermal Analysis to the Nanoscale

Operating Principle
High-Resolution
AFM Image
Deflection
Heater
control
Local Tg & Tm
Current
Temperature
measurement
2/15/2012
Nanoscale Thermal Analysis Solutions
2/15/2012
10
PS/LDPE Blend on Silicon

Clear ID Domain vs Matrix
Matrix (PS, Tg)
Before
After
Domains (LDPE, Tm)
8 x 4 m Scan
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11
Food Packaging
Understand/Design/(Reverse-)Engineer Starting with AFM
Distinct layers, distinct fine structure. Material and function?

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12
Food Packaging
Understand/Design/(Reverse-)Engineer Nanothermal Analysis
VITA clearly distinguishes

the two outside layers
from the inside one.
VITA provides
quantitative local Tm,
aiding material ID.
In packing applications
the outside layers often
consist of HDPE and the
inside (barrier) layer is
EVOH.
30m scan
2/15/2012
13
Toner Particle
Analyzing Composition and Core Shell Structure
74.3 C
70.4 C
60.4 C
2/15/2012
Sample: Toner particles embedded

in epoxy and microtomed
15 x 7.5 m topographic scan
Toner Particle
Center Region
Middle layer
Outer layer
Epoxy
14
Nanoscale Drug Analysis

Formulation: Crystallinity
The existence of different solid-state forms, such as polymorphs, solvates, hydrates,

and crystallinity in pharmaceutical drug substances and excipients, have
downstream consequences in drug products and biological systems.
Indomethacin
Crystalline only
Crystalline and amorphous
Data courtesy of M. Reading, D Craig and L. Harding, UEA

2/15/2012
15
PEO/SPP Blend
(1) Microscale Analysis
Matrix (sPP, Tm)
Domains (PEO, Tm)

2/15/2012
15 m Scan
16
PEO/SPP Blend
(2) Uncovering Additional Nanoscale Variation
sPP Melt Transition

PEO Melt Transition
Measurement Location
Small PEO
domains on sPP
Height
2/15/2012
4 m Scan
Phase
17
Correlation with Bulk Thermal Analysis

Validation of nano-TA
Three crystalline samples and three amorphous samples were measured

by bulk ThermoMechanical Analysis (TMA) and compared against VITA
measurements
NanoTa Onset
300
0.1C/s
250
1C/s
200
10C/s
y = 1.0088x - 3.8173
R2 = 0.9811
y = 1.0027x + 0.2778
R2 = 0.9701
y = 1.0047x + 2.9657
R2 = 0.9581
150
100
50
0
0.0
100.0
200.0
300.0
TMA onset
Slopes: 1.003 - 1.009

Offsets: -4 to +3C
Data courtesy of G. Meyers and A. Pasztor, DOW
2/15/2012
18
Summary Nanothermal Analysis

Quantitative characterization & material ID
Nanothermal analysis provides phase transition

temperatures (Tg/Tm) with sub-100nm resolution
Enables local material identification in heterogeneous

samples for R&D or Failure Analysis, in
blends/composites/multilayers
Good correlation with results from standard Bulk TMA, a

trusted method at macro-level
High probe temperature enables use with most polymers
2/15/2012
19
But Thats Not All

Missing a Key Part
How much more

complexity in this
PEO/SPP blend?
Thermal property variations may not correlate with

topography
Neither bulk nor single-point nanoscale measurements
capture the distribution of properties
Nanoscale property variation is intrinsic to polymers
2/15/2012
20
Completing the Picture with Fast Automated Mapping
2/15/2012
21
AFM Configurations for
2/15/2012
22

Applications Example (1)
1. Multilayer films revisited
Complex: support, adhesive, functional layers

Here: reveal property variation in tie layer
Obtain complete property distribution
2/15/2012
23
1. Navigation & point / array selection
Import AFM
image to
navigate and
define locations
for initial single
point
measurements.
2/15/2012
24
2. Automatic peak softening detection
Automatic peak
detection
guarantees
unbiased
extraction of
transition
temperatures
from raw data.
2/15/2012
25
3. Embedded cursor for effortless data mgt
Retains information about location of measurements, guaranteeing correct spatial correlation in

analysis post acquisition.
2/15/2012
26
4. TTM mapping for structure property correlation
Fully automated acquisition and analysis. Reveals

transition temperature variations within the tie layer
that would not have been expected or predicted
based on AFM image alone or based on single point
nano-ta measurements.
2/15/2012
27
6. Histogram analysis
Provides complete
statistics on nanoscale
thermal property
variation, characterizing
variations within each
layer.
Note: Currently released
version provides the
measurement data. Builtin histogram function
planned for next SW
release.
37
2/15/2012
70
103
136
169
202
235
28

Applications Example (2)
2. Solvent recrystallized surface

Surface modification and coatings are common
Evades bulk characterization
Here: gradient of solvent concentrations,
nontrivial property distribution
2/15/2012
29
Solvent Crystallization Example

Spatial Variation
Transition temperature
microscopy maps out
surface thermal
properties after
crystallization. Sample
was exposed to gradient
of high (left) to low
(right) solvent
concentrations resulting
in measurable increase in
softening temperature.
2/15/2012
30
Solvent Crystallization Example

Histogram Analysis
Quantifying thermal property distribution as function of surface treatment

2/15/2012
31

Applications Example
3. Pharmaceutical copolymer
In-situ measurement on pharmaceutical delivery vessel
Elucidates variation in copolymer blending that is not
obvious from other measurements
2/15/2012
32
Pharmaceutical Copolymer
Spatial Variation
AFM does not reveal obvious variation in mixing

and the rough surface of the in situ sample
(sectioning not an option) presents a challenge to
mechanical measurements and phase imaging.
Transition temperature microscopy clearly shows spatial variations in thermal properties indicating
variation in copolymer mixing.
2/15/2012
33
Pharmaceutical Copolymer
Histogram Analysis
Systematic, automated
execution of literally 100s
of nano-ta measurements
provides valid statistics,
allowing true quantification
of thermal property
distribution and therefore
mixing variation.
2/15/2012
34
Summary
Quantitative Sample Characterization with TTM
Transition temperature microscopy reveals nanoscale spatial variation in

thermal properties
Transition temperature microscopy provides fully automated execution

of large numbers of nanoscale thermal measurements
Those variations may not be reflected in other (mechanical, electrical) AFM

property measurements, so single point nanothermal measurements with
location chosen based on an AFM image would miss them.
Uncovers new information beyond single point and average quantities: The
finite property distribution that is intrinsic to polymers and relevant to their
application in many cases.
Transition temperature microscopy perfectly complements Brukers

exclusive PF QNM and PFTUNA
Making Dimension Icon and MultiMode8 the platforms that provide the most
complete property information on polymer samples
2/15/2012
35
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Nanoscale Thermal Analysis

Quantitative Nanoscale Property Mapping

Bruker Nano Thermal Analysis

Correlation With Bulk Measurements

Transition Temperature Microscopy

Summary & Conclusions

Tool for Nanoscale Topographic Information

Monolayer of C60H122 alkane, 600nm scan

Array of engineered DNA, 2m scan

Bruker NanoSurfaces Division

What you want to know about polymers

PeakForce QNM can quantitatively and

Comparison of the adhesion and phase

Section plot illustrates ability to measure the

Multilayered polymer film,

Bruker NanoSurfaces Division

What you want to know about polymers

High-resolution current mapping on organic photovoltaics

Current map on PEDOT-P3HT

Achieving highest resolution

Very soft samples cannot be

Only possible with PeakForce

Bruker NanoSurfaces Division

What you want to know about polymers

Bruker NanoSurfaces Division

Conventional Material Analysis

Thermal Mechanical Analysis (TMA) setup shown

Bruker NanoSurfaces Division

Bringing Thermal Analysis to the Nanoscale

Bruker NanoSurfaces Division

Bringing Thermal Analysis to the Nanoscale

Bruker NanoSurfaces Division