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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.
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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


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Introduction to AFM:

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

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Bruker NanoSurfaces Division

Introduction to AFM:

What you want to know about polymers


- 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

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Bruker NanoSurfaces Division

Introduction to AFM:

What you want to know about polymers


- 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
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Bruker NanoSurfaces Division

Conventional Material Analysis


Quantitative, bulk

Thermal Mechanical Analysis (TMA) setup shown

TMA
Material-specific information, but no spatial resolution
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Bringing Thermal Analysis to the Nanoscale


The Tip

Topography

Phase

Controllable probe
temperatures up to
400C
0.7 mm scan
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Bruker NanoSurfaces Division

Bringing Thermal Analysis to the Nanoscale


Operating Principle

High-Resolution
AFM Image
Deflection

Heater
control

Local Tg & Tm
Current

Temperature
measurement

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Bruker NanoSurfaces Division

Nanoscale Thermal Analysis Solutions

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Bruker NanoSurfaces Division

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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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Bruker NanoSurfaces Division

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Food Packaging

Understand/Design/(Reverse-)Engineer Starting with AFM

Distinct layers, distinct fine structure. Material and function?


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Bruker NanoSurfaces Division

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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
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Bruker NanoSurfaces Division

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Toner Particle

Analyzing Composition and Core Shell Structure

74.3 C

70.4 C

60.4 C

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Sample: Toner particles embedded


in epoxy and microtomed
15 x 7.5 m topographic scan

Toner Particle
Center Region
Middle layer
Outer layer
Epoxy

Bruker NanoSurfaces Division

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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


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Bruker NanoSurfaces Division

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PEO/SPP Blend

(1) Microscale Analysis

Matrix (sPP, Tm)

Domains (PEO, Tm)


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15 m Scan
Bruker NanoSurfaces Division

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PEO/SPP Blend

(2) Uncovering Additional Nanoscale Variation

sPP Melt Transition


PEO Melt Transition

Measurement Location

Small PEO
domains on sPP

Height
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4 m Scan
Bruker NanoSurfaces Division

Phase
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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
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Bruker NanoSurfaces Division

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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

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Bruker NanoSurfaces Division

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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

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Transition Temperature Microscopy

Completing the Picture with Fast Automated Mapping

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AFM Configurations for

Transition Temperature Microscopy

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Transition Temperature Microscopy


Applications Example (1)

1. Multilayer films revisited

Complex: support, adhesive, functional layers


Here: reveal property variation in tie layer
Obtain complete property distribution

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1. Navigation & point / array selection

Import AFM
image to
navigate and
define locations
for initial single
point
measurements.

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2. Automatic peak softening detection

Automatic peak
detection
guarantees
unbiased
extraction of
transition
temperatures
from raw data.

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3. Embedded cursor for effortless data mgt

Retains information about location of measurements, guaranteeing correct spatial correlation in


analysis post acquisition.

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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.

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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.

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103

136

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235

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Transition Temperature Microscopy


Applications Example (2)

2. Solvent recrystallized surface


Surface modification and coatings are common
Evades bulk characterization
Here: gradient of solvent concentrations,
nontrivial property distribution

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Bruker NanoSurfaces Division

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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.

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Solvent Crystallization Example


Histogram Analysis

Quantifying thermal property distribution as function of surface treatment


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Transition Temperature Microscopy


Applications Example

3. Pharmaceutical copolymer
In-situ measurement on pharmaceutical delivery vessel
Elucidates variation in copolymer blending that is not
obvious from other measurements

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Bruker NanoSurfaces Division

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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.
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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.

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Bruker NanoSurfaces Division

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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

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Bruker NanoSurfaces Division

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