An Integrated Analytical Approach to Solving Complex ... Event/201… · 21 An Integrated Analytical Approach • Use multiple analytical techniques to solve the technical questions

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An Integrated

Analytical Approach

to Solving Complex

Polymer Problems

Scott D. Hanton and Chanell Brown

Intertek Allentown

October 2015

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Acknowledgments

Intertek colleagues

• Sherri Bassner

• Todd McEvoy

• Devon Shankweiler - GPC

• Scott Voth – DSC + TGA

• Ann Kotz - NMR

• Sharon Gardner – FTIR & TGA/IR

• Ellen Link – Failure Analysis

• Menas Vratsanos – DMA

• Jackie Sturgeon – SEM/EDS

• Ed Sydlik – ICP

• Cindy Mengel-Smith – XRF

• Steve Deppen – GC/MS

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Outline

• Intertek introduction

• Polymer analysis

• High performance SEC

• Integrated analytical approach

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Extensive Global NetworkE

More than

1,000 laboratories and offices

•FTSE 100 company in the

Support Services sector

•Revenues of $3.5 billion in 2014.

More than

120 countries

Approximately

38,000 people

Introduction to Intertek

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Intertek Allentown

Your Problem-Solving Partner

Problem-Solving Teams

Inorganic Analysis

Microscopy, metallurgy, surface science, diffraction,

failure analysis, , particle size

Residue ID, ceramics, polymer

structure, electronic and nano-materials

Titrations, trace metals

System stability, impurity analysis, gases/chemicals

Material Properties

Rheology, thermal analysis/hazards,

sorption

Polymer systems, catalysis, reaction

studies, gas separation

Organic Analysis

Chromatography, MS, NMR,

spectroscopy

Chemical structure identification, degradation

analysis, impurity analysis

Mechanical/

environ.

Testing

(Pittsfield)

Extractables

and

Leachables

(Whitehouse)

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Introduction

• Polymer chemistry continues to be vital

• New products

• New uses

• New research

• Significant challenges presented in polymer analysis

• Multiple monomers

• Solubility

• Complex structures

• Complex formulations

• Require multiple and powerful tools to analyze polymers

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Polymer Detective

• What is it?

• What are its properties?

• How does it behave?

• What else is in it?

• Where is it?

• How big is it?

• How much of it is there?

• What is its chemical structure?

• How is it connected?

• What’s on the end?

What?

Where?

How?

Who?

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Polymer Analysis Decision Tree

Identity

FTIR

Raman

CHNOS

SEC

Material Properties

Density

Rheology

DSC

TMA

Sorption

Morphology

SEM

AFM

Components

TGA

XRF

GC

LC

Chemical Structure

NMR

MS

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GPC Offerings

• Traditional GPC

• Organic solvents: THF, DMF, NMP, CHCl3, …

• Aqueous

• Amine separation methods

• High temperature GPC

• Solvent = TCB

• Triple detection

• GPC fraction collection

• High performance SEC

• Waters APC

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GPC Fraction Collection

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GPC Fraction Collection of Polyolefin

Blank

Sample 1 injection 1

Sample 1 injection 2

Sample 1 injection 3

• GPC fractions for FTIR analysis for end group analysis

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GPC Fraction Collection of Polyolefin

• FTIR clearly identifies Anhydride end group

EsAc

EsAnhFraction #1

EsAcEs

AnhFraction #2

Anh

Fraction #3

Anh

Fraction #4

Anh

Fraction #5

AnhFraction #6

Anh

Fraction #7

Anh

Fraction #8

-0.04

-0.03

-0.02

-0.01

0.00

0.01

0.02

0.03

Ab

sor

ba

nc

e

1000 1500 2000 2500 3000 3500 4000

W avenumbers (cm-1)

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GPC Fraction Collection of Polyolefin

• Anhydride end group concentration inverse to MW

Bulk

Sample

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Benefit of Higher Performance SEC

• Fast new solvent equilibration time (2 – 4 hours)

• Many different solvents

• Columns operate under high back pressure

• Improved resolution

• Sub 3µm hybrid particle column technology

• Low dispersion

• Fast analysis time (10 – 15 minutes)

• Waters’ Advanced Polymer Chromatography

(APC)

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APC Analysis: Polyurethane Prepolymer

Total Run Time 15

min @ 0.6ml/min flow

rate

Mn 2000

Mw 7000

RSD ≤1%

• Clearly characterize MWD

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APC Analysis of Polyurethane Prepolymer

• Obtain MWD and slice table for PMN

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APC Analysis of Polyesters

Sample 1 Mn 1,200 Mw 5,900 PD 4.9

Sample 2 Mn 1,300 Mw 6,900 PD 5.3

• Show differences between competitive products

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APC Analysis of Polyisobutylene

• Show MWD variation across a family of products

Mn range from

5k – 34k D Mw range from

16k – 135k D

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APC Analysis of Lubricants

• Distinguish a series of different lubricating oils

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Integrated Analytical

1. Polypropylene plastic bowls

2. Styrene-butadiene copolymer

3. Polycarbonate failure analysis

4. Plasticized PVC

5. Black specks in polycarbonate

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An Integrated Analytical Approach

• Use multiple analytical techniques to solve the technical questions

• GPC to determine molecular weight distribution

• TGA to determine concentration of filler

• TGA-IR to determine volatiles released during heating

• DSC to determine melting behavior and crystallinity

• FTIR, NMR, and GC/MS to determine chemical composition

• Microscopy to examine fractography

• SEM-EDS, ICP-OES, and XRF to determine elemental composition

• DMA to determine rheological properties

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1. Characterization of Polypropylene Plastic Bowls

• HT-GPC shows competitor has higher MWD

Mw = 364kD

Mw = 224kD

Log MW

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Sample 1

Sample 2

1. Characterization of Polypropylene Plastic Bowls

• TGA shows competitor has higher inorganic filler (1.7% vs 1.1%)

500 C 800 C

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DSC Plot – Second Heating

1. Characterization of Polypropylene Plastic Bowls

• DSC shows competitor has additional melts

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2. Characterization of Styrene-Butadiene Copolymer

• GPC shows heat aging leads to higher MWD of polymer

Copolymer

region

Low mass

additives

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2. Characterization of Styrene-Butadiene Copolymer

• FTIR shows little chemical difference from heat aging

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2. Characterization of Styrene-Butadiene Copolymer

• 1H and 13C NMR shows differences additive concentrations

13C NMR spectra of carbonyl region

P P P P P E

E

E

E E

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3. Polycarbonate Failure Analysis

• Cracking away from bolt holes

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3. Polycarbonate Failure Analysis

• FTIR confirmed PC and found no significant chemical changes

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3. Polycarbonate Failure Analysis

• GPC, TGA-IR, and DSC found no significant differences

Identical

MWD

by GPC

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3. Polycarbonate Failure Analysis

White debris and cracking Mud cracking was noted on the

exposed surface of the hole.

The fracture exhibited limited

microductiliy

• Optical and SEM cracking from chemical attack

SEM

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3. Polycarbonate Failure Analysis

• SEM-EDS show variety of elements in white deposits

Ice melt may

be responsible

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4. Compare Two Different Polymer Materials

• FTIR and NMR show the polymers to be plasticized PVC

FTIR spectra

are essentially

the same for

both materials

FTIR spectra shows the plasticizer to be phthalate esters

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4. Compare Two Different Polymer Materials

• FTIR and NMR show the polymers to be plasticized PVC

NMR spectra

are essentially

the same for

both materials

NMR spectra shows the plasticizer to be 45% of the materials

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4. Compare Two Different Polymer Materials

• GC/MS – didecyl phthalate and other small differences

BHT

1-dodecanol

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4. Compare Two Different Polymer Materials

• GPC shows differences between the polymers

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4. Compare Two Different Polymer Materials

• XRF shows small differences between the polymers

Element (wt. %) Sample 2 Sample 1

Si 0.062 0.10

Zn 0.011 0.005

Ca 0.007 0.021

P 0.006 0.012

S 0.006 0.005

Fe 0.004 0.012

Al 0.003 0.040

Ti <0.002 0.005

K <0.002 0.004

Organics

(balance) 99.90 99.80

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4. Compare Two Different Polymer Materials

• ICP-OES

• Sample 1 – 60 ppm Tin

• Sample 2 – 99 ppm Tin

• Use Tin concentration to calculate the concentration

of stabilizer

• Sample 1 – 0.028% stabilizer

• Sample 2 – 0.046% stabilizer

• ICP quantifies stabilizer differences between the polymers

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4. Compare Two Different Polymer Materials

Sample 2B

Sample 2A

Sample 1

DMA Frequency Sweep Data at 25oC

E’

Tan (δ)

• DMA shows modulus differences between the polymers

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5. “Good vs “Bad” Polycarbonate

• GPC shows low mass species in “Bad” sample

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5. “Good vs “Bad” Polycarbonate

• FTIR shows no difference between samples

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5. “Good vs “Bad” Polycarbonate

• FTIR shows phenolic resin in black specks in “Bad” sample

Subtraction Result:*106420.04 / D2601216, bad CH# 311257 / dark material from inclusion a, sec'n a / Continuum microscope miuns clear

0.0

0.2

0.4

0.6

0.8

Ab

s

Subtraction Result:*106420.04 / D2601216, bad CH# 311257 / dark material from inclusion a, sec'n b / Continuum microscope miuns clear

0.0

0.2

0.4

Ab

s

Subtraction Result:*106420.04 / D2601216, bad CH# 311257 / dark material from inclusion b, sec'n a / Continuum microscope minus clear

0.00

0.05

0.10

0.15

Ab

s

Subtraction Result:*106420.04 / D2601216, bad CH# 311257 / dark material from inclusion b, sec'n b / Continuum microscope minus clear

0.00

0.10

0.20

0.30

Ab

s

1000 1500 2000 2500 3000 3500 4000

Wavenumbers (cm-1)

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Summary

• SEC/APC

• Solving wide range of polymer science problems

• Benefit from high performance APC

• Developed GPC fraction collection methods

• Integrated analytical

• Combine many different analytical methods

• Solve complex problems

• Unknown materials

• Failure analysis

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Questions?

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Valued Quality. Delivered.