Hyphenated Spectroscopy Techniques Thermal Analysis and Rheology Short Course Concord, NH April 10, 2018 The world leader in serving science Analytical Instruments Overview Chromatography & Mass Spectrometry Life sciences mass spectrometry Liquid, ion, gas chromatography Inorganic/trace elemental analysis Laboratory informatics Materials & Structural Analysis Electron microscopy Molecular and elemental spectroscopy 2D/3D imaging software Chemical Analysis Instruments Portable analytical instruments Air-quality monitoring Radiation safety and security Process instruments Corp. Fin. to update to LTM Revenue ending in Q1 2017 Industry-leading technologies to solve a broad range of complex challenges 2 1
The widest range of analytical methods to drive deeper materials insights Electron Microscopy XPS EDS Raman FTIR XRF XRD UV-Vis Multiscale imaging & analysis of various materials Surface analysis quantitative chemical state Elemental imaging at high spatial resolution Chemical compound identification Identification of both organic and inorganic materials Chemical compound identification Identification of organic materials in bulk state Bulk state elemental composition Structural crystallinity and composition Quantitative measuremen t of reflection or transmission properties of a material We deliver a full spectrum of analytical tools that enable customers to advance their research, product development, and quality control capabilities 3 The Electromagnetic Spectrum visible Range x-rays ultraviolet near-ir mid - IR far-ir radio Wavenumbers (cm -1 ) 10 7 10 6 10 5 10 4 10 3 10 2 Technique XRF UV-Vis Infrared Wavelength (µm) 10-3 0.01 0.1 1 10 100 4 2
The Power of Molecular Spectroscopy Work fast Little or no sample prep, rapid screening on a range of samples Organics, inorganics, films, coatings, paper, fibers, more and answer fundamental questions What is this stuff? How much is in there? In what form? Analyze samples from cradle to grave R & D, process control, QA/QC, failure analysis, waste 5 Core Molecular Spectroscopy Techniques FTIR Chemical fingerprint Fast analysis picospin NMR Benchtop NMR No cryogens Raman Spectroscopy Chemical fingerprint Fast analysis Greater sampling options microscopy options 6 3
General Rules for Molecular Spectroscopy Peaks Response Energy Energy varies along the x-axis Wavelength in nanometers or microns, Wavenumber (cm -1 ) Response is along the y-axis Absorbance, transmittance, reflectance Different molecules absorb light differently ( Peaks ) This is what enables spectroscopy to tell us something! 7 Breaking it Down Polymer Deformulation Studies using FT-IR Coupled to TGA The world leader in serving science 4
Overview Deformulation What is it? Why do it? Common materials FT-IR as a deformulation tool Classical technique TGA coupled with FT-IR Physical property correlation with chemical data 9 Deformulation Reverse Engineering Unknown material composition Failure Analysis Known material gone wrong Polymers Plastics Fillers Formulation Rubber Carbon Black: O-Rings, Tires Epoxies, Resins, Adhesives Entrained solvents, Breakdown products Fabrics, Paper products 10 5
TGA-IR: The Basics Temperature Ramp Weight Loss Curve Derivative Weight Loss Curve IR Balance Pan Heated Transfer Line Vapor Infrared Series File Quantitative: How much is coming off? T G A Gravimetric Analysis Qualitative: What is coming off? FT-IR Chemical information 11 TGA-FTIR: Experiment IR Beam FT-IR Spectrometer TGA Gas Cell 1.0 1.0 0.90 0.9 0.9 0.85 0.80 0.8 0.8 0.75 0.7 0.70 0.7 0.65 0.6 0.60 0.6 0.55 0.5 0.50 0.5 0.45 0.4 0.40 0.4 0.35 0.3 0.30 0.3 0.25 0.2 CH 4 0.20 H 2O IR Beam 0.1 CH 4 H 2O CH 4 H 2O 0.05 0.0 Absorbance 0.15 0.10 Absorbance 4000 Infrared Spectrum 3500 3000 2500 2000 1500 1000 Wavenumbers (cm-1) 3500 3500 3000 3000 2500 2500 2000 2000 1500 1500 1000 1000 500 500 Wavenumbers (cm-1) (cm-1) H 2O Exhaust Heated Transfer Line TGA Furnace CH CH 4 4 CH 4 Sample Transfer Gas In TGA Gas Cell 12 6
Experimental Set-up TGA Conditions Sample size: 10 15mg TGA program: N 2 Purge Isothermal Temperature : Ambient up to 650 C Low Volume IR Gas Cell FT-IR Conditions Transfer line temp: 300 C TGA-IR Module temp: 300 C Data Collection: 8 cm -1, 5 scans/spectrum 13 Simple Situation Calcium Oxalate Three weight-loss peaks H 2 O ; CO + CO 2 ; CO 2 H 2 O 14 7
Example Applications Polymers Textiles Coatings Residual solvent Product stability Additive analysis 15 Classic Root Cause Analysis Gasket analysis Good Good Bad Subtraction Bad Search result 16 8
Deformulating Nanoparticles These nanoparticles are stabilized by ligands Heating breaks down the complexes, releasing ligand TOPO ODPA 17 Outgassing of Electronic Component A critical electronic component, in a sealed chamber, was degrading Concern was for outgassing of other materials in the chamber The insulation of a wire was found to be the cause Water Formaldehyde 18 9
Complete Analysis: Mercury TGA 19 PC+ABS Characterization Polycarbonate/Poly(acrylonitrile:butadiene:styrene) (PC+ABS) Polycarbonate Poly(acrylonitrile:butadiene:styrene) Blended Polymer Complex Matrix 20 10
PC+ABS Characterization: Preliminary Evaluation OMNIC Mercury TGA software analyzes the complete data set Principle component analysis followed by multi-component search Guides the interpretation and additional searching Two Wt Loss Areas 21 PC+ABS Characterization Early Weight Loss Extract data from first weight loss region 420 440 C range Mixture search using OMNIC Specta software Primarily Styrene and related materials 22 11
PC+ABS Characterization: Major weight loss Extract data from 2 nd weight loss region 510-540 C range Direct search in OMNIC provides enough information Bisphenol A is the major component 23 PC+ABS Characterization Something s missing Nitrile component predicted by structure Not readily pulled out of this complex mixture OMNIC Specta - Peak Search comes in handy Isocyanic acid based on nitrile peaks between 2300 & 2200 cm -1 24 12
Environmental Stress Cracking (ESC) Investigation Environmental Stress Cracking is the premature embrittlement and subsequent cracking of a plastic due to the simultaneous and synergistic action of stress and contact with a chemical agent Stress ESC Failure Mechanism: Chemical agent permeates into molecular structure lower ductility Mechanism includes interference with inter-molecular forces bonding polymer chains Reduces energy required for disentanglement/slippage to occur producing a shift in the preferred mechanism from yielding Plastic Chemical Jeffrey A. Jansen jeff@madisongroup.com 25 Environmental Stress Cracking (ESC) Investigation 26 13
Environmental Stress Cracking (ESC) Investigation Scrape samples with Diamond ATR: Fracture Zone & Intact Area Subtract the two spectra followed by Multi-Component Search Some clues, but overall unsatisfactory result 27 Environmental Stress Cracking (ESC) Investigation TGA-IR Analysis: Early weight loss area 300 360 C Extracted spectrum subjected to OMNIC Specta Multi-Component Search Identified acetic acid and medium-chain length methyl ester 28 14
Environmental Stress Cracking (ESC) Investigation TGA-IR Analysis: Main weight loss area 390 440 C Extracted spectrum subjected to OMNIC Specta Multi-Component Search Identified an aromatic alcohol, longer-chain length methyl ester 29 EPDM Characterization Poly(ethylene:propylene:diene) (EPDM) 30 15
EPDM Characterization EPDM Compounding - Hydrocarbon Plasticizers Paraffinic: Naphthenic: Aromatic: 31 EPDM Characterization: TGA Analysis - Quantitative Sample: EPDM Rubber Size: 12.7140 mg Method: Isothermal for Weight (%) 100 80 60 40 189 C 10.88% Plasticizer (1.38mg) TGA 393 C Run Date: 10-Oct-2014 15:40 Instrument: TGA Q5000 V3.15 Build 263 486 C 1.2 1.0 41.26% EPDM 0.8 (5.25mg) 0.6 0.4 Deriv. Weight (%/ C) 20 0.2 0.0 0 0 100 200 300 400 500 600 700 Temperature ( C) Universal V4.7A TA Instruments 32 16
EPDM Characterization: TGA-IR Results Qualitative Plasticizer: Paraffinic hydrocarbon EPDM Breakdown: Unsaturated hydrocarbon 33 Textile Example The world leader in serving science 17
Diamond ATR Of Fabrics (Pre-TGA) Diamond ATR shows difference between fabrics Many unique peaks seen below 1000cm -1 NYCO FR Absorbance 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 35 NYCO TGA-IR Data Temp (C) 600 400 200 Temperature ( C) vs. Time (min) Temp ramp profile (imported from TGA software) Wt. Loss (mg) 6 4 2 Weight loss (mg) vs. Time (min) Weight loss profile (imported from TGA software) 0 Gram-Schmidt (GS) 0.08 IR Intensity 0.06 0.04 0.02 GS shows total IR response as function of time -Peaks in GS correlate to sample weight loss and significant off-gassing detected For NYCO, 1 major thermal event was observed at ~26min - Next slide will show IR spectra in that time region 5 10 15 20 25 30 Time (minutes) 36 18
0.0135 0.0130 0.0125 0.0120 0.0115 0.0110 0.0105 0.0100 0.0095 0.0090 0.0085 Linked spectrum at 26.377 min. 3100 3050 3000 Wavenumbers (cm-1) 2950 2900 0.0150 0.0148 0.0146 0.0144 0.0142 0.0140 0.0138 0.0136 0.0134 0.0132 0.0130 0.0128 0.0126 0.0124 0.0122 0.0120 0.0118 0.0116 0.0114 Linked spectrum at 26.377 min. 1050 1000 950 Wavenumbers (cm-1) 900 850 Basic Theory and Instrument Design of FT-IR NYCO Evolved Gas Spectra 0.20 0.18 0.16 Linked spectrum at 25.782 min. Linked spectrum at 26.122 min. Linked spectrum at 26.377 min. Linked spectrum at 26.632 min. Major evolved gas is CO 2 at 26min Just before CO 2 evolution, small signal observed at ~3000 and ~900cm -1 See next slide for ID of these peaks 0.14 Absorbance 0.12 0.10 0.08 Absorbance Absorbance 0.06 0.04 0.02 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 500 37 NYCO 26.37min Detailed Spectral Analysis 4 components observed including CO 2, CO, methane and ammonia Spectral overlay shows peaks that match to each species Absorbance Linked spectrum at 26.377 min. 3016 2357 2177 964 930 2112 Ammonia Methane Carbon dioxide Carbon monoxide 3500 3000 2500 2000 Wavenumbers (cm-1) 1500 1000 500 38 19
FR Fabric TGA-IR Data Temp (C) 600 400 Temperature ( C) vs. Time (min) 200 Wt Loss (mg) 6 4 Weight loss (mg) vs. Time (min) 2 IR Intensity 0.010 0.008 0.006 0.004 Gram-Schmidt For FR Fabric, 3 major thermal event was observed at ~16, 26, 31mins - Next slide will show IR spectra in that time region 0.002 5 10 15 20 25 30 Time (minutes) 39 FR Fabric Evolved Gas Spectra Absorbance (Abs) 0.005 0.000-0.005 Time (minutes)=15.8 min, point #186 345 C See next slide for library search 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumbers (cm-1) Absorbance (Abs) 0.010 0.005 Time (minutes)=25.7 min, point #302 542 C Spectrum matches to CO 2 evolution 0.000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumbers (cm-1) 0.020 Time (minutes)=31.0 min, point #364 Absorbance (Abs) 0.015 0.010 0.005 650 C Spectrum matches to CO 2 and CO evolution 0.000 3800 3600 3400 3200 3000 2800 2600 2400 2200 2000 1800 1600 1400 1200 1000 800 600 Wavenumbers (cm-1) 40 20
345 C Linked Spectrum Library Search Best match is brominated species Species was not seen in NYCO sample 41 Conclusions - Deformulation using FT-IR & TGA TGA coupled to FT-IR advances capabilities to break materials down OMNIC Series, Mercury TGA and OMNIC Specta software provide tools for analysis of complex mixtures Understanding the chemistry of the materials being analyzed is important 42 21
Other Applications for Spectroscopy The world leader in serving science Add the Right Tools Transmission Preferred method for quantitative analysis Sample mixed and pressed; good sensitivity Attenuated total reflectance (ATR) The sample must contact the crystal Simple and fast, generally non-destructive Diffuse reflectance (DRIFTS) Dilute sample in a matrix (like KBr) Simple, but requires mixing Specular reflectance Sample must be reflective or on a mirror Signals can be very weak 47 22
ATR of Heat Shrink Tubing: Inner Wall ATR and OMNIC Specta reveal two components: Polymer and Mg(OH) 2 Mg(OH) 2 is used as a flame retardant Poly(ethylene-co-vinyl acetate) 14 wt. % vinyl acetate Magnesium Hydroxide 48 ATR of Heat Shrink Tubing: Outer Wall Outer wall shows something else Subtract outer inner Tyzor 131 is found This is a cross-linker Causes tubing to shrink! 49 23
Black Rubber Gasket Run on Ge ATR Multiple components Base polymer Silane slip-aid 50 24