3 Steps to Simpler QA/QC of Polymeric Materials

Transcription

1 3 Steps to Simpler QA/QC of Polymeric Materials Agilent Technologies Webinar Speakers: Alan Rein, Ph.D., Market & Strategy Manager, FTIR Mobile Products Ned Davis, Product Manager, In-Lab FTIR Products

2 3 Steps to Simpler QA/QC of Polymeric Materials via FTIR Spectroscopy 1. Select specific method for polymer from spectrometer menu 2. Follow visual instructions provided by instrument 3. Read results of method library search provides identity and match quality Pre-calibrated method yields quantitative answers But, analysis simplicity is a result of careful instrument design

3 Achieving Simpler QA/QC of Polymeric Materials via FTIR Spectroscopy 1. Simplify Analysis through Innovative Sampling Technology eliminate sample preparation 2. Make Sampling Technology and Software work in partnership 3. Provide true non-destructive analysis of polymeric materials and objects, regardless of size and location Thoroughly understand application & user requirements - innovate to meet those needs

4 Simpler QA/QC of Polymeric Materials via FTIR Spectroscopy In Methods Development, QA/QC, and In-process Control Labs The Agilent Cary 630 FTIR Simplify Analysis through Innovative Sampling Technology Make Sampling Technology and Software work in partnership

5 The Agilent Cary 630 FTIR Spectrometer Most compact routine use FTIR Class leading performance No-alignment optics No-alignment slide in sampling technology Highly intuitive, visually assisted software RFID ensures method selected, visual display and sampling technology match Exclusive sampling technology such as DialPath/TumblIR for polymer films and cupped ATR for polymer beads

6 Flexibility Required for Polymer Analysis Incoming Material ID via ATR & Diffuse; Additive analysis via transmission & Dialpath/TumblIR Dialpath 630 Engine TumblIR Diffuse Reflectance Transmission Diamond ATR Agilent Confidential

7 Why FTIR for QA/QC of Polymers? Suitable for quantitation of many of the additives at low levels that give polymers their distinctive properties. Antioxidants Antistatic Agents Clarifiers Nucleating agents And more Provides data and insight on the molecular structural properties of the polymer Comonomer incorporation quantity and distribution Isotacticity of PP Estimate of average molecular chain length of PE 7 June 20, 2012

8 1. Analysis of Polymer Beads Cary 630 FTIR with ATR cupped solids press firmly holds rounded bead in place. Single reflection diamond ATR quickly provides superior spectra (5 second acquisition) Visual, intuitive software allows less experienced users to get great results Real-time instant refresh screen shows when good contact is made between bead and diamond ATR sensor On board library and rapid search algorithm gives instantaneous identification and confirmation of composition

9 1372 Absorbance Analysis of Vinyl Acetate (VA) in Ethylene Vinyl Acetate Copolymer (EVA) Ratio of the polymers in EVA define the physical characteristics of the final product Seven standard samples of EVA with varying concentrations of VA were analyzed with the Cary 630 equipped with diamond ATR Polyethylene Polyvinyl acetate The ratio of the 1236 cm-1 VA absorbance band to that of the 1467 cm-1 PE absorbance band was found to be optimum for developing a method Wavenumber

10 Vinyl Acetate (wt.%) Analysis of Vinyl Acetate (VA) in Ethylene Vinyl Acetate Copolymer (EVA) Calibration plot of the VA concentration as a function of VA/PE band ratio exhibited excellent linearity; R 2 = shows strong correlation. The slope and offset from the plot was added to the method editor in the MicroLab software to create the method Once the method is implemented in Cary 630 MicroLab software, the percentage of VA in an unknown sample of EVA can be automatically calculated and displayed Quant Validation Plot for Vinyl Acetate pct R²=0.999 y = (x) Peak Area Ratio (1236cm-1 / 1467cm-1)

11 Analysis of Vinyl Acetate (VA) in Ethylene Vinyl Acetate Copolymer (EVA) To evaluate analytical performance of method, EVA samples containing 1% VA and 0.55% VA were prepared and measured with the method implemented on the Cary 630 A 5 sec scan time at 4 cm-1 resolution was used and repetitive measurements were made. Standard deviation of 0.01% VA was calculated and limits of detection and limits of quantitation of 0.03% and 0.1% respectively Validation Sample 0.55% VA 1.00% VA Rep Rep Rep Rep Rep Standard Deviation Average

12 2. Analysis of Polymer Films by Cary 630 with DialPath Technology Additives that influence polymer properties must be incorporated at just the right level to produce a profitable resin Too much expensive additive increases production cost; too little negatively impact resin performance Low level concentration of additives require longer pathlength, i.e. ATR is good for polymer ID; Transmission needed for quantitative measurement of additives 12 June 20, 2012

13 What s needed to make the measurements? Cary 630 FTIR spectrometer and DialPath or TumblIR sample interface with a 1000 μm path length. Hydraulic press and heated platens to form polymer film from beads or powder 13 June 20, 2012

14 Advantages of Cary 630 with DialPath Technology for Analysis of Polymer Films DialPath Simplifies Measurement and Provides Additional Benefits Simple to use simply slide the pressed polymer film between the closed windows of DialPath technology and you re ready to make the measurement. No fringing, so no interfering bands see lower components more effectively. More flexible measurements as opposed to older fixed transmission cells, the DialPath method allows the polymer film to be easily moved so that multiple spots can be examined; great for heterogeneous polymer films Analyze samples more rapidly no sample compartment to purge and larger samples can be accommodated

15 Absorbance The DialPath advantage for polymer films rapidly sample multiple points on a film GMS = 0.83% GMS = 0.84% 0.8% Glycerol Monostearate (GMS) in Polypropylene, 0.6mm Thick, Hot Pressed Coupon Right of Center, 0.92% GMS Right Area ( %GMS), GMS Coupon 1738 Left and Center Areas ( % GMS) GMS = 0.98% GMS = 0.99% GMS = 0.92% Wavenumber 15 Confidentiality Label June 20, 2012

16 Calibrating the methods Standards preparation and analysis Polymer Additives Blend known amounts of the additive with polymer powder Prepare polymer films as prescribed by the method Analyze each of the polymer film standards with Cary 630 Construct a linear least squares plot of (A analyte / A reference ) versus concentration Result is the calibration equation. Molecular Properties Resins covering the range of interest are analyzed by a primary technique such as Nuclear Magnetic Resonance Spectroscopy to determine the value of interest for each standard. Using the values measured by the primary technique as the known concentration for each standard, prepare films, measure the infrared absorption bands as directed by the method, and construct a linear least squares calibration curve as detailed above. 16 June 20, 2012

17 Cary 630 FTIR polymer analytical methods Pre-built MicroLab polymer methods Method Name Analyte Matrix (Polymer) Determination of Irganox 1010 in Polyethylene by Infrared Spectroscopy Determination of Irganox 1010 in Polypropylene by Infrared Spectroscopy Determination of Irganox 3114 in Polypropylene by Infrared Spectroscopy Irganox 1010 Irganox 1010 Irganox 3114 Polyethylene Polypropylene Polypropylene Determination of Vinyl Content of Polyethylene Vinyl Group Polyethylene Percent Ethylene in Statistical Copolymers Statistical Ethylene Polypropylene Percent Glycerol Monostearate in Polypropylene by Infrared Spectroscopy Glycerol Monostearate (GMS) Polypropylene 17 June 20, 2012

18 Conclusion 3 Steps Obtain fast accurate results with ease + + Cary 630 FTIR with DialPath Analytical Procedure Built-in MicroLab Method 18 June 20, 2012

19 Overall Advantages of Cary 630 FTIR for Polymer Analysis Levels of quantitation for the polymeric components better than 0.1 wt% results from class leading optical performance Sample analysis requiring just 5 sec of collection time as a result of fast scan speed combined with superior optical performance Single bounce diamond ATR that slides into place on the spectrometer module and requires no alignment. Truly Plug and Play spectroscopy for the analysis of polymer beads DialPath technology offers a new and exclusive means to analyze polymer films Innovative Microlab software that visually guides the user through the proper use of the sampling technology and the steps for analysis of the polymer RFID autorecognition so that correct methods are used with the ATR sampling technology for the analysis of the polymers Real-Time Analysis feature of the Microlab software aids in ensuring the highest quality data is obtained. The ease of which methods are developed and implemented.

20 Simpler QA/QC of Polymeric Materials via FTIR Spectroscopy For Methods Development, QA/QC, and Troubleshooting The Agilent 4100 ExoScan Materials Analysis Workstation Provide true non-destructive analysis of polymeric materials and objects, regardless of size and location

21 Innovation in optical design, how have things changed? lbs 3.6 lbs Agilent 4100 Exoscan Today 1.9 lbs Agilent Cary Confidentiality Label June 20, 2012

22 Exoscan Materials WorkStation - the Dual-Use FTIR System for Polymer Analysis For the Lab Carry our routine measurements of polymeric materials Analyze data obtained from out of lab measurements Develop qualitative and quantitative methods Out of the Lab Measure large polymeric objects or materials without the need to excise a sample true non-destructive analysis Measure objects regardless of shape or condition of surface Make actionable decisions on the spot improving productivity Triage send less samples back to the lab for analysis Focus on important areas to analyze on an object and reduce unnecessary measurements for improved time to results

23 Typical Applications of ExoScan FTIR in Out of Lab Measurements of Polymers Confirm polymer identity and composition for QA/QC and recycling applications Measure degree of cure in polymeric materials Measure thickness, uniformity and identity of polymer coatings on metal surfaces Measure additives and other chemical components of polymeric materials to ensure composition meets required specifications Detect counterfeit or misidentified materials before they enter the production workflow. Ensure that correct polymer seals, gaskets and o-rings are used in critical applications Measure degradation of polymer materials based on weathering, aging or use. Identify surface contaminants that can affect overall performance of polymeric objects No need to remove a sample true non destructive analysis regardless of shape and size of polymer material or object

24 Dual Nature of the Exoscan Materials Analysis WorkStation - in the lab, out of the lab Method development for field applications is often accomplished in the lab Exoscan was designed to specifically meet this need Docking Station Convert handheld system into bench-top system PC connection Sample stages Interchangeable sample interfaces for polymers diffuse, ATR, external reflectance After development, methods are deployed on ExoScan in handheld configuration 24

25 Applications of ExoScan to QA/QC of Polymers 1. Analysis of carbon black filled seals 2. Thermal degradation in epoxy resin carbon fiber Composites 3. Analysis of contaminants and adulterants on the surface of tires used in racing applications 4. Recycling of carbon black polymers

26 1. Hand Held FTIR Material Identification Germanium ATR Selectivity of FTIR is ideal for material identification. - Well suited to polymers and elastomers - Ge ATR ideal for carbon filled material Industrial need for positive ID - Chemical and manufacturing industry - O-rings and seal materials Safety requirement to prevent leaks 26

27 Sample Interface Considerations - ATR ATR s ease of use SHOULD make it ideal for hand held use No sample preparation High signal to noise Consistent path length High acceptance in lab BUT one feature makes hand held use difficult -> CONTACT Crystal/sample contact is the key - > Flatness not pressure In Lab, press brings crystal and sample in line In Field, contact is made with hand movement hard to keep steady Crystal Geometry is the ANSWER Spherical surface makes good contact at many angles Strong absorbance is observed even with a light touch 27

28 Hand Held FTIR Material Identification O-ring and Seal Identification Exoscan can identify all 10 groups of seals Fluorosilicone, Silicone, Viton, EPR/EPDM, Neoprene, Butyl, Kalrez, NBR, Polyurethane, Natural Rubber Easy Identification by spectral search Highest correlation = correct ID Demonstration 15 samples Exoscan correctly identified all samples Only one sample had a close second match 28

29 2. Effect of Heat Exposure on Carbon Fiber Epoxy Polymer Resin Composite for Commercial Aircraft ExoScan with Diffuse Reflectance Sampling Interface was used to measure spectral changes in the cured epoxy composite matrix as a function of exposure to thermal stress Changes in infrared spectra were correlated to changes in mechanical strength as measured by short beam shear testing Calibrated methods, which correlated with the temperature excursion and subsequent loss of strength, were developed for the ExoScan Exoscan successfully measures oxidation of polymer matrix as a result of heat exposure

30 Absorbance Heat Damage in Carbon Fiber Epoxy Composites correlation between IR spectra and mechanical strength measurements RMS Error % Error r High damage Calibration Cross Validation Prediction Set No damage Wavenumber Prediction Set

31 Y (inches) Composite Panel Non-Uniform Heating and Mapping to Reveal Damage 1C 2C Large Composite Panels are thermally stressed via heat blanket with varied levels of insulation to obtain non-uniform damage 4C C BMS F / 465F / 490F X (inches) T ( O F) 31

32 Analysis of Epoxy Resin Carbon Fiber Composites Via ExoScan Results Robust Calibrations for thermal and UV exposure were successfully developed Certified Standards have been prepared and are commercially available ExoScan is included in Boeing 787 Service Repair Manual Early 787 commercial airlines have acquired ExoScans and certified calibration standards with their new aircraft Other aircraft manufacturers are evaluating ExoScan for their specific applications Composites Serve as Primary Structural Material Carbon laminate Carbon sandwich Other composites Aluminum Titanium Titanium 15% Steel 10% Aluminum 20% Other 5% CFRP 43% Misc. 9% Composites 50%

33 3. Detecting Tire Manipulation in Professional Racing Using Handheld FTIR Currently no onsite testing for accidental or intentional tire alteration Tire alteration includes: Soaking in fuel, engine oil, brake cleaner spray, or gear oil Anything that softens rubber and improves grip ExoScan was used at 2011 DTM races with Porsche Carrera Cup Cars to determine if tires were treated Spherical germanium ATR was chosen as sampling technology

34 Tire Manipulation The Result An ExoScan method was developed using pre-race and in-race qualifying tires Tires can be tested immediately before qualifying laps FTIR method can be used on hot or cold tires

35 Absorbance Absorbance The FTIR spectra of treated racing tires (Blue) and untreated tires (Green and Red) Gear oil Wavenumber Racing petrol fuel Wavenumber

36 Tire Analysis FTIR Tire Method Ratio of hydrocarbon abs 2929cm- 1 relative to butadiene 905cm-1 abs Elevated ratio indicates tires have been tampered with Thresholds are > marginal (yellow) and >10 critical (red) Ratio technique eliminates effects of temperature and surface irregularities New non-scuffed tires need the mold-release agent removed Sample Name Hydrocarbons Butadiene Ratio Blank 8.20 Blank Repeat 7.72 Flat spot Brake cleaner spray Gear Engine oil Fuel Gear oil soak Front tire new Front tire new buffed 6.98 Rear tire new Rear tire new buffed 7.67 Front tire hot 6.70 Rear tire hot 7.09

37 4. Electronic Industry Plastics Recycling Some recycling companies use a method known as tap, burn and sniff to differentiate polymers Many plastics are carbon black filled and thus are a challenge to instrumental methods ExoScan, with its proven ability to handle carbon black filled materials, is an effective analyzer for these materials and an improvement over tests that require the human senses Spherical diamond ATR sampling interface is ideal for these measurements

38 Comparison of FTIR and Sensory Method for Recycling Five samples were tested via Exoscan and empirical sensory method The human expert identified the samples as polyoxymethylene (POM) FTIR spectra of the five samples also indicated that the five samples were POM FTIR and Expert tester were in agreement Spectra Name Best Match POM_01 POM (91%) POM_02 POM (92%) POM_03 POM (87%) POM_04 POM (90%) POM_06 POM (86%)

39 Comparison of FTIR and Sensory Method for Recycling Eight samples were tested via Exoscan and empirical sensory method The human expert identified the samples as polyphenylene oxide (PPO) FTIR spectra of the eight samples that the samples were a variety of polymers and polymer mixtures Expert s sensory results were not confirmed by ExoScan Spectra Name Best Match PPO_01 PPO + PS (80%) PPO_02 PPO + PS (80%) PPO_03 PC (95%) PPO_04 PMMA (82%) PPO_05 PC (90%) PPO_06 PC (85%) PPO_07 PET (94%) PPO_08 PEGT (95%)

40 Advantages of ExoScan Materials Workstation for QA/QC Dual Nature of the system permits methods development in the lab and then rapid deployment of methods to at-site locations Non destructive analysis means no need to excise samples analyze any size or shape object Make instant, actionable decisions on what to analyze and where to analyze on an object Superior performance of optics and sampling technology provides superior data and information Analyzes carbon black and carbon fiber filled polymers with ease Develop methods on laptop, deploy methods on PDA with results displayed as visual, color status of sampling area No alignment, instantly interchangeable sampling technology affords analysis of virtually any type of polymeric material Innovative spherical germanium or diamond ATR and high collection diffuse reflectance sampling technology coupled with ultra fast system optics provides superior data for most challenging analyses

41 Simplify QA/QC of Polymers Via FTIR Cary 630 FTIR with DialPath 4100 ExoScan Materials Analysis Workstation 41 Confidentiality Label June 20, 2012