Analytical Investigations: Case Studies Involving Plastics & Polymers. UL PROSPECTOR Webinar

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1 Analytical Investigations: Case Studies Involving Plastics & Polymers UL PROSPECTOR Webinar April 30, 2015

2 Today s Outline Evans Analytical Group (EAG) Chemir / EAG Materials expertise Analytical tools and techniques Case Studies Presented at NPE 2015 Abstracts from various analytical projects Issue; Approach; Solution Finding a Solution When to consider a contract lab Internal vs. external capabilities What to look for in a testing lab

Chemir Analytical Services CHEMIR, A division of Evans Analytical Group (EAG) EAG: Leading fully integrated independent laboratory network Complex problem

3 Chemir Analytical Services CHEMIR, A division of Evans Analytical Group (EAG) EAG: Leading fully integrated independent laboratory network Complex problem solving through analytical investigations and scientific consulting Worldwide leader in contract laboratory services: >700 employees, 23 sites, 7 countries

East Windsor, NJ Raleigh, NC EU Locations Reading, U. K.

4 Evans Analytical Group (EAG) US Locations Sunnyvale, CA Santa Clara, CA Phoenix, AZ St. Louis, MO Boston, MA Detroit, MI Minneapolis, MN Irvine, CA San Diego, CA Austin, TX Syracuse, NY East Windsor, NJ Raleigh, NC EU Locations Reading, U. K. (Sales) Toulouse, France (Lab) Asian Locations Tokyo, Japan (Sales) Seoul, Korea (Sales) Singapore (Sales) Hsinchu, Taiwan (Lab) Shanghai, China (Lab)

5 Industries Served Plastic and Polymer Related Industries Packaging Pharmaceutical Medical Device Food and Beverage Paints, Coatings, Adhesives and Sealants Industrial & Consumer Products Home, Health and Beauty

6 Analytical Strengths Surface Analysis Materials Identification Contaminant Identification Failure Analysis (physical and chemical testing) Polymer Analysis Deformulation / Reverse Engineering On-Site Sampling Custom Synthesis... everything comes down to chemistry

7 Our Analytical Instruments SEPARATIONS Gas Chromatography Electronic Conductivity Detection (ECD) Flame Ionization Detection (FID) Mass Spectrometry (GC-MS) High Performance Liquid Chromatography Spectrophotometric (UV-Vis) Fluorescence Mass Spectrometry (LC-MS) Evaporative Light Scattering (ELSD) Electrospray Ionization-Ion Trap Mass Spectrometry (ESI-IT-MS) Atmospheric Pressure Chemical Ionization- Ion Trap Mass Spectrometry (APCI-IT-MS) MOLECULAR SPECTROSCOPY Ultraviolet-Visible Spectrophotometry (UV-Vis) Fourier Transform Infrared Spectroscopy (FTIR) Ion Trap Mass Spectrometry (ITMS) Triple Quadrupole Mass Spectrometry (TQMS) Quadrupole Time-of-Flight (Q-TOF) Raman Spectroscopy Nuclear Magnetic Resonance Spectroscopy (NMR): 400 MHz 1 H, 13 C, 31 P, 19 F ELEMENTAL SPECTROSCOPY Inductively Coupled Plasma-Optical Emission Spectroscopy (ICP-OES) Cold Vapor Atomic Absorption (CVAA) Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) Laser Ablation-Inductively Coupled Plasma- Mass Spectrometry (LA-ICP-MS) 1 of 3

8 Our Analytical Instruments MICROSCOPY Transmission Electron Microscopy (TEM) Scanning Transmission Electron Microscopy (STEM) Atomic Force Microscopy (AFM) Optical Microscopy Focused Ion Beam (FIB) Imaging Scanning Electron Microscopy-Energy Dispersive X-Ray Spectroscopy (SEM-EDS) Optical Profilometry (OP) Electron Energy Loss Spectroscopy (EELS) BULK ANALYSIS X-Ray Fluorescence (XRF) Glow-Discharge Mass Spectrometry (GDMS) Instrumental Gas Analysis (IGA) SURFACE ANALYSIS Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS) Secondary Ion Mass Spectrometry (SIMS) X-Ray Photoelectron Spectroscopy/Electron Spectroscopy for Chemical Analysis (XPS/ESCA) Energy Dispersive X-Ray Spectroscopy (EDS) Rutherford Backscattering Spectroscopy (RBS) Auger Electron Spectroscopy (AES) Low Energy X-Ray Emission Spectroscopy (LEXES) Total Reflection X-Ray Fluorescence Spectroscopy (TXRF) X-Ray Reflectivity (XRR) X-RAY DIFFRACTION (XRD) Micro-XRD High Temperature-XRD Powder Diffraction-XRD 2 of 3

9 Our Analytical Instruments THERMAL TESTING Flash Point Thermogravimetric Analysis (TGA) Modulated Differential Scanning Calorimetry (mdsc) Thermal Mechanical Analyzer (TMA) Differential Thermal Analysis (DTA) WET CHEMICAL TECHNIQUES And Other Equipment Karl Fischer Volumetric Titration ph Ion Selective Electrodes (ISE) Soxhlet Extraction Glass Capillary Viscometers Brookfield Viscometers Weathering Chambers

10 EAG Bubble Chart

11 Comparing Select Analytical Techniques Depth of Analysis ~ ~ ~ ~

12 Investigational Analyses Designing Analytical Studies Studies customized / unique Technical discussions with client Materials Objectives Analytical Focus Information from client the more the better Technical data sheets MSDS Specifications Other analytical reports

13 Investigational Analyses Polymer and Polymer Additive Expertise Polyolefins: PP, PE, PIB, EPR Engineering Resins: PMMA, Nylons, PU, flexible and rigid PVC, others Adhesives / Coatings / Rubber Products: epoxies, EVA, EPDM, siloxanes, TPE, Neoprene, SIS, SBS, NBR, EVA, PUR, silicone and more Specialty Materials: multi-layer films, multilayer composites

14 Case Studies Presented at NPE 2015 Materials Identification Quality Issue / Product Contaminant Multi-layer Film Characterization Finished Product Failure Processing Issue Method Development Packaging Failure Polymer Identification Surface Analysis

15 Past Chemir Case Study Presentations Lots of Project Data

16 Today s Chemir Case Study Presentations Abstracts Analytical Case Studies Abstracts to provide broad scope of analytical skill sets Material issue Analytical approach / analytical techniques Conclusions / Answers / Resolution No analytical data!

17 Today s Chemir Case Study Presentations Abstracts Analytical Case Studies Abstracts to provide broad scope of analytical skill sets Material issue Analytical approach / analytical techniques Conclusions / Answers / Resolution No analytical data! Chemir to Offer GoTo On-Line Meetings Single case study details 15 minutes maximum Dates and times to be provided in follow-up

18 CASE STUDY 1: Identification of Inorganic Filler

19 Identification of Inorganic Filler Project Background Analysis of toll manufactured polypropylene (PP) bottle caps to confirm inorganic additive Technical Request Confirm presence of TiO 2 Suspected use of CaCO 3 Analytical Technique X-Ray Diffraction (XRD)

20 X-ray Diffraction (XRD) Rutile (TiO 2 ) observed

21 CASE STUDY 2: Characterization of Multi-Layer Composite???

22 Analysis of Multi-Layer Composite Project Background Analysis of commercial product to understand current laminate technology Technical Request Identify and/or characterize individual layers in laminate Analytical Technique Raman spectroscopy

23 The Raman Microscope 23

24 Relative Intensity Relative Intensity Confocal Raman Microscopy of Multi-Layer Laminate Film Top layer: PDMS Middle layer: PDMS/PDPS Bottom layer: PDMS Wavenumbers (cm-1) Wavenumbers (cm -1 ) 24

25 CASE STUDY 3: Quality Issue / Product Contaminant

26 Quality Issues Contamination Physical Failures Raw Material Issues Production Lot Variability Process Control Material Compatibility and Stability

27 Quality Issue / Product Contaminant Project Background Injection molder noticed a visible contaminant entrained in their plastic packaging system used for a personal care product Technical Request Identify and/or characterize contaminant to assist in root cause investigation Prevent future occurrence

28 Quality Issue / Product Contaminant Analytical Techniques Optical Microscopy with imaging Sample preparation / contaminant isolation Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM-EDS) Fourier Transform Infrared Spectroscopy (FT-IR)

29 Quality Issue / Product Contaminant Project Conclusion Contaminant was consistent with a Quinacridone Lake pigment The pigment had not dispersed thoroughly in the compounded polymer Client used this information to correct a manufacturing process / dispersant issue

30 CASE STUDY 4: Specialty Polymer Film Characterization

31 Polymer Characterization: Multi-Layer Film Project Background Client involved with R&D efforts to design specialty multi-layer polymer film Film designed to provide physical integrity with unique and specific barrier properties gas, moisture, microbe, others Technical Request Quality check of prototype film Confirmation of polymer film number of layers, layer thicknesses, presence of specific inorganic filler, additive dispersion

32 Polymer Characterization: Multi-Layer Film Analytical Techniques Sample preparation / cross-sectioning Scanning Electron Microscope (SEM) Energy Dispersive X-Ray Spectroscopy (EDS) Inductively Coupled Plasma with Mass Spectral Detection (ICP-MS) Raman Spectroscopy Physical property evaluation

33 Polymer Characterization: Multi-Layer Film Project Conclusions Analyses confirmed four of five targeted compositional specifications Data from missed specification provided client with information needed for alternate material selection All results matched client s internally generated data. Their customer requested 3 rd party testing.

34 CASE STUDY 5: Plastic Failure Investigation

35 Plastic Failure Investigation Project Background A fluorescent light fixture manufacturer received customer complaints: bulbs were falling from the installed fixtures The manufacturer noticed 1) white residue on the reflector and 2) the sockets ( tombstones ) discolored and cracked Prior to replacing the tombstones, the manufacturer needed to know the cause of the failure 1) to assess liability and 2) prevent future issues Objective To determine the cause of the failure with the fluorescent light fixture tombstones

36 Project Strategy Comparative analysis between control and failed samples Initial Inspection Plastic Failure Investigation Identify the base plastic (if not known) Optical microscopy and/or Scanning Electron Microscopy Elemental analysis Thermal properties Review literature references to suggest potential causes to failures

Analytical Techniques Plastic Failure Investigation Polymer and Degradant Characterization Micro-Fourier Transform Infrared Spectroscopy (FT-IR) Horizontal Attenuated Total Reflectance

37 Analytical Techniques Plastic Failure Investigation Polymer and Degradant Characterization Micro-Fourier Transform Infrared Spectroscopy (FT-IR) Horizontal Attenuated Total Reflectance Infrared Spectroscopy (HATR) Nuclear Magnetic Resonance Spectroscopy (NMR) Gas Chromatography with Mass Spectral detection (GC/MS) Solvent extractions / pre-concentration of degradants

38 Analytical Techniques Plastic Failure Investigation Failure Site Characterization Optical Microscopy Scanning Electron Microscopy (SEM) Energy Dispersive Spectroscopy (EDS) Accelerated Stability Study Part exposure to suspected chemical-attack compound Reproduced part failure / degradation

Analytical Techniques Plastic Failure Investigation Failure Site Characterization Optical Microscopy Scanning Electron Microscopy (SEM) Energy

39 Analytical Techniques Plastic Failure Investigation Failure Site Characterization Optical Microscopy Scanning Electron Microscopy (SEM) Energy Dispersive Spectroscopy (EDS) Accelerated Stability Study Part exposure to suspected chemical-attack agent Reproduced part failure / degradation

40 Plastic Failure Investigation Conclusions/Future Data suggested dicyclohexylamine was responsible for the degradation of the polycarbonate by aminolysis After discussions with client, they found the dicyclohexylamine was used as a corrosion inhibitor in the cutting fluid Current work involves an exposure study between the control tombstones, nylon tombstones, and dicyclohexylamine Client is planning to switch to nylon tombstones for harsh environments

41 CASE STUDY 6: Processing Failure: Phenolic Epoxy Laminate

42 Processing Failure: Epoxy Laminate Project Background Client manufacturers phenolic epoxy laminate for aerospace application Client purchases all raw materials per their contracted product specifications Several years of successful production Observes sporadic wetting issue between glass fiber and non-cured phenolic epoxy Recent issues resulted in >$375,000 of lost product Client performed thorough check of all raws to confirm they re within specifications no issues identified

43 Processing Failure: Epoxy Laminate Technical Request Determine root cause for wetting issue Prevent high rate of lost product

44 Processing Failure: Epoxy Laminate Analytical Techniques Optical microscopy Customized sample preparation Fourier Transform Infrared Spectroscopy (FT-IR) Gas Chromatography with Mass Spectral detection (GC/MS) Nuclear Magnetic Resonance Spectroscopy ( 1 H- NMR) Gel Permeation Chromatography (GPC) Scanning Electron Microscope with Energy Dispersive X-Ray Analysis (SEM-EDXA) Physical Property Measurements / Viscometry

45 Processing Failure: Epoxy Laminate Analytical Approach Review of Production Records No changes in their process or materials (per the client) No variability in process parameters Line speed Throughput Process temperatures Wetting issue prior to cure steps Wetting issue correlates to three specific production lots

46 Processing Failure: Epoxy Laminate Conclusions/Future All production lots of epoxy were within manufacturer s specifications Lower range of specifications did not work in their process Results allowed our client to revise raw material specifications New specification for minimum % free phenol set at 0.50% No issues since revision of product specifications

47 CASE STUDY 7: Product Contaminant: Packaging Failure

48 Product Contaminant: Packaging Failure Project Background Food distributor observes discoloration of food product packaged with PVC film Same PVC film supplier for several years Specialty film for sponsor s marketing campaign Aesthetics issues can t sell food product with discoloration Compromised product integrity? Safety issue?

49 Product Contaminant: Packaging Failure Technical Request Determine root cause for product discoloration Help assess liability PVC film Resin supplier Resin convertor Packager Food product

50 Product Contaminant: Packaging Failure Technical Request Determine root cause for product discoloration Help assess liability PVC film Resin supplier Resin convertor Packager Food product

51 Product Contaminant: Packaging Failure Analytical Techniques Customized sample preparations / contaminant isolation High Performance Liquid Chromatography (HPLC) Liquid Chromatography with Mass Spectral detection (LC/MS) Ultraviolet - Visible Spectroscopy (UV-Vis) Gas Chromatography with Mass Spectral detection (GC/MS)

52 Product Contaminant: Packaging Failure Technical Design Comparative study of key materials involved o Packaging film standard film specialty film o Food products control discolored

53 Project Conclusions Product Contaminant: Packaging Failure Organic colorant identified in both the specialty film and in the discolored food product (low ppm levels) Analysis of control and suspect films indicated difference in additive packages ESO additive in suspect film shouldn t be there ESO solubilizes fat-soluble dye ESO/dye migrate from film into fatty food product

54 Project Conclusions Product Contaminant: Packaging Failure Organic colorant identified in both the specialty film and in the discolored food product (low ppm levels) Analysis of control and suspect films indicated difference in additive packages ESO additive in suspect film shouldn t be there ESO solubilizes fat-soluble dye ESO/dye migrate from film into fatty food product Liability: PVC film manufacturer confirmed use of different formulation in specialty film

55 Polymer Coating: Method Development CASE STUDY 8: Polymeric Coating Quantitative Method Development

56 Polymer Quantitation: Method Development Project Background Client wanting to expand existing woven polymer fiber in new market Existing fiber uses process proprietary polymeric coating that has regulations in new market Need to quantitate level of polymeric coating subsequent to wash processing Technical Issue Quantitation of polymer coating at 10 ppm No existing analytical method for quantitation

57 Polymer Quantitation: Method Development Analytical Techniques Fourier Transform Infrared Spectroscopy (FT-IR) Nuclear Magnetic Resonance Spectroscopy (NMR) Gas Chromatography with Mass Spectrometry (GC/MS) Liquid Chromatography with Mass Spectrometry (LC/MS) High Performance Liquid Chromatography (HPLC) Wet chemistry sample preparation

58 Polymer Quantitation - Method Development Strategy Identify the base polymer in the coating Explore potential analytical techniques: HPLC GPC NMR Evaluate instrument detection limit for planning sample preparation Evaluate linearity, specificity, and possibility of detecting at a 1 ppm level

59 Polymer Quantitation Method development Polymer Identification Yarn: Poly(ethylene terephthalate) Coating: Sulfonated Polyester FT-IR, 1 H-NMR, and Pyrolysis GC/MS Isophthalic Acid is the di-acid in the coating polyester O Polyester Coating H [ O O O O [ n OH

60 Digestion and HPLC Polymer Quantitation Method Development O H [ O 95% EtOH/5% H 2 O + O O O Polyester Coating [ OH n 1M KOH Isophthalic Acid

61 Project Conclusions Polymer Quantitation Method Development Developed analytical method for polymer coating quantitation Qualified the method for 10 ppm quantitation Deliverable to client was a written procedure to transfer to their internal QC lab

62 Analytical Issues - Finding a Solution When to consider a contract lab What to look for in a contract lab

63 When to Use a Contract Lab We don t have the internal capabilities Contract labs often specialize in certain areas and are therefore more experienced and cost effective with the testing you need We don t have the instrumentation It is often cheaper to use an outside lab than to buy needed equipment. Analytical instrumentation is expensive! We don t have the capacity Contract labs can help when overflow or emergency testing needs is required Potential for Legal Claims Legal issues such as patent infringement, product failure, product recall, etc. often require an independent testing lab

64 What to Look for in a Contract Lab Routine vs. Non-Routine Quality & Communication Final Deliverable Turnaround Time & Cost Experience with Legal Claims

65 Routine vs. Non-Routine Routine Labs Often specialize in a particular method or matrix/sample type Higher level of experience and throughput in those areas Non-Routine Labs Specialize in solving obscure and complex problems that often require unique and inventive approaches Use a variety of investigative analytical techniques Diverse experience regarding problems and how to solve them

Who will be my contact? Will they be available to answer my questions?

66 Quality and Communication Quality Accreditation Company quality policies Communication Detailed discussion of issue(s) Are the right questions before beginning the project? Who will be my contact? Will they be available to answer my questions? Are they qualified to answer my questions? How will results be communicated? And when? Regular updates Flexibility in reporting

67 Final Deliverable Results are best presented in a comprehensive report Conclusions Methods and observations Original data should be included along with scientific interpretations

68 Turnaround Time & Cost Be prepared for increased costs for expedited services Costs for expedited testing may be balanced against manufacturing down time or potential legal challenges When comparing contract laboratory fees make sure you are looking at similar investigative analyses A customized laboratory will cost more than a routine lab Take care to make apples to apples comparisons when evaluating costs or comparing proposals from different labs

69 Experience with Legal Claims Deposition / Expert witness training Sample control procedures Sample log-in Photography Locked storage Chain of custody Rigorous attention to detail required by courts

70 Wrap Up Reasons for Plastics Testing Materials Identification Competitive Product Analysis Quality Issues Finding a solution When to consider a contract lab Internal vs. external capabilities What to look for in a testing lab

71 Questions? Chemir Analytical Services A division of Evans Analytical Group, LLC Christopher Andren Sr. Technical Specialist Analytical Services Tel: candren@eag.com

72 Today s Chemir Case Study Presentations Abstracts Analytical Case Studies Abstracts to provide broad scope of analytical skill sets Material issue Analytical approach / analytical techniques Conclusions / Answers / Resolution No analytical data! Chemir to Offer GoTo On-Line Meetings Single case study details 15 minutes maximum Dates and times to be provided in follow-up s

raw materials C V Mn Mg S Al Ca Ti Cr Si G H Nb Na Zn Ni K Co A B C D E F

raw materials C V Mn Mg S Al Ca Ti Cr Si G H Nb Na Zn Ni K Co A B C D E F Today s advanced batteries require a range of specialized analytical tools to better understand the electrochemical processes that occur during battery cycling. Evans Analytical Group (EAG) offers a wide-range