MATERIALS TESTING AND RESEARCH SOLUTIONS FROM AGILENT Polymers and Rubbers Application Compendium AGILENT TECHNOLOGIES MATERIALS TESTING AND RESEARCH SOLUTIONS From the extraction of raw materials through the Examples of advanced materials include: development, manufacturing and utilization of advanced materials, to material reuse and recycling, Agilent (cid:129) Aero and automotive (metals, composites) Technologies offers innovative, reliable analytical solutions (cid:129) Polymers and composites for your business. Our comprehensive line of instruments (cid:129) Glass/ceramics/optics and photonics (lenses and for materials testing and research will ensure you coatings, eyewear) consistently and cost-effectively deliver the highest quality finished products and materials. (cid:129) Specialty films and surface coatings (paint, adhesives, resins) Materials market overview (cid:129) Semiconductor and electronics (LEDs, LCDs, disk The materials market comprises the industries involved drives, thin-film electronics, fuel cells, solar cells) in the extraction of raw minerals from the earth (cid:129) Textiles, paper and packaging (geosciences, mining and mineralogy) and the subsequent characterization and transformation of those raw minerals (cid:129) Consumer goods (jewelry, gemstones, cosmetics) into metal alloys, ceramics, glass, and other engineered (cid:129) Construction (cement, architectural glass, metal alloys) materials — described collectively as “advanced materials”. These advanced materials are developed with purpose specific characteristics and properties in a wide variety of industries. Materials market lifecycle AGILENT TECHNOLOGIES SOLUTIONS FOR POLYMERS AND RUBBERS When accuracy and reliability in measuring the quality and Agilent solutions chemical composition of plastics and polymers is critical to Agilent FTIR spectrometers, microscopes and chemical your success, choose Agilent. imaging systems deliver: Agilent molecular spectroscopy products provide the (cid:129) Detailed structural analysis of polymer and rubber information required for development, QA/QC and to based products. monitor the in-use service of these materials. Laboratory (cid:129) QA/QC support in the production of polymer and rubber. FTIR bench and microscopy systems provide insight into both bulk and detailed structure of polymers and (cid:129) Defect analysis and analysis of layered materials via rubber materials. Mobile FTIR spectroscopy affords non- FTIR microscopy. destructive analysis of polymer, composite and rubber- (cid:129) Nondestructive, in situ analysis of polymer and rubber based objects, regardless of location, shape or size. based objects in support of determining effect of use on In addition, Agilent atomic force microscopy (AFM) longevity and performance. systems permit the detailed surface characterization (cid:129) Handheld FTIR for nondestructive analysis of polymer, of polymers and rubbers at the nanoscale. These high- composites and rubber in any shape, size or location precision, modular AFM systems offer industry-leading environmental/temperature control and electrical Use Agilent LC systems for: measurement capabilities to keep moving R&D forward. (cid:129) Investigating very small differences between the Agilent also offers an innovative, extremely compact field- chemical structures of polymers emission scanning electron microscopy (FE-SEM) system optimized to provide high surface contrast using low- (cid:129) Analysis of additives in polymers, such as phenolic voltage imaging techniques. When mechanical properties antioxidants and erucamide slip additives. characterization at the nanoscale is needed, user friendly (cid:129) Screening and qualitative identification of antioxidant Agilent nanoindentation systems ensure unrivaled polymer additives. accuracy and outstanding versatility. Agilent’s GPC/SEC portfolio provides: Polymers and rubber are used across industry in an (cid:129) High-performance analysis of engineering polymers ever widening set of products and subassemblies. As such as PEEK and polybutylene terephthalate, synthesized materials, their properties, performance polyolefins such as polyethylene and polypropylene, and longevity are directly related to achieving proper low molecular weight resins such as epoxy resins, composition and structure. These materials have finite polyesters and phenolic resins, or elastomers such as lifetimes, which are directly related to environmental styrenebutadiene and natural rubber affects, additives and stabilizers and overall usage. (cid:129) A comprehensive portfolio of GPC/SEC columns and calibrants for polymer analysis. Agilent AFM and FE-SEM systems facilitate: (cid:129) Surface properties characterization in various environments (for example, heat, cold, gases). (cid:129) Electrical testing of charged polymers. Agilent nanoindentation systems enable: (cid:129) Indentation and scratch testing of coatings on plastics. (cid:129) Mechanical properties characterization of tires, PVC, and polyethylene. AGILENT TECHNOLOGIES APPLICATIONS FOR POLYMERS AND RUBBERS SPECTROSCOPY Fourier Transform Infrared (FTIR) Spectroscopy Quantitative Analysis of Copolymers Using the Cary 630 FTIR Spectrometer Determination of Percent Polyethylene in Polyethylene/Polypropylene Blends Using Cast Film FTIR Techniques Rapid Identification of O-rings, Seals and Gaskets Using the Handheld Agilent 4100 ExoScan FTIR A New Approach to Sample Preparation Free Micro ATR FTIR Chemical Imaging of Polymer Laminates Identification of Contaminants in Vehicle Fuel Tank Caps Using FTIR ATR-Microscopy Component Failure Analysis of Vehicle Spark Plugs Using FTIR Spectroscopy With a Micro-ATR Large Sample Objective Material Analysis by Infrared Mapping: A Case Study Using a Multilayer Paint Sample Analytical Methods for the Agilent Cary 630 FTIR Determination of Irganox 3114 in polypropylene by infrared spectroscopy Determination of percent ethylene in ethylene-propylene statistical copolymers Determination of Irganox 1010 in polyethylene by infrared spectroscopy Determination of Irganox 1010 in polyproplene by infrared spectroscopy Determination of the vinyl content of polyethylene resins Determination of percent glycerol monostearate in polypropylene by infrared spectroscopy Atomic Force Microscopy (AFM) and Field-Emission Scanning Electron Microscopy (FE-SEM) Advanced Atomic Force Microscopy: Exploring Measurements of Local Electric Properties Agilent 5600LS AFM High-resolution Imaging Molecular-level Understanding of n-Alkanes Self-Assembly onto Graphite Several Aspects of High Resolution Imaging in Atomic Force Microscopy Compositional Mapping of Materials with Single-Pass Kelvin Force Microscopy Atomic Force Microscopy Studies in Various Environments Young’s Modulus of Dielectric ‘Low-k’ Materials Nanoindentation Nanoindentation, Scratch, and Elevated Temperature Testing of Cellulose and PMMA Films Measuring the Complex Modulus of Polyethylene Using Instrumented Indentation Complex Shear Modulus of Commercial Gelatin by Instrumented Indentation AGILENT TECHNOLOGIES APPLICATIONS FOR POLYMERS AND RUBBERS CHROMATOGRAPHY Liquid Chromatography (LC) Sensitive Polymer Analysis using Critical Point Chromatography and ELSD Fast Analysis of Phenolic Antioxidants and Erucamide Slip Additives in Polypropylene Homopolymer Formulations Using 1200 Rapid Resolution Liquid Chromatography (RRLC) with Rapid Resolution High Throughput (RRHT) Columns and Method Translator Analysis of Phenolic Antioxidant and Erucamide Slip Additives in Polymer by Rapid-Resolution LC Developing a UHPLC Method forUV-based Detection and Quantification of Primary Aromatic Amines in Low Concentrations Determination of Polymer Additives and Migration Products Prevalent in Food Packaging Material Determination of Phthalate Migration From Toys Analysis of Bisphenol A Leaching from Baby Feeding Bottles High Sensitivity Analysis of Phthalates Using HPLC with Low Temperature Evaporative Light Scattering Detection Agilent 1290 Infinity LC with AgilentPoroshell Columns for Simultaneous Determination of Eight Organic UV Filters Gel Permeation Chromatography (GPC) Stable Baselines in the Analysis of Poly(lactide-co-glycolide) Polymers by GPC with ELSD Analyze Injection-Molding Polymers on Agilent PLgel 5 µm MIXED-C by GPC Artifact Free Analysis of Lignins by GPC using Agilent PolarGel-M GPC and Agilent PolarGel-M Columns for the True Representation of Novolac Resins Analysis of Polysaccharides by GPC Viscometry using the Agilent 390-MDS Multi Detector Suite Characterization of Block Copolymers Synthesized via Transition Metal Mediated Living Radical Polymerization Analysis of Biodegradable Polymers by GPC Analysis of Poly(styrene/butadiene) Copolymers by Conventional Gel Permeation Chromatography on the Agilent PL-GPC 50 Plus Size Exclusion Chromatography (SEC) Size Exclusion Chromatography for the Analysis of Dental Polymers SEC Analysis of a Water Soluble Copolymer SEC Analysis of a Acrylamide Copolymer GPC/SEC Analysis of biodegradable polymers by GPC/SEC Analysis of polyolefins by GPC/SEC Analysis of engineering polymers by GPC/SEC Analysis of elastomers by GPC/SEC Low molecular weight resins and prepolymers Quantitative analysis of copolymers using the Cary 630 FTIR spectrometer Application note Materials testing and research Author Frank Higgins and Alan Rein Agilent Technologies Danbury, CT, USA Introduction FTIR spectrometers employing attenuated total refl ectance (ATR) sampling interfaces are a proven and powerful tool for the analysis of polymeric materials. Because of its unique combination of features and class- leading performance, the new Agilent Cary 630 FTIR spectrometer makes quantitative analysis of polymers especially fast and easy. In this application note, the amount of key components in two important copolymeric materials are measured — the styrene content in styrene butadiene rubber (SBR) and the ratio of polyethylene to vinyl acetate in polyethylene vinyl acetate (PEVA) polymer. The Cary 630 FTIR equipped with its single refl ection Diamond ATR sampling accessory (Figure 1) is used for these measurements. Figure 2. Polymer is placed directly on ATR sampling accessory. Uniform, constant pressure is provided by the sample press, ensuring that high quality spectra are obtained. Real-time analysis software provides an immediate indicator of spectral quality To develop a quantitative FTIR method, four commercial Figure 1. Agilent Cary 630 FTIR spectrometer equipped with single refl ection SBR calibration standards, with polystyrene Diamond ATR sampling accessory concentrations of 0%, 5%, 23%, and 45%, were measured in triplicate using the Cary 630 FTIR. Styrene concentration in SBR polymer The spectra reveal the expected polystyrene (PS) absorbance bands (Figure 3) at 699 cm-1, 759 cm-1, and a Styrene butadiene rubber (SBR) is the most common weaker band at 1031 cm-1. Spectral bands at synthetic rubber material and its main use is in the 911 cm-1, 964 cm-1, and 995 cm-1 arise from manufacture of tires, which accounts for nearly 70% unsaturations (vinyl and trans CH wag) in polybutadiene, of its production. The properties of SBR rubber can which decrease as the PS bands increase. The be altered by varying the ratio of styrene to butadiene exception is the pure polybutadiene, which has far monomers in the manufacturing process. The normal more cis unsaturations relative to the other polymers, ratio is 3:1 butadiene to styrene (25% styrene). Higher since it is not cross-linked and in liquid form. The PS styrene concentrations make the material harder, but absorbance bands appear to follow Beer’s Law by less elastic. Most performance industries, such as increasing proportionately with concentration, and racing tires and specialty military applications, are therefore are excellent candidates for quantitative requiring more consistent SBR product, which drives the analysis. need for better quality assurance and control by both end users and manufacturers. The plot of the peak height absorbance for the strongest IR band of PS at 699 cm-1 as a function of concentration The measurement of a polymer sample by the Cary indicates great linearity and a strong correlation 630 FTIR equipped with an ATR accessory is extremely coeffi cient of R2=0.999 in the calibration (Figure 4). straightforward. The polymer material is placed on Using the linear regression slope and offset from this the diamond crystal and the sample pressure press is calibration, a method is added to the MicroLab FTIR rotated downward until adequate pressure is placed on software that enables the polystyrene percentage in the sample to observe a spectrum in the Cary 630’s real- an unknown sample to be automatically displayed. The time analysis MicroLab FTIR software (Figure 2). The limit of detection for the quantitative analysis of PS in real-time analysis mode provides instantaneous spectral SBR is 0.09%, calculated as three times the standard update and makes it easy for even novice users to get deviation of the 0% replicate data (StDev= 0.03% PS). highly repeatable results. The sample press on the Cary 630 is designed so that it cannot be over-tightened, thus protecting the diamond crystal against over-pressure. 2 Figure 3. The FTIR spectra of four SBR rubber standards with increasing polystyrene concentrations: 0% (purple), 5% (red), 23% (green), and 45% (blue) Since the ratio of polyethylene (PE) to vinyl acetate (VA) in PEVA can affect the physical properties of the fi nal product, it is important for manufacturers to have a fast, easy measurement procedure for these components. As in the previous example, the Cary 630 FTIR spectrometer with single refl ection diamond ATR is ideal for this measurement. In this example, seven commercially-available standards of PEVA were measured with the Cary 630 FTIR system. The calibration standards used were: • Polyethylene, low density (0% vinyl acetate) • Ethylene/vinyl acetate copolymer #506 (9 wt% vinyl Figure 4. FTIR calibration curve for polystyrene in SBR rubber using the acetate) 699 cm-1 peak height absorbance; R2=0.999. • Ethylene/vinyl acetate copolymer #243 (14 wt% vinyl acetate) Ratio of polyethylene to vinyl acetate in PEVA • Ethylene/vinyl acetate copolymer #244 (18 wt% vinyl acetate) Polyethylene vinyl acetate (PEVA) is very common in • Ethylene/vinyl acetate copolymer #245 (25 wt% everyday products used in the home, sports equipment, vinyl acetate) industrial and medical applications. In the latter • Ethylene/vinyl acetate copolymer #316 (28 wt% applications, medicines can be mixed in solution with vinyl acetate) PEVA and then the mixture dried to produce biologically- inert, slow-release plastic implants and transdermal • Ethylene/vinyl acetate copolymer #326 (40 wt% patches. vinyl acetate) 3 The calibration samples were measured with one were made by diluting (by weight) the 9% VA with the minute collection times, at a resolution of 4 cm-1. The pure PE (0% VA) standards to make 1% and 0.55% VA FTIR spectra exhibit strong acetate ester carbonyl bands samples. The polymer validation samples were then at 1737 cm-1 and an ester C-O stretch band at 1236 cm-1 dissolved in toluene and heated to 75 °C until all the (Figure 5) arising from polyvinyl acetate (VA). Both of polymer dissolved. The toluene mixtures were then cast these bands are ideal for quantitative analysis of the VA as thin fi lms onto aluminum foil over a 60 °C hotplate in the polyethylene (PE) matrix. The characteristic PE and allowed to dry. The resulting polymer validation absorbance bands are located at 2921cm -1, 2852 cm-1, samples were then measured with the stored method. 1467 cm-1 and 720 cm-1. The best calibration is obtained These validation samples were measured with a much by a peak area ratio of the 1236 cm-1 VA absorbance shorter scan time (5 seconds) than the calibration band ratioed to the PE absorbance at 1467 cm-1. This set of spectra (60 seconds). This allows for multiple IR absorbance ratio technique corrects for random measurements of incoming raw materials in a very short variables that may affect the measurement, such as time; this fast sample analysis is important for quality contact pressure or contact area of the polymers on the assurance and quality control (QA/QC) analysis. The ATR diamond crystal. This is important since reliable speed of this analysis is also a benefi t for incoming raw ATR measurements require the sample to make good materials analysis in which a batch of PEVA can have optical contact with the diamond, and hard, round some uniformity differences, requiring sampling from polymer beads may not contact the whole diamond multiple areas of the container or on a molded part. The surface. results of this fast analysis (5 second) yield exceptional repeatability and accuracy (Table 1) on the validation Polyvinylacetate 1236 samples. A standard deviation of nominally 0.01% VA was obtained with limits of detection (LOD) and limits 0.6 1737 of quantitation (LOQ) of 0.03 wt% VA and 0.10 wt% VA, 0.5 Polyethylene respectively. When a sample is run using this calibrated FTIR method, the results can also be displayed in color- Absorbance000...342 29212852 1372 1020 ciTonofh- distshep edee ncqf aou(brgamlrleeiatseyt n ao()nFf, i mgtohupaerere rgm ai7nta)oat, reli nrt(ioydae ilgc.l leaottwi na) g,r aotphr iaodtu, tvth iosefu ssaapl meincpd l(ierc eaisdt o).r 0.1 1467 Table 1. VA prediction values from the calibrated VA FTIR method for validation standards at 0.55% VA and 1.00% vinyl acetate in polyethylene. These validation samples were run with only 5 second collection times 0.0 Validation sample 0.55% VA 1.00% VA 3500 3000 2500 2000 1500 1000 Wavenumber(cm-1) Rep 1 0.53 0.97 Figure 5. Spectral overlay of the calibration standards for polyethylene vinyl Rep 2 0.54 0.96 acetate). The spectra are all scaled to the polyethylene absorbance. The blue spectrum is 40 wt% VA, and the red spectrum is 0% VA Rep 3 0.55 0.96 Rep 4 0.56 0.96 The resulting linear regression calibration curve from Rep 5 0.55 0.99 the above peak area ratio is excellent (Figure 6) with a correlation coeffi cient of R2 = 0.999. The slope and Standard deviation 0.0114 0.0130 offset for the linear regression is easily inserted into Average 0.55 0.97 the MicroLab FTIR method editor (Figure 6), and the resultant method is now permanently calibrated. To test the robustness of the method, validation standards 4 40 Quant Validation Plot for Vinyl Acetate pct 22 R2=0.999 35 y = 5.310 (x) -0.084 30 %) 20 wt.25 19 Vinyl Acetate (2105 17 18 10 16 5 0 1145 0 1 2 3 4 5 6 7 Peak Area Ratio (1236 cm-1/1467 cm-1) Figure 6. The method editor in the MicroLab FTIR software and the calibration plot for VA in PE Figure 7. The result for the 1% VA validation standard — green color indicates an in-spec sample Conclusion The Agilent Cary 630 FTIR equipped with ATR sampling technology is an exceedingly effective spectrometer for analyzing copolymer blends. The combination of its compact size, sampling technology, performance, speed of analysis, and intuitive software enables quantitative methods for polymers to be rapidly developed and deployed in quality assurance and quality control 5 applications. The measurement of both SBR and PEVA copolymers yields highly linear calibrations with excellent quantitative accuracy and reproducibility. www.agilent.com/chem Agilent shall not be liable for errors contained herein or for incidental or consequential damages in connection with the furnishing, performance or use of this material. Information, descriptions, and speci cations in this publication are subject to change without notice. © Agilent Technologies, Inc. 2011 Published September 1, 2011 Publication number: 5990-8676EN