Understanding the Frontier Multi-Shot Pyrolyzer

Seminar with Lab Sessions October 19 e.g., Irganox 1076 and 1010, Eyeliner deformulation; Biomass; Phthalates in PVC ASTM D-7823;. Data review techniques F-Search hands-on workshopDave Randle, Bob Freeman, Itsuko Iwai, Roger Tank, Terry Ramus Frontier Lab Technology Center, Antioch, CA 4} Frontier Laboratories, Ltd. was founded in 1991 by Dr. Chu Watanabe. His experience working at Hewlett Packard’s Analytical Division and Dow Chemical made him uniquely qualified to design and market analytical instruments for materials characterization. Dr. Watanabe, with the support of polymer scientists at Nagoya University in Japan, developed a pyrolyzer based on a vertical micro-furnace design. Today the patented fourth generation vertical micro-furnace serves as the cornerstone for the 3000 Series of products developed and marketed worldwide by Frontier Laboratories. } The main products, supported by a number of accessories and software, include the EGA/PY-3030D Multi-functional Pyrolysis System, the PY-3030S Single-Shot Pyrolyzer, the 3050 series of Rapid Screening Reactors for catalyst screening, and a line of Ultra ALLOY stainless steel capillary columns. } For Agilent Technologies GC and GC/MS systems, Frontier Lab products are sold and serviced in North America by Quantum Analytics, an Agilent Technologies Premier Solution Partner. } There are thousands of Frontier Lab systems in use globally, with over 50 used on a daily basis by companies in North America such as Dow Chemical, BASF, 3M, Sherwin Williams, PPG, Covestro, The Getty Conservation Institute, Smithsonian, U. of MN, IA St. U., Dow AgroSciences, Shell, General Motors, Volkswagen, Michelin, Goodyear, ExxonMobil, Chevron, Phillips 66, Boston Scientific, St. Jude Medical, H. B. Fuller, NASA, NREL, St. of MN Crime Lab, and many others. 5Application Areas using Multi -functional Pyrolyzer Polymers characterization, quality assurance, deformulation Additives surfactants, plasticizers, residual monomers, solvents, volatile catalysts, impurities Plastics resins, plasticizers, mold release agents, UV -antioxidants, films, foams, gels Coatings pigments, solvents, driers, film formers Fibers blends, natural materials, non -woven Elastomers sulfur -compounds, natural rubbers, synthetics, silicones Adhesives thermoplastics, anaerobics , acrylics, epoxy Inks pigments, resins, solvents, defoamer, waxes, toners Paper coatings, sizing Product Areas textiles, personal care products, packaging Related Scientific forensic evidence, degradation studies, environmentalPolymers, additives, adhesives, elastomers Wide market use from petrochemical, automotive, biopharmaceutical to medical devices Coatings Ranges from inks, paints, and sealers in forensics, museums, and industrial uses Energy Biomass analysis for producing biofuels in universities and industry. Oil shale. Consumer products Packaging, cloth fibers, cosmetics, and food Applications by Market Applications by MarketAIChE Webinar archived now https//www.youtube.com/watchv0ZcZ2PUq2_Y Now on YouTube} 100-200 g 0.1-0.2 mg total in sample cup is sufficient for most analyses } Introducing too much sample is the 1 issue we find with customers having analysis problems It’s a small world 10} Best is thin film method ◦ Dissolve sample in solvent, add to cup, evaporate solvent } Fine particles are excellent ◦ Use Polymer Prepper or Freeze Pulverization } Finely chopped pieces are good 1 mm X10 Sharp cutting edge SEM Image of CuttingSurfaceof Polymer Preppermedium Flat bottom surface Polymer Preppermedium Freeze pulverization 5min 1mm Fig. 1 Particle Shapes of Polystyrene Powdered by Polymer Prepperand Freeze Pulverization Fine powder Small particles cutting method Sample form Thin film Polymer Prepper medium Freeze pulverization 4 pieces 0.4mm square 1piece 1mm square R.S.D. of SSS/S1.07 1.97 2.11 3.64 8.90 Pyrolysis temp 550 C Sample size ca. 0.5mg SSS Styrene trimer S Styrene monomer 11} Polymer Prepper ◦ 2 sided nickel file with fine 0.5, 0.75, 1.25, 2.0, 3.0, 4.0 and 5.0 mm diameter of micro- puncher and cutting mat 65 x 75 mm. Dried paint Leaves 1213Step 1 14 Sample preparation Sample preparation Filed; Cryo milled Micro syringe Knife Micro puncher Ready for Analysis Polymer Prepper GC MS Pyrolyzer Sample cup Step 3 Weigh a sample into the sample cup No solvent extraction Step 2 50-200g SampleApproach in characterizing unknown materials Unknown material Unknown material Thermograms Chromatograms Pyrograms Volatiles / non -volatiles Additives volatile Polymer non-volatile Analytical targets Analytical method Thermal desorption TD Thermal desorption TD Flash pyrolysis Py Flash pyrolysis Py Evolved gas analysis EGA Evolved gas analysis EGA Double -Shot GC/MS analysis Complexity of the material and thermal distribution of its components Components that could be released by heat. Solids that can only be broken down at high temperature 40-800 o C 40-420 o C 420-1050 o C Typical Temp Range Remarks Temp Prog. 20 o C/min Temp Prog. or isothermal Isothermal, typical 6 00 o CSample RxPy PY HC TD EGA EGA Evolved Gas Analysis TD Thermal Desorption HC Heart-Cutting PY Pyrolysis RxPy Reactive PyrolysisEGA TD HC PY RxPy EGA Evolved Gas Analysis TD Thermal Desorption HC Heart-Cutting PY Pyrolysis RxPy Reactive PyrolysisEGA TD HC 800 C 20 C/Min 100 C Isothermal or Temp. ProgrammedPY RxPy Typically 250-380 C Typically 500-800 C Sample Reagent i.e., TMAH Thermally assisted chemolysis and derivatization Thermolysis} EGA Evolved Gas Analysis is performed with a short inert tube not an analytical column and produces a thermogram. } Frontier has found the information in an EGA thermogram so valuable that we created an entire EGA-MS library with 268 polymers for our customers. } Once an EGA thermogram is generated for an unknown sample we then install an analytical column into the GC/MS. ◦ This change over time is very fast using our Vent-free adapter VFA. ◦ The information gained from the EGA guides the analyst on what “thermal” blades are needed to slice the sample into pieces to simplify the chromatograms and provide better information. } The next slides shows examples of how to use the EGA information to perform a thermal desorption TD of the volatile portion of the sample followed by a pyrolysis Py of the polymeric portion of the sample. We call this a Double-shot. 3030D. “D” is for Double -shot21 GC oven 300C isothermal Double-Shot Pyrolyzer 50 – 700C 20C/min EGA tube 2.5m, 0.15mm id. Deactivated SS only This is not an analytical column Flow diagram and analytical conditions for EGA Analysis Temperature controller Vent Free GC/MS Adapter VFAHe EGA tube GC Oven 320 C MS EGA -MS Thermogram EGA -MS Temperature C 100 200 300 400 500 600 TD chromatogram （TD -GC/MS 100˚C-300˚C 20˚C/min Time Pyrogram Py -GC/MS at 600˚C 10 20 30 40 min VFA -EGA-MS is the recommended first step to characterize a sample, and uses an uncoated metal tube 2.5m x 0.15mm i.d. to connect the GC inlet to the MS. -Subsequent analyses TD-GC/MS and Py-GC/MS are performed using an analytical column. 30m x 0.25mm x 0.25m . -Switching from the tube to the column takes only minutes using the Vent-free GC/MS Adapter VFA. 100ᵒ C – 700ᵒ C 20ᵒ C/min TD followed by PY on a single sample is called a Double-Shot. GC Oven Temperature Program He TD-GC/MS Py -GC/MS MS Separation column VFA MJT 22} Plastic bottle samples } File or cut small amount onto piece of paper } Tare sample cup } Weigh 100-200ug } Record weight, sample name and your name } Place in sample rack and note position Plain paper 23EGA Thermograms of Water bottle On-line micro reaction 30M x 0.25u x 0.25u Oven Temp 40 o C 2min -20 o C/min-320 o C 13min Pyrolysis GC/MS Data Book of Synthetic Polymers, 2011 Tsuge, Ohtani, WatanabePyrolysis GC/MS Data Book of Synthetic Polymers, 2011 Tsuge, Ohtani, WatanabePyrolysis GC/MS Data Book of Synthetic Polymers, 2011 Tsuge, Ohtani, WatanabeAvailable Now From Elsevier 30M x 0.25u x 0.25u Oven Temp 40 o C 2min -20 o C/min-320 o C 13minPyrolysis GC/MS Data Book of Synthetic Polymers, 2011 Tsuge, Ohtani, Watanabe39 Characterization of Polymers by Py -GC/MS A Identification of polymeric materials Unknown materials PP/ PVC/ SBR B Structural characterization of polymers C Mechanisms and kinetics of polymer degradation stereo regularity CC-C-C*-C-C*-C-C C C C C [ ] D Qualitative and quantitative analysis of additives Various monomers chain -end MW /Sequence distributions x -n-m-n Blend or copolymer XY or XY X [ CH 2 CHCHCH 2 ] – [CH 2 CHCN] -[ CH 2 CHC 6 H 5 ] ] x [ n m y X Random scission – Polyolefins polyethylene, polypropylene, polybutylene, etc. – C-C bonds break to produce fragment patterns of increasing oligomer sizes see prior PE example Depolymerization – Polymer thermally degrades into monomeric units – Polystyrene shows monomer S, dimer SS and trimer SSS see page 42 in Py- GC/MS Data Book* Side group elimination – Side groups i.e. Cl attached to the side of a polymer chain break before C bonds. – Cl removes H from polymer chain unsaturated polyenes HCl. These polyenes form aromatic compounds. – Polyvinyl chloride PVC is an example. PVC pyrolyzates contain single aromatic rings BTEX, double rings i.e naphthalene and even triple rings i.e. anthracene. Big peak of HCl. see page 110 in Py- GC/MS Data Book* Polymer degradation mechanisms *Pyrolysis GC/MS Data Book of Synthetic Polymers, 2011 Tsuge, Ohtani, Watanabe Most “big” pyrolyzates are not in NIST MS libraries S SS SSS 40