3D Printing Polymers Using Pyrolysis-GC/MS

Material Characterization of 3D Printing Polymers Using Pyrolysis-GC/MS

FRONTIER LAB Why Pyrolysis GC/MS?

Manufacturers are always seeking new technologies and developments that increase production efficiency and the quality of the produced parts. Many analytical protocols used to analyze 3D printing and coating components require multi-step sample preparation prior to chromatographic analysis. These procedures often include solvent extraction, filtration, and concentration. These traditional techniques are cumbersome, time-consuming, and suffer from analyst-to-analyst variability while producing data of limited value. Samples are analyzed “as is” when using the Frontier pyrolyzer. No sample preparation is needed. Eliminating the solvent extraction process enhances the precision of quantitative analysis while virtually prevent sample contamination and improves analytical efficiency. These are three of the primary reasons many manufacturing and polymer development laboratories utilize the Frontier Pyrolyzer.

The Frontier Multi-Shot Pyrolyzer can be configured in a number of different ways, so that a sample can be characterized using various analytical techniques, including evolved gas analysis, thermal desorption, flash pyrolysis, double-shot, Heart-Cutting of individual EGA thermal zones, and reactive pyrolysis. Initially, such diversity may be perceived as a complicated decision process: what analytical mode will give us the most insight into the nature of the sample in the least amount of time? To assist, Frontier scientists have created a “method map”. An overview of the “method map” is provided on page 45.

FRONTIER LAB Table of Contents

Polylactic acid (PLA) for 3D Printing 4 Epoxy Adhesives and Resins as Thermosets 8 Polysiloxane - PDMS and Adhesive Compositions 12 Polyphenylene Ether (PPE) Plastic Resins 16 Polyphenyelene Sulfide (PPS) Resins and Filaments 20 ULTEM or Polyetherimide (PEI) High Performance Polymer 23 Polyetheretherketone (PEEK) High Performance Polymers 26 Nylon 12 Powder Resins and SLS 3D Printing 29 Polycarbonate (PC) Plastic Resins 32 Nylon 6 and Polyphenylene sulfide (PPS) Blended Polymers 35 Thermoset Polymer Resin Coated Proppant 38 What is Pyrolysis GC/MS Technique? 42 Simplify and Improve Data Interpretation by F-search 44 “Method Map” Providing Direction 45 Pyrolysis-GC/MS System Configuration 47

FRONTIER LAB Polylactic acid (PLA) for 3D Printing

Background: There is a high interest in bio-derived Plastics. Polylactic acid or polylactide (PLA or PLLA) is a thermoplastic polyester derived from renewable biomass (monomer) from fermented plant starch such as corn, cassava, sugarcane or sugar beet pulp. They range from amorphous glassy polymer to semi-crystalline and highly crystalline polymer with a glass transition temperature (Tg) of 60 °C and melting points of 130-180 °C. It is one of the most produced bioplastics. The mechanical properties of PLA are between those of polystyrene and PET. The melting temperature, Tm, of PLA can be increased by 40– 50 °C and its heat deflection temperature can be increased from approximately 60 °C to up to 190 °C by physically blending the polymer with PDLA (poly-D-lactide). Polylactic acid can be processed like most thermoplastics into fiber (for example, using conventional melt spinning processes) and film. With high surface energy, PLA has easy printability which makes it widely used as a filament in 3-D printing.

Problem: Although PLA is commonly used as a 3D Printing polymer filament material, the composition in most filaments is unknown, including the presence of PDLA or any compatible additives or modifiers. While IR spectroscopy can be used for screening, it is not sufficient for composition determination or distinguishing between other types of polyester blends or PLA sources.

Solution: Using Pyrolysis-GC/MS techniques, perform Evolved Gas Analysis (described in page 46) followed by a single shot/flash pyrolysis to confirm the presence of the PLA or its monomer and the general absence of other additives.

FRONTIER LAB 4 [%] 110 Experimental: Evolved Gas Analysis 100 90 (EGA) was performed to identify the 80 thermal composition of a 3D printed PLA 70 sample. To perform EGA, around 100 µg 60 was cut from a 3D printed dogbone 50 40 shape specimen and placed into the inert 30 Flash Pyrolysis 500°C Eco-Cup. The micro-furnace was then 20 programmed from 100 to 700°C 10 0 100 300 500 700 (20°C/min). The GC oven was kept Temperature (oC) isothermal at 320°C. Compounds [%] 110 100 56 “evolved” continuously from the sample 90 as the temperature increases. The 80 EGA-MS result (9.949 to 14.987 min) 70 2943 obtained EGA-MS was summarized from 60 10 min to 15 min (300-400 oC), and the 50 40 reference was directly suggested by the 30 200 128 20 272 F-Search EGA-MS library. 100 344 10 72 416 145 217 488 0 173 243 289 441 471 532 560 604 632 m/z -->0 100 200 300 400 500 600 Results: The EGA thermogram indicated [%] 110 o 100 56 that the PLA starts to degrade at 300 C 90 and will be totally degraded at 400oC. 80 Reference of Poly(lactic acid) 70 (F-search library result) Library search is done by F-search 60 (interpretation library described in page 50 45 40 44) , which fits well with the EGA-MS of 30 29 sample, giving a result that the 3D printed 20 10 128 200 73 100 272 dogbone is consist of PLA. 0 173 217 344 416 m/z -->0 100 200 300 400 500 600

FRONTIER LAB 5 Flash pyrolysis was then performed at 500°C. By extracting the chromatogram of typical ion of compounds, they are obviously observed out of all peaks. For additives which has minor fraction in the material, they can be detected by scaling up the sample to 10 times and refocus the peak in Thermal Desorption (TD) or Heart-cut (HC).

[%] 100 [%] 100 Thermal Desorption(TD) 100-300˚C 80 80 Single shot at 500˚C 60 60 40 40

20 20

0 10 times more sample 0 min --> 0 5 10 15 20 25 min --> 0 5 10 15 20 25

[%] 100 [%] 100 Extracted ion chromatogram m/z: 646 Extracted ion chromatogram m/z: 646 80 80

60 60 40 40 20 20 0 0 5 10 15 20 25 min --> 0 min --> 0 5 10 15 20 25

110 110 [%] [%] 441 100 441 100 90 Mass Spectrum of Single Shot 90 Mass Spectrum of TD 80 peak @ 20.726 min 80 peak @ 20.747 min 70 70 60 60 50 50 40 40 57 57 30 30 20 20 147 207 147 646 10 646 10 41 191 281 308 41 91 191 237 308 73 91 133 237 329 355 385 29 69 105 131 281 329 355 385405 474 506 540 589 0 405 479 508 540 589 631 0 m/z -->0 100 200 300 400 500 600 700 m/z -->0 100 200 300 400 500 600 700 110 110 [%] [%] 441 100 441 100 90 Reference of Irgafos 168 90 Reference of Irgafos 168 80 80 70 57 70 57 60 60 50 50 40 40 30 30 20 147 20 147 41 646 41 646 10 10 29 91 308 29 91105 131 191 308 69 105 131 191 219237 329 385 69 219237 273 329 385 0 273 533 589 0 533 589 m/z -->0 100 200 300 400 500 600 700 m/z -->0 100 200 300 400 500 600 700

FRONTIER LAB 6 [%] For the Thermal Desorption 100 (TD) analysis, the heating 80 Thermal Desorption(TD) 100-300˚C

occurs below 300˚C, thus the 60

majority peaks are ascribed to 40

small molecules in their original 20 form without chemical 0 decomposition. min --> 0 5 10 15 20 25 [%] 100

Monomers, additives and 80 Extracted ion chromatogram m/z: 239

solvent residue are always 60

shown in this part. 40

20 Here, the Palmitic acid 0 monoglyceride is isolated by min --> 0 5 10 15 20 25 TD-GC/MS and its mass [%] 100 43 98 239 spectrum is highly consistent Mass Spectrum of TD 80 57 with the reference. 74 peak @ 15.852 min 60 84 134 69 40 257 29 112 20 129 299 61 154 168 182 227 270 196 213 283 343 371 396 m/z --> 0 100 200 300 400 [%] 100 98 239 Reference of Palmitic 43 80 57 acid monoglyceride 74 60 84 69 134 40 112 257 29 129 20 61 154 182 227 270 299 168 199 213 283 313 331 m/z --> 0 100 200 300 400

FRONTIER LAB 7 Epoxy Adhesives and Resins as Thermosets

Background: Epoxy resins are a class of reactive prepolymers and polymers which contain epoxide (oxirane) groups. Reaction is based on either catalytic homopolymerization, or with a wide range of co- reactants including polyfunctional amines, acids (and acid anhydrides), phenols, alcohols and thiols (usually called mercaptans)- Part A & B. These co-reactants are often referred to as hardeners or curatives (Part B), and the cross-linking reaction is commonly referred to as curing. This results in a thermosetting polymer, often with favorable mechanical properties and high thermal and chemical resistance. Epoxy has a wide range of applications, including metal coatings, use in electronics/electrical components/LEDs, high tension electrical insulators, paint brush manufacturing, fiber-reinforced plastic materials (composites) and structural adhesives.

Problem: Although Epoxy is a commonly used resin and adhesive material, their commercial compositions vary enormously, and the determination of the reactive equivalent is of then the only quantifiable reaction parameter. Moreover, their use as a 3D printing material is only currently being studied. To study the composition and additives of a 3D printed objective, normal method could be destructive and requires a larger sample and preparation methods.

Solution: Using Pyrolysis-GC/MS techniques, perform EGA to determine the thermal profile of the sample. Then using the Hear- Cut mode of operation, perform deformulation analysis to identify the additive and the pyrolysis mechanism with minimum damage to the 3D printed objective.

FRONTIER LAB 8 Experimental: Evolved Gas Analysis (EGA) was performed to obtain a clear picture of the thermal profile of the 3D printed object. To perform EGA, around 100 µg was cut from a 3D printed epoxy object and then placed in an inert Eco-Cup. The micro-furnace was then programmed from 100 to 800°C (20°C/min). The GC oven was kept isothermal at 320°C. After the EGA results, the Hear-Cut technique were performed to thermally slice the sample in three zones. Zone A: 100 oC-260 oC; zone B: 300 oC to 420 oC; and zone C: 420-550 °C. About 300 µg was cut from the 3D printed object and placed in the Eco- Cup. Gas evolved in each zone was refocused by cryo-trap. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320 oC by 20 oC/min and hold 320 oC for 10 minutes.

Results: The EGA is directly performed on a cut of cured Epoxy 3D printed objective, without any preparation step. EGA chromatogram exhibit the clear three zone of epoxy. By utilizing Hear-Cut technique, these three zone can be focused separately. This technique provide detailed information on the composition of epoxy, additives and the pyrolyzing mechanism of epoxy.

[%] 110 100 Zone Zone Zone 90 A B C 80 70 60 50 40 30 20 10 0 100 300 500 700

FRONTIER LAB 9 [%] 110 100 90 Zone A 80 Zone A implied the presence of 70 dibutyl phthalate as a plasticizer. 60 50 40 30 A major peak of bisphenol A and 20 minor peak of phenol is detected in 10 0 zone B, which suggest the breaking min --> 0 5 10 15 20 25 [%] 110 of C-O is dominated in this 100 temperature zone and also supported 90 Zone B that the epoxy resin is bisphenol A 80 epoxy. 70 60 50 In zone C, C-C breaking is more 40 30 likely to happen. Phenol, p-cresol and 20 p-isopropylphenol were detected as 10 0 major peak while bisphenol A is minor min --> 0 5 10 15 20 25 peak. Alkyl segment is detected, [%] 110 which may come from the hardener. 100 90 Zone C 80 The result suggests that the Py- 70 GC/MS is a strong technique to study 60 the additive and its influence on 50 pyrolysis mechanism of thermosets 40 like epoxy. 30 20 10 0 min --> 0 5 10 15 20 25

FRONTIER LAB 10 [%]100 TIC Zone C TIC: Epoxy zone C_2.D F.S.:259496

0 min -->0 5 10 15 20 25

C5 [%] 100 m/z: 55 F.S.:6971 C6 EIC m/z:55 C7 C8 C10 50 C9 C11 Zone C C12 C13 C14 C16 C15 C17 0 min -->0 5 10 15 20 25

[%] 100 C6 m/z: 57 F.S.:9197 C9 EIC m/z:57 C7 C10 Zone C 50 C8 C11 C5 C12 C13 C15 C14 C16 C17 0 min -->0 5 10 15 20 25 In Zone C, the carbon chain fragments are separated by the number of carbon and the shortest chain comes out first. From C5 to C17, all chains can be picked out by ion chromatogram extraction and distinguished by their mass spectrum.

FRONTIER LAB 11 Polysiloxane - PDMS Adhesive and Resin Compositions: Thermoset Elastomers

Background: Polydimethylsiloxane (PDMS), also known as dimethylpolysiloxane or dimethicone, belongs to a group of polymeric organosilicon compounds that are commonly referred to as silicones. PDMS is the most widely used silicon-based organic polymer and is particularly known for its unusual rheological (or flow) properties. PDMS is optically clear, and, in general, inert, non-toxic, and non-flammable. It is one of several types of silicone oil (polymerized siloxane). Its applications range from contact lenses and medical devices to elastomers; it is also present in shampoos (as dimethicone makes hair shiny and slippery), food (antifoaming agent), caulking, lubricants and heat-resistant tiles. As an adhesive, it is one of the most common formulated materials. When cured as a rubber or adhesive, it is classified as a thermoset elastomer. There is a high interest on using silicones and formulated adhesives for 3D Printing.

Problem: Although silicones is a commonly used resin and adhesive material, their properties and formulation chemistry vary with different formulators and manufacturers. While IR spectroscopy and be used for screening, it is not sufficient for composition determination or distinguishing the presence of PDMS resins or sources. The materials used was a commercially available resin that is used for DIY adhesives and was subsequently used for 3D Printing.

Solution: Perform EGA followed by a single shot analysis to confirm the presence of the PDMS or its other polymer contents and the general presence of other additives.

FRONTIER LAB 12 Experimental: Evolved Gas Analysis (EGA) was performed first from 100 to 700°C (20°C/min). The GC oven was kept isothermal at 320°C. A single shot GC/MS analysis was then performed. As shown in the figure, using the F-Search EGA-MS library, the intense peaks in all the EGA thermograms were identified as PDMS compositions.

110 [%] Results: The EGA chromatogram 100 207 90 EGA-MS result demonstrated the 3D printed porous 80 o PDMS starts to degrade at 460 C and 70 will be totally degraded at 660oC. The 60 50 281

EGA-MS was created by summarize the 40 73 o o 221 spectra from 460 C to 660 C. Library 30 147 341 20 search is done by F-search, which fits 295 429 133 369 10 327 415 96 503 29 4559 119 461 535 563 637 well with the EGA-MS of sample. 0 m/z --> 0 100 200 300 400 500 600 700 800

110 [%] 100 207 90 Reference of Silicone rubber [%]110 80 (F-search library result) 100 70 90 60 80 70 50 73

60 40 281 50 30 40 30 20 96 133 20 10 355 324559 119 221 429 10 459 503 545 605 677 0 737 795 0 100 200 300 400 500 600 700 800 0 100 300 500 700 m/z --> Temperature (oC)

FRONTIER LAB 13 Single shot result was analyzed by using F-search compound library. A major peak of D3 is detected, demonstrating the small slicing of PDMS chain. Other minor peak stands for the higher order of D4, D5, D6, D7 and D8, standing for the larger fragment of PDMS chains. This results prove the presence of PDMS in the 3D printed porous object.

[%] 110 100 90 80 70 60 50 40 30 20 10 min --> 0 0 5 10 15 20 25

FRONTIER LAB 14 Thermal desorption of tem times more samples dramatically exaggerate the presence of additives. After locating the ion size at m/z 149 and search in the compound library, this additive is proved to be dibutyl phthalate (DBP).

110 [%] 149 [%] 100 100 90

80 Mass Spectrum of PDMS @ 13.496 min 80 Thermal Desorption with 70

10 times more sample 60 60 50

40 40 30

20 20 223 10 205 41 76 104 29 65 93 121 193 278 0 0 250 327341355 378 396 415428 451 475488 508 540 min --> 0 5 10 15 20 25 m/z -->0 100 200 300 400 500 110 [%] [%] 100 100 149

90 80 m/z: 149 80 Reference of Dibutyl phthalate (DBP) 70 60 60

50 40 40

30 20 20

10 223 0 41 56 76 104 205 0 5 10 15 20 25 93 121 278 min --> 0 m/z -->0 100 200 300 400 500

FRONTIER LAB 15 Polyphenylene Ether (PPE) Resins and Filaments

Background: Poly(p-phenylene oxide)(PPO) or poly(p-phenylene ether) (PPE) is a high-temperature thermoplastic. It is rarely used in its pure form due to difficulties in processing. It is mainly used as a blend with polystyrene, high impact styrene-butadiene copolymer or polyamide. PPO is a registered trademark of a commercial Innovative Plastics and is commercially known as Noryl. There is a high interest in using PPO or PPE for 3D Printing. PPE blends are used for structural parts, electronics, household and automotive items that depend on high heat resistance, dimensional stability, and accuracy. They are also used in medicine for sterilizable instruments made of plastic. This plastic is processed by injection molding or extrusion; depending on the type, the processing temperature is 260-300 °C. The surface can be printed, hot-stamped, painted or metalized. Welds are possible by means of heating element, friction or ultrasonic welding. It can be glued with halogenated solvents or various adhesives.

Problem: Although PPE is a commonly used high performance polymer resin and 3D printing material, their properties and formulation chemistry vary with different formulators and manufacturers. While IR spectroscopy and be used for screening, it is not sufficient for composition determination or distinguishing the presence of PPO resins or sources. The materials used was a commercially available resin that is used for 3D Printing.

Solution: Perform EGA followed by a single shot analysis to confirm the presence of the PPE or its other polymer contents and the general presence of other additives of a commercial filament.

FRONTIER LAB 16 Experimental: Around 100μg of an extruded filament from commercial pellet was cut into an inert Eco- Cup and placed in the auto sampler. To perform EGA, the micro-furnace was then programmed from 100 to 800°C (20°C/min). The GC oven was kept isothermal at 320°C. A single shot analysis was done at 600 oC, determined from EGA thermogram. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320oC by 20 oC/min and hold 320 oC for 10 minutes. The result was analyzed by F-search library of component.

Results: The EGA chromatogram demonstrated the PPE filament starts to degrade at 440oC and will be totally degraded at 600oC. [%]110 100 121 The EGA-MS was created by summarize 90 EGA-MS of PPE filament o o the spectra from 440 C to 600 C. Library 80 107 70 search is done by F-search, which fits well 60 135 with the EGA-MS of sample. 50 7791 242 40 30 228 256 362 376 20 39 5165 165 211 10 348 [%]110 430 496 0 288 540 602 100 m/z --> 0 100 200 300 400 500 600 90 [%] 110 80 100 121 70 Library search of PPE 60 90 50 80 40 70 107 60 30 135 242 20 50 40 91 10 77 362 0 30 228 100 300 500 700 20 376 211 348 482 Temperature (oC) 10 39 5165 165 0 588 m/z --> 0 100 200 300 400 500 600

FRONTIER LAB 17 By utilizing pyrolysis at 600oC, the fragments of PPE filament can be studied. o-Cresol, dimethylphenol and trimethylphenol were detected which suggested the presence of monomer. Dimers were also detected from 10 min to 15 min, while trimers were observed at 17 min. These results proved the presence of PPE polymer.

[%]110 100 90 80 70 60 50 40 30 20 10 0 min --> 0 5 10 15 20 25

Polyphenylene ether(PPE)

FRONTIER LAB 18 Thermal Desorption (TD) mode of operation was also [%] 100 TIC used to confirm the presence of two additives. TD was performed from 100-380°C. The Total Ion Chromatogram 50 (TIC) is shown on the right-hand side. The Extracted Ion Chromatograms (EICs) of m/z:84 and m/z:149 indicates 0 N-Butylidenebutylamine and Dibutyle Phthalate (DBP), min --> 0 5 10 15 20 25 respectively.

EIC EIC [%] 100 m/z: 84 [%] 100 m/z: 149

50 50

0 0 min --> 0 5 10 15 20 25 min --> 0 5 10 15 20 25

[%]110 [%]110 84 149 100 100 90 Mass Spectrum of PPE @6.308 min 90 Mass Spectrum of PPE @13.405 min 80 80 70 70 60 57 60 50 50 40 41 40 30 70 30 20 20 99 41 112 10 76 104 205 223 10 30 57 93 121 160 184 255 281295 315 341355 377 401 432445 470 488 508 535 0 126 147 167 207 255 267 327 341 429 0 m/z --> 0 100 200 300 400 m/z --> 0 100 200 300 400 500 110 [%]110 [%] 84 149 100 100 90 Reference of N-Butylidenebutylamine 90 Reference of Dibutyl phthalate (DBP) 80 80 70 70 60 60 50 57 50 40 40 42 30 70 30 29 20 20 99 10 112 10 41 65 76 93104 121 205 223 126 209 0 278 m/z -->00 100 200 300 400 m/z --> 0 100 200 300 400 500

FRONTIER LAB 19 Polyphenyelene Sulfide (PPS) Resins and Filament

Background: Polyphenylene sulfide (PPS) is a high-performance polymer consisting of aromatic rings linked by sulfides. Synthetic fiber and textiles derived from this polymer resist chemical and thermal attack. PPS is used in filter fabric for coal boilers, papermaking felts, electrical insulation, film capacitors, specialty membranes, gaskets, and packings. PPS is the precursor to a conductive polymer of the semi-flexible rod polymer family. The PPS, which is otherwise insulating, can be converted to the semiconducting form by oxidation or use of dopants. PPS as a high-performance polymer can be molded, extruded, or machined to tight tolerances. In its pure solid form, it may be opaque white to light tan in color. Maximum service temperature is 218 °C (424 °F). PPS has not been found to dissolve in any solvent at temperatures below approximately 200 °C (392 °F). There is high interest in using these materials for additive manufacturing.

Problem: Although PPS is a commonly used high performance polymer resin and 3D printing material, their formulation chemistry vary with different formulators and manufacturers. While IR spectroscopy and be used for screening, it is not sufficient for composition determination. Solid state NMR can provide detailed information of composition, while it’s sophisticated to operate and interpret.

Solution: Pyrolysis-GC/MS provides a simple and rapid determination of composition analysis of an extruded PPS filament. EGA followed by a single shot analysis are performed to confirm the presence of the PPS.

FRONTIER LAB 20 Experimental: 100 µg sample was cut from an extruded PPS filament and placed into the inert Eco-Cup sample. The micro-furnace was then programmed from 100 to 800°C (20°C/min) to perform EGA. The GC oven was kept isothermal at 320°C. Flash pyrolysis technique was done by using single shot mode at a 700oC. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320oC by 20 oC/min and hold 320 oC for 10 minutes.

Results: The EGA thermogram indicates that PPS started to degrade at 480oC and completely at 700oC. Therefore, flash pyrolysis was performed at 700oC.

[%] 110 100 90 80 70 60 50 40 30 20 10

0 100 300 500 700 800 Temperature (oC)

FRONTIER LAB 21 In the single shot mode, PPS was flash pyrolyzed at 700 oC, all the obtained peaks were assigned by using F-search libraries. Monomer PPS (Benzenethiol), PPS dimer(3-phenylthiolbenzenethiol) were detected as major peak.

Dithiolbenzene, diphenylsulfide, phenylbenzenethiol, dibenzothiolphene, 3-thiol dibenzothiolphene, 1,3- bisphenylthiobenzene, 2-(phenylthio)dibenzothiophene and 3-((3 (phenylthio)phenyl)thio)benzenethiol were detected as the minor peak. These result demonstrated the complete presence of PPS.

FRONTIER LAB 22 ULTEM or Polyetherimide (PEI) Resins and Filament

Background: Polyetherimide (PEI) is an amorphous, amber-to-transparent thermoplastic with characteristics similar to the related plastic PEEK. Ultem is a family of PEI products manufactured by a commercial supplier. Ultem resins are used in medical and chemical instrumentation due to their heat resistance, solvent resistance and flame resistance. Ultem 1000 (standard, unfilled polyetherimide) has a high dielectric strength, inherent flame resistance, and extremely low smoke generation. Ultem has high mechanical properties and performs in continuous use to 340 °F (170 °C) and is easily machined and fabricated with excellent strength and rigidity. The glass transition temperature of PEI is 217 °C. It is able to resist high temperatures with stable electrical properties over a wide range of frequencies. This high strength material offers excellent chemical resistance and ductile properties suitable for various applications, even for 3D Printed objects and parts.

Problem: Although PEI is a commonly used high performance polymer resin and 3D printing material, their properties and formulation chemistry vary with different formulators and manufacturers. While IR spectroscopy and be used for screening, it is not sufficient for composition determination or distinguishing the presence of PEI resins or sources. The materials used was a commercially available resin that is used for 3D Printing.

Solution: Perform EGA followed by a single shot analysis to confirm the presence of the PEI or its other polymer contents and the general presence of other additives.

FRONTIER LAB 23 Experimental: About 100 µg of sample was cut from an extruded filament, placed in the inert Eco-Cup and into the auto sampler. To perform EGA, the micro-furnace was then programmed from 100 to 800°C (20°C/min). The GC oven was kept isothermal at 320°C. Flash pyrolysis technique was done by using single shot mode at a 700oC (this optimal temperature was obtained from the EGA thermogram). The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320oC by 20 oC/min and hold 320 oC for 10 minutes.

110 [%] Results: EGA provided a clear picture of the 100 94 90 thermal profile of the Ultem filament sample. 80 According to the result, Ultem started to 70 EGA-MS of Ultem filament o o 60 44 degrade at 500 C and completed at 660 C. 50 65 107 210 Therefore, flash pyrolysis will be performed at 40 77 238 30 51 700oC. 119 195 20 165 10 252 267 289 329 430 0 379395 478 512 540 616 647 m/z -->0 100 200 300 400 500 600

[%]110 94 [%]110 100 100 90 44 90 80 80 Library search of PEI 70 70 60 60 50 50 66 40 40 30 30 107 77 51 20 20 210 10 197 10 119 0 165 100 300 500 700 0 0 100 200 300 400 500 600 Temperature (oC) m/z -->

FRONTIER LAB 24 [%] 110 100 90 80 70 60 50 40 30 20 10 min --> 0 0 5 10 15 20 25

Single shot GC/MS result was analyzed by using F-search library. A major peak of mixture of aniline and phenol is detected. Minor peaks stands for bisphenylether derivatives were detected, demonstrating the R group of the structure showing below is ether.

FRONTIER LAB 25 Polyetheretherketone (PEEK) High Performance Plastics

Background: Polyether ether ketone (PEEK) is a colorless organic thermoplastic polymer in the polyaryletherketone (PAEK) family, used in engineering applications. PEEK polymers are obtained by step- growth polymerization by the dialkylation of bisphenolate salts. Typical is the reaction of 4,4'- difluorobenzophenone with the disodium salt of hydroquinone, which is generated in situ by deprotonation with sodium carbonate. The reaction is conducted around 300 °C in polar aprotic solvents - such as diphenyl sulfone. PEEK is a semi crystalline thermoplastic with excellent mechanical and chemical resistance properties that are retained to high temperatures. The processing conditions used to mold PEEK can influence the crystallinity and hence the mechanical properties. This high strength material offers excellent chemical resistance and ductile properties suitable for various applications, even for 3D Printed objects and parts.

Problem: Although PEEK is a high-performance polymer resin and is a very challenging 3D printing material, their properties and formulation chemistry vary with different formulators and manufacturers. While IR spectroscopy can be used for screening, it is not sufficient for composition determination or distinguishing the presence of PEEK resins or sources. The materials used was a commercially available resin that is used for 3D Printing.

Solution: Perform EGA followed by a single shot analysis to confirm the presence of the PEEK or its other polymer contents and the general presence of other additives.

FRONTIER LAB 26 Experimental: Two commercial filament samples for 3D printing were investigated. EGA was performed first to obtain a clear picture of the thermal profile of the unknown sample. About 100 µg of sample was cut from a 3D printed object. The micro-furnace was then programmed from 100 to 800°C (20°C/min). The GC oven was kept isothermal at 320°C. Flash pyrolysis technique was done by using single shot mode at a 700oC. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320oC by 20 oC/min and hold 320 oC for 10 minutes.

Results: EGA of 3D printed PEEK object was performed. According to the result, PEEK-Intamsys demonstrates a slightly higher degradation temperature than PEEK-Indmatec, which probably indicate the difference in molecular weight.

PEEK-Intamsys

PEEK-Indmatec

100 300 500 700 Temperature (oC)

FRONTIER LAB 27 [%]110 Both 3D printed samples 100 PEEK-intamsys demonstrated a major peak 90 of phenol and minor peak 80 of dimer phenyl ether and 70 benzophenone, which 60 proved the presence of 50 40 PEEK. 30 The results demonstrated 20 that there is no big 10 difference in composition of 0 min -->0 2 4 6 8 10 12 14 16 18 20 22 24 the two PEEK commercial [%]110 samples, the difference in 100 PEEK-Indmatec degradation temperature 90 may be related to the 80 molecular weight. 70 60 50 40 30 20 10 0 min -->0 5 10 15 20 25

FRONTIER LAB 28 Nylon 12 Powder Resins and for SLS 3D Printing

Background: Nylon 12 is a polymer with the formula [(CH2)11C(O)NH]n. It is made from ω-aminolauric acid or laurolactam monomers that each have 12 carbons, hence the name ‘Nylon 12’. It is one of several nylon polymers including the common Nylon 6 and Nylon 66. Nylon 12 can be produced through two routes. The first being polycondensation of ω-aminolauric acid, a bifunctional monomer with one amine and one carboxylic acid group. The second route is ring-opening polymerization of laurolactam at 260-300˚C. Ring-opening polymerization is the preferred route for commercial production. Nylon 12 exhibits properties between short chain aliphatic nylons. At 178-180 °C, the melting point of nylon 12 is the lowest among the important polyamides. Its mechanical properties, such as hardness, tensile strength, and resistance to abrasion, low water absorption and density, 1.01 g/mL, result from its relatively long hydrocarbon chain length, which also confers its dimensional stability. This highly desirable engineering polymer material offers excellent chemical resistance and ductile properties suitable for various applications, even for 3D printed objects and parts from powders via selective laser sintering (SLS) and filaments.

Problem: Although Nylon 12 is a highly desirable resin their properties and formulation chemistry vary with different formulators and manufacturers. While IR spectroscopy and be used for screening, it is not sufficient for composition determination or distinguishing the presence of Nylon 12 resins or sources. The materials used was a commercially available resin that is used for 3D Printing.

Solution: Perform EGA followed by a single shot analysis to confirm the presence of the Nylon 12 or its other polymer contents and the general presence of other additives.

FRONTIER LAB 29 Experimental: About 100 µg of sample was cut from a 3D printed object to perform EGA. The micro-furnace was programmed from100 to 800°C (20°C/min). The GC oven was kept isothermal at 320°C. Flash pyrolysis technique was done using single shot mode at a 700oC. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320oC by 20 oC/min and hold 320 oC for 10 minutes.

[%]110 55 Results: The EGA thermogram 100 41 demonstrated Nylon 12 materials 90 30 EGA-MS result o 80 (14.022 to 20.025 min) start to degrade at 300 C and will 70 o be totally degraded at 540 C. 60 50 97 Library search is done by F-search, 69 which fits well with the EGA-MS of 40 83 30 198 sample, giving a result that the 3D 20 122 136 156 251 printed object is Nylon 12 10 170 210 238 394 266 294 322 351 376 540 0 430 474 506 m/z --> 0 100 200 300 400 500

[%]110 100 55 Reference of nylon-12 90 (F-search Library Reference) [%] 110 80 3041 100 97 70 90 80 60 69 83 70 50 60 40 50 198 40 30 156 30 20 136 251 20 170 10 210 238 394 10 266 294 322 351 376 431446 476 0 0 100 300 500 700 m/z --> 0 100 200 300 400 500 Temperature (oC)

FRONTIER LAB 30 [%] 110

100

10 min --> 0 0 2 4 6 8 10 12 14 16 18 20 22 24

Single shot GC/MS result was analyzed by F-search compound library. A major peak of 11-dodecenenitrille is detected, demonstrating the length of alkyl chain. Another major peak stands for the mixture of two form of linear dimer of Nylon 12. A minor peak of cyclic Nylon 12 dimer was detected, which also supported the presence of Nylon 12.

FRONTIER LAB 31 Polycarbonate (PC) Plastic Resins

Background: Polycarbonates (PC) are a group of thermoplastic polymers containing carbonate groups in their chemical structures. Polycarbonates used in engineering are strong, tough materials, and some grades are optically transparent. They are easily worked, molded, and thermoformed. Because of these properties, polycarbonates find many applications. Unlike most thermoplastics, polycarbonate can undergo large plastic deformations without cracking or breaking. As a result, it can be processed and formed at room temperature using sheet metal techniques, such as bending on a brake. Even for sharp angle bends with a tight radius, heating may not be necessary. This makes it valuable in prototyping applications where transparent or electrically non-conductive parts are needed, which cannot be made from sheet metal. This highly desirable engineering polymer material offers excellent chemical resistance and ductile properties suitable for various applications, even for 3D Printed objects and parts from filaments.

Problem: Although PC is a highly desirable resin, their properties and formulation chemistry vary with different formulators and manufacturers. While IR spectroscopy and be used for screening, it is not sufficient for composition determination or distinguishing the presence of PC resins or sources. The materials used was a commercially available resin that is used for 3D Printing.

Solution: Perform EGA followed by a single shot analysis to confirm the presence of the PC or its other polymer contents and the general presence of other additives.

FRONTIER LAB 32 Experimental: About 100 µg of commercial PC filament was cut from a commercial PC filament to perform EGA from 100 to 800°C (20°C/min). The GC oven was kept isothermal at 320°C. Flash pyrolysis technique was done using single shot mode at a 620oC. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320oC by 20 oC/min and hold 320 oC for 10 minutes.

[%] 110 Results: The EGA thermogram 100 213 demonstrated that the PC filament start to 90 Unknown Mass Spectrum of EGA-MS result o 80 degrade at 320 C and will be totally 70 degraded at 600oC. Library search is done 60 (11.986 to 23.026 min) 50 by F-search, which fits well with the EGA- 40 30 MS of sample, giving a result of good fitting 119 20 228 with PC reference. 39 65 7791 10 55 107 239 29 134 165 197 506 543567 0 282 301 332 369390 418 445 m/z --> 0 100 200 300 400 500 600 [%]110 100 213 [%]110 90 100 80 Reference of Polycarbonate(solution 90 70 method) ; SM-PC 80 70 60 60 50 (F-search Library reference) 50 40 40 30 30 119 228 20 91 20 107 10 10 39 65 77 165 197 181 329 0 0 303 389 407 min -->100 300 500 700 m/z --> 0 100 200 300 400 500 600 Temperature (oC)

FRONTIER LAB 33 The single shot GC/MS was analyzed by F-search compound library. A major peak of bisphenol A is detected, demonstrating the breaking of ester bonds. Phenol, cresol and isopropylphenol were detected which demonstrate the C-C breaking at higher temperature. This result proves the presence of PC.

[%]110 100 90

80 70 60 50 40 30 20 10 0 min -->0 5 10 15 20 25

FRONTIER LAB 34 Nylon 6 and Polyphenylene Sulfide (PPS) Polymer Blend

Problem: Blending polymers can be sophisticated due to their difference in miscibility, structure and thermal property especially for high performance engineering plastics. Due to the high melting point of PPS, blending PPS with other low degradation temperature polymers can be challenging. To characterize the blended polymer, an accurate and reliable method is necessary. While IR spectroscopy be used for screening, it is not sufficient for composition determination or distinguishing the blended polymer. Microscope technology (AFM, SEM) can be used for characterization of uniformity, while sophisticated sample preparation and high-level operation skill is required.

Solution: Py-GC/MS provides the easiest way to characterize polymer blend of a targeted point on the sample, providing detailed composition information about the two polymers. Quantitative study is also available after calibration.

FRONTIER LAB 35 Experimental: EGA was performed to obtain a clear picture of the thermal profile of the 3D printed object. To perform EGA, around 100 µg of an extruded Nylon6-PPS blend filament was cut from a 3D printed epoxy object and then placed in an Eco-Cup. The micro-furnace was then programmed from 100 to 800°C (20°C/min). The GC oven was kept isothermal at 320°C. According to the EGA, the Hear-Cut technique were performed to slice the sample in two zones. Zone A: 360 oC- 500 oC; zone B: 500 oC-700 oC. Around 300 µg of an extruded Nylon6-PPS blend filament was cut from the 3D printed object and placed in the Eco-Cup. Gas evolved in each zone was refocused by cryo-trap and injected separately. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320 oC by 20 oC/min and hold 320 oC for 10 minutes. Results: According to the EGA result, two clear signal were detected. The first signal is dominated at the region of 360oC to 500oC, which may represent the degradation of Nylon 6. The second is located in between 500oC and 700oC, which may stand for the degradation of PPS. By utilizing the Heart-Cut technique, the two region can be separated and study independently.

[%]110 Zone A Zone B 100 90 80 70 60 50 40 30 20 10 0 100 300 500 700 Temperature (oC)

FRONTIER LAB 36 By separating zone A and [%] 110 zone B, the degradation of the 100 Zone A 360 oC-500 oC two polymer can be studied 90 separately. In zone A, a major 80 peak of lactam is detected, 70 which demonstrated this zone 60 is mainly degradation of Nylon 50 6. Minor peak of N-(5- 40 cyanopentyl)pent-4-enamide 30 also supported that the region 20 is dominated with Nylon 6. 10 0 min --> 0 5 10 15 20 25 In zone B, no lactam was detected, which suggested the [%] 110 Zone B 100 Nylon 6 was completely 500 oC-700 oC degraded before 500oC. 90 Benzenethiol, dimer PPS, 80 trimer PPS and their isomers 70 were detected as major peaks, 60 which imply this zone is 50 degradation of PPS. 40 These results demonstrated 30 that Py-GC/MS is a powerful 20 technique in studying polymer 10 blend degradation. min --> 00 2 4 6 8 10 12 14 16 18 20 22 24

37 FRONTIERFRONTIERLABLAB 37 Thermoset Polymer Resin Coated Proppant

Background: Proppant is solid particle material which is widely used in hydraulic fracturing to maintain a permeable channel to the well bore – a productivity tool. Typical proppant includes sands, treated sand and ceramics. Polymer resin coating technology increases the property of sand proppants in different kinds, such as productivity, long term stability, crush resistance and reduce flowback issue. These polymers can be made from phenol-formaldehyde, epoxy, polyurethane, etc. as thermosets. On the other hand, there is also high interest in using thermoplastic coatings for proppants.

Problem: Resin coating is a strong technique to improve the productivity and strength of proppant. However, techniques to characterize resin coated on proppant is limited by the nature of crosslinking. While IR spectroscopy or solid-state NMR be used for screening, it is not sufficient for composition determination or distinguishing the presence of additives

Solution: Utilize Pyrolysis-GC/MS to identify the resin and its additive of a commercial resin coated proppant. Compared to other technique such as TGA-IR and Solid-State NMR, Pyrolysis-GC/MS posses the advantages of no sample preparation required, easy to interpret and giving detailed information of additives.

FRONTIER LAB 38 Experimental:

1) Evolved Gas Analysis (EGA) was performed first to obtain a clear picture of the thermal profile of the unknown resin coated sand. About 10 pieces of resin coated sand is placed in the sample cup and placed in the auto sampler. The micro-furnace was then programmed from 100 to 800°C (20°C/min). The GC oven was kept isothermal at 320°C. Compounds “evolved” from the sample as the temperature increases.

2) About 10 pieces of resin coated sand is added to the sample holder. A double shot technique (TD/PY-GC-MS) was programmed as follows:

• For the thermal desorption, the temperature was set at 100 oC and increased to 300 oC by 20 oC/min. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320oC by 20 oC/min and hold 320 oC for 10 minutes. • For the flash pyrolysis step, the temperature was set at 700 oC. The oven temperature is programed to equilibrium at 40 oC for 2 min, increase to 320oC by 20 oC/min and hold 320 oC for 10 minutes.

FRONTIER LAB 39 Result: EGA technique show a rapid determination of the coating material. EGA mass spectrum was generated by summary the spectra from 0 min to 30 min. The obtained spectrum was identified to be phenol formadehyde by F-search libraries.

EGA- spectrum of Resin Coated Sand

Library spectrum of PF resin

FRONTIER LAB 40 [%]110 Thermal Desorption (TD) To study detailed information 100 about the resin coated sand, 90 Double shot technique was 80 utilized. In the first step (TD) 70 methylenediphenol and phenol 60 were detected, which suggested 50 the structure of phenol 40 formadehyde. 30 20 Besides, isocynato-octane, 10 0 palmitic acid were detected, min --> 0 5 10 15 20 25

which suggest that the use of [%] 110 emulsifier in PF resin 100 Pyrolysis (PY) preparation. 90 80 70 From the pyrogram, cresol and 60 xylenol were detected, which 50 supported the conclusion that 40 the coating is PF resin. 30 20 10 0 min --> 0 5 10 15 20 25

FRONTIER LAB 41 What is Py-GC/MSTechnique?

Pyrolysis GCMS is a powerful and straightforward technique that The Frontier Pyrolyzer is interfaced directly to the GC inlet. The utilizes a Frontier Pyrolyzer as a programmable temperature inlet sample is placed in a small deactivated inert cup which is, in to a Gas Chromatography-Mass Spectrometer (GCMS) system. turn, positioned in a micro-furnace. The temperature of the The material of interest (liquid or solid) is uniformly heated in an sample is carefully controlled (±0.1 °C) to ensure that the inert atmosphere. Volatile organics evolve at temperatures below sample-to-sample thermal profile is identical. Frontier’s well- 300 °C. At higher temperatures, covalent bonds break and the engineered technology ensures that the sample is maintained at complex structure is degraded into smaller (stable and volatile) ambient temperature, in an inert atmosphere, prior to pyrolysis; molecules which are referred to as pyrolyzates. The pyrolyzates thus eliminating evaporation, thermal degradation, and formed and their relative intensities provide insight into the thermosetting before analysis. structure of the original material.

The technical data in this monograph were obtained using one or more of the listed accessories. Each accessory is described in more detail in the system configuration section.

FRONTIER LAB 42 Easy Sample Preparation

This technology allows multiple analysis on a single sample. There is no need for solvent and sample preparation as the sample is simply introduced into the GCMS by the Frontier Pyrolyzer.

Step 1 Step 2 Step 3

Knife Weigh the sample into the sample cup Pyrolyzer

Polymer Prepper Sample cup

Filed; Cryo milled No Solvent Extraction Micro Syringe MS GC

Ready for Micro Puncher Analysis !!

Sample

FRONTIER LAB 43 F-Search Engine

SIMPLIFYING AND IMPROVING THE ACCURACY OF DATA INTERPRETATION

Polymeric materials often contain a variety of additives such as antioxidants, UV absorbers, etc. to assist during the production phase and determine the physical and chemical characteristics of the final product.

These compounds are identified using commercial mass spectral (MS) libraries; however, these general- purpose MS libraries contain very few entries for pyrolyzates and additives which severely limits their utility for polymer characterization.

Frontier Laboratories developed a search engine and Polymer Pyrolyzate-MS Library libraries called F-Search. The ions associated with hundreds of polymers, their degradation products (i.e., pyrolyzates) and hundred of additives are used to identify and thus characterize the sample as it is heated in the Py.

The libraries include both chromatographic and mass spectral data. There are four unique libraries which allow users to select among them for specific purposes. The ability to create in-house specialty libraries is incorporated into the standard software. Updating these libraries is straightforward.

FRONTIER LAB 44 “Method Map” for Material Characterization

Frontier Lab has developed a sequence of tests referred to as the The “method map” provides scientists with two simple “method map” to chemically characterize samples using the steps for determining the organic composition of any EGA/PY-3030D Multi-Functional Pyrolyzer System in conjunction unknown material: with a benchtop GC/MS. This sequence is applicable when characterizing virtually any organic material from volatiles to high molecular weight polymers.

i. The first step is to perform an Evolved Gas ii. The second step is to use the EGA thermogram and Analysis (EGA). In this technique, the sample is selected ion chromatograms (EIC) to define the thermal dropped into the furnace which is at a relatively low zones of interest and then perform one or a combination temperature (ca. 40-100 ˚C). The furnace is then of the following techniques: programmed to a much higher temperature (ca. 600- Use the links below for more information. 800 ˚C). Compounds “evolve” continuously from the sample as the temperature increases. A plot of detector Thermal Desorption (TD) response versus furnace temperature is obtained. Flash Pyrolysis (Py)

Heart Cutting (HC) Reactive Pyrolysis (RxPy)

FRONTIER LAB 45 EGA & “MethodMap”

EGA Configuration: No column is used; a short, small diameter (1.5m X 0.15mm id) deactivated tube connects the injection port to the detector. All thermal zones (interface temperature, GC injection port, column oven and detector cross-over) are held at elevated temperatures to prevent condensation. The figure below shows the EGA-MS configuration and a typical EGA thermogram. Following EGA, the instrument is re-configured. The EGA tube is replaced by an analytical column. The Frontier Vent-Free Adaptor enables this to be done easily and quickly; there is no need to vent the MS. MS vacuum equilibrium is re-established within a few minutes, and the exposure of the ion source to oxygen is minimized. In this example, a double-shot analysis (TD of the thermally stable and the volatile components followed by Py of the residual sample in the cup) was performed to characterize the two thermal zones shown on the EGA thermogram. One sample is analyzed two times; the sequence is fully automated.

TD-GC/MS Py-GC/MS He He 100ᵒC – 700ᵒC @20ᵒC/min As shown in the Figure, information about the organic ‘volatiles’ in the sample is generated by simply introducing the sample at 300 ˚C, Vent-Free only the compounds evolving below 300 ˚C will evolve from the Adaptor Micro-Jet Cryo Trap sample and be transported to the head of the column. If there is EGA tube Separation column MS MS interest in both the volatile fraction and the higher boiling compounds, this can be done in two steps, and it may be necessary GC Oven : 320 ºC GC Oven: Temperature Program to add a micro-cryo trap. Thermal desorption is performed over time, e.g., 100 to 250 ˚C at 20 ˚C /min takes 7.5 minutes. The micro-cryo trap re-focuses the volatile analytes of interest at the head of the Thermogram (EGA-MS) TD Chromatogram (TD-GC/MS) column so that the full separating power of the column can be (100˚C- 300˚C @ 20˚C/min) utilized.

Pyrogram (Py-GC/MS) at 600˚C If there are more than two zones in the obtained EGA thermogram, Heart-cutting (HC) technique, which utilizes an accessory called a 100 200 300 400 500 600 Selective Sampler, slices the thermal zones out of the sample and Temperature ºC 10 20 30 40 min Time separate the components chromatographically with detection by MS.

FRONTIER LAB 46 Use these links for more information.

Py-GC/MS System Configuration

1. Auto-Shot Sampler (AS-1020E) 2. Carrier Gas Selector (CGS-1050Ex) Up to 48 samples can be automatically analyzed using The device allows switching of the gas, e.g., He and air, any of the analytical modes (e.g., TD, Py, Double-Shot, surrounding the sample during analysis. Heart-Cutting. Etc) with enhanced reliability.

FRONTIER LAB 47 Use the links below formore information. 3. Selective Sampler (SS-1010E) Any temperature zone as defined by the EGA thermogram, that is Heart-Cutting either manually or automatically, can be introduced to a separation column.

4. MicroJet Cryo-Trap (MJT-1035E) 5. Ultra ALLOY® Metal Capillary Column By blowing liquid nitrogen jet to the front of separation By multi-layer gradient deactivation treatment, these column, volatile compounds are cryo-trapped while separation columns have high flexibility, high maintaining the temperature at -196ºC using only one temperature, and contamination resistances. third of the amount of liquid nitrogen required for competitors products. It supports automated analysis.

FRONTIER LAB 48 Use the links below formore information. 6. Vent-free GC/MS Adapter Without venting MS, separation column and/or EGA tube can be switched.

7. F-Search System (Libraries and Search 8. Micro-UV Irradiator (UV-1047Xe) Engine) With a strong Xe UV light source, photo, thermal, and oxidative degradation of polymers can rapidly be This software system supports identification of polymers evaluated. and additives from data obtained by evolved gas analysis, thermal desorption, or pyrolysis GC/MS analysis.

FRONTIER LAB 49 PLEASE VISIT OUR WEB SITE FOR OTHER APPLICATIONAREAS

Visit Frontier Lab web site at www.frontier-lab.com to find more materials categorized by the following application areas:

ADDITIVES ...... PLASTICIZERS, RELEASING AGENTS, SURFACTANTS, RESIDUAL MONOMERS, SOLVENTS, VOLATILES, IMPURITIES

ADHESIVES...... ACRYLICS, EPOXY, THERMOPLASTIC, ANAEROBIC

COATINGS ...... PIGMENTS, DYES, SOLVENTS, DRIERS, FILM FORMERS

CONSUMER PRODUCTS ...... TEXTILES, PERSONAL CARE PRODUCTS, PACKAGING, TOBACCO, FIBERS

ELASTOMERS ...... NATURAL SYNTHETIC RUBBERS, SILICONES, SULFUR COMPOUNDS

ENERGY ...... BIOMASS, OILS, COAL, HYDROCARBONS, GEOCHEMISTRY, BIOCHEMISTRY

ENVIRONMENTAL ...... VOLATILES, POLLUTANTS, PESTICIDES

FORENSIC AND SECURITY ...... FORENSIC EVIDENCES

INKS AND PAINTS ...... PIGMENT, RESIN, SOLVENT, DEFOAMER, WAX, PHOTOCOPY TONER

PAPER AND FIBERS ...... WOODS, PULP, COATINGS, SIZING AGENTS

POLYMER PROCESSING ...... POLYMER CHARACTERIZATION TECHNIQUES

OTHERS ...... MISCELLANEOUS APPLICATIONS

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