# Emissions of Volatile Compounds and Solids during Additive Manufacturing by the FFF Method
## 2 Materials and Methods  
The aim of the study was to identify organic compounds emitted into the air during 3D printing. The technique used was solid phase microextraction (SPME), in combination with gas chromatography coupled with mass spectrometry (GC-MS). The first research object was a Zortrax M200 3D printer with a closed chamber and without a cleaning filter, made from Olsztyn, from Poland. This printer had one printing nozzle and a heated table. Four objects from four different materials were printed. The manufacturing of each sample lasted for, on average, 90 min. The emission tests were conducted with a standard setup for each material based on the manufacturers' suggestion. The research sample was manufactured from the following filaments: black ABS, colorless PET-G, black PLA, and natural PVA. The print parameters are included in Table 1.  
The measuring station (Figure 4) consisted of the Zortrax M200 printer that printed the research object (Figure 5). Research was carried out in two variations. In the first method (Figure 6), the research sample was collected with an SPME fiber made of PDMS (polydimethylsiloxane). The SPME fiber was exposed in the printer chamber during the 3D printing process for 1 h. The desorption was carried out in the chromatograph dispenser for 10 min. In the second method, the research sample was collected with SPME fiber made of PDMS. For this experiment, 3 g of crushed plastic was placed in a headspace vial and conditioned at 200 \({}^{\circ}\)C for 25 min. The SPME fiber was then exposed inside the test vial for 5 min, and the desorption was carried out in the chromatograph dispenser for 10 min. Flow charts of the research plan are presented in Figures 7 and 8. Figure 5: Dogbone manufactured for the purpose of the research; (**a**) finished product (150 mm \(\times\) 10–20 mm \(\times\) 8 mm); (**b**) printed product before post-processing. Figure 6: Sample collection with the SPME fiber during the 3D printing process. The designation was carried out using the Bruker 436-GC gas chromatograph coupled with the Bruker Scion SQ mass spectrometer (single quadrupole, EI ion ionization), made  
Figure 8: Flow chart of the research plan of the second method. Figure 7: Flow chart of the research plan of the first method. \begin{table}
\begin{tabular}{c c c} \hline \hline
**No.** & **Retention Time (min)** & **Compound Name** \\ \hline
1 & 4.14 & Toluene \\
2 & 5.11 & Cyclotrisiloxane, hexamethyl- \\
3 & 5.49 & Cyclohexene, 4-etheryl- \\
4 & 6.01 & Ethylenehene \\
5 & 6.67 & Styrene \\
6 & 7.29 & Benzene, (1-methylethyl)- \\
7 & 7.69 & Cyclohexane, 1,2-diethyl-, cis- \\
8 & 7.90 & Benzene, propyl- \\
9 & 8.04 & Benzaldehyde \\
10 & 8.70 & Heptene, 2,2,4,6,6-pentamethyl- \\
11 & 8.98 & Benzene, 1-methyl-2-propyl- \\
12 & 9.32 & D-Limonene \\
13 & 9.98 & Acetophenone \\
14 & 11.23 & Cyclohexane, 1,2,4-triethenyl- \\
15 & 12.22 & Decanal \\
16 & 12.99 & Methyl 6,9,12,15-hexadecetraenoate \\
17 & 14.05 & Benzenebutanenitrile \\
18 & 14.81 & Dodecanal \\
19 & 14.93 & Quinoline, 2,4-dimethyl- \\
20 & 15.18 & Benzene, 1,1\({}^{\prime}\)-(1,2-cyclobutanediy!)bis-, cis-Dup1 \\
21 & 15.38 & Cyclododecane \\
22 & 15.44 & Benzene, 1,1\({}^{\prime}\)-(1,2-cyclobutanediy!)bis-, cis-Dup2 \\
23 & 15.51 & 5-Octadecene, (E)- \\
24 & 15.56 & Hepadecane \\
25 & 16.67 & Benzene, 1,1\({}^{\prime}\)-(1,3-propanediy!)bis- \\
26 & 16.74 & 1,3-di-iso-propyl naphthalene \\
27 & 16.79 & 2-Propenoic acid, triticely ester \\
28 & 16.82 & 1-Decanol, 2-hexyl- \\
29 & 16.92 & Benzene, 1,1\({}^{\prime}\)-(1,2-cyclobutanediy!)bis-, cis- \\
30 & 17.03 & Benzene, 1,1\({}^{\prime}\)-(2-butene-1,4-diy!)bis- \\
31 & 17.20 & Benzene, 1,1\({}^{\prime}\)-(1,2-cyclobutanediy!)bis-, trans- \\
32 & 17.32 & Naphthalene, 1,2,3,4-tetrahydro-1-phenyl- \\ \hline \hline \end{tabular}
\end{table} 
Table 6: Black ABS heating in headspace vial—compound identification.