Analysis of Selected Organophosphorus Compounds and Nano-Additives on Thermal, Smoke Properties and Quantities of CO and CO2 of Epoxy Materials
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Sample Preparation
2.3. Analytical Techniques
2.3.1. Cone Calorimeter Method
2.3.2. Thermogravimetric Method
2.3.3. Single-Chamber Test Method
3. Results
3.1. Results of Heat Release Rate Analysis of Selected Epoxy Blends
3.2. Results of Thermogravimetric Analysis
3.3. An Analysis of Concentrations of the Main Toxic Products Obtained from the Study of the Thermal Decomposition and Combustion Products of the Epoxy Materials Tested
4. Discussion
5. Conclusions
- All the applied fire-retardant additives to the epoxy resin Epidian 5 effectively changed the fire properties of the epoxy materials tested. The heat release rate was reduced compared to the non-fire-modified material. The HRRmax and HRRav values of all fire-retardant modifications were lower compared to the corresponding HRR values of the unmodified Epidian 5 material (HRRmax lower by 9–59%, HRRav lower by 1–49%).
- The solid-phase inhibitory effect of the applied flame retardants and their mixtures has been confirmed by the formation of layers of char.
- Applied anti-pyrenes containing phosphorus were found to be less thermally stable and have lower starting temperatures of thermal decomposition, but they exhibited multilevel thermal decomposition with higher efficiency of the carbonised residue.
- For samples 5F and 5B + 10M, the highest value of time to ignition of the gas phase was obtained (38 s). The main action of the additives took place in the solid phase. This was also evidenced by the higher residue values after thermal decomposition and combustion (by 76–790%) compared to the unmodified sample.
- The blended compositions had a lower onset temperature of thermal decomposition of the first phase compared to Epidian 5.
- The introduction of 5 wt.% magnesium hydroxide into Epidian 5 increased the initial temperature of thermal decomposition of phase I by 7 °C.
- Majority of the fire-retardant modifications of the epoxy resin were characterised by a higher ash weight (%) in relation to Epidian 5. The exception was sample 5F (3% lower value in relation to Epidian 5).
- The introduction of 5 wt.% magnesium hydroxide caused an increase in ash weight (%) in the thermogravimetric analysis to the highest differential level of 7.30%, as compared to all single-component flame-retardant modifications.
- CO and CO2 were identified in the toxic gases included in the smoke from the combustion of the samples analysed, according to the research methodology selected for the study.
- The concentration of CO (ppm) in thermal decomposition and combustion increased throughout the analysis lasting 600 s.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Parameter | Characteristic Features |
---|---|
Melting point/freezing point | 30–50 °C |
Glass transition temperature | −16 °C |
Ignition temperature | 266 °C |
Vapour pressure (20 °C, 50 °C) | 4.6 × 10−8 Pa |
Density (20 °C) | 1.16 g/cm3 |
Viscosity (25 °C) | 20,000–30,000 mPas |
Item | Sample Name | Sample Composition |
---|---|---|
1. | Ep5 | Ep5 |
2. | 5B | Ep5 + 5 wt.% Roflam B7 |
3. | 5A | Ep5 + 5 wt.% Al(OH)3 |
4. | 5M | Ep5 + 5 wt.% Mg(OH)2 |
5. | 5F | Ep5 + 5 wt.% Roflam F5 |
6. | 10F + 5M | Ep5 + 10 wt.% Roflam F5 + 5 wt.% Mg(OH)2 |
7. | 10F + 5A | Ep5 + 10 wt.% Roflam F5 + 5 wt.% Al(OH)3 |
8. | 10B + 5M | Ep5 + 10 wt.% Roflam B7 + 5 wt.% Mg(OH)2 |
9. | 10B + 5A | Ep5 + 10 wt.% Roflam B7 + 5 wt.% Al(OH)3 |
10. | 5F + 10M | Ep5 + 5 wt.% Roflam F5 + 10 wt.% Mg(OH)2 |
11. | 5F + 10A | Ep5 + 5 wt.% Roflam F5 + 10 wt.% Al(OH)3 |
12. | 5B + 10M | Ep5 + 5 wt.% Roflam B7 + 10 wt.% Mg(OH)2 |
13. | 5B + 10A | Ep5 + 5 wt.% Roflam B7 + 10 wt.% Al(OH)3 |
Item | Sample Name | HRRmax (kW/m2) | HRRav (kW/m2) | THR * (MJ/m2) | SEAav (m2/kg) | TSP ** (m2) | Time Until Ignition (s) | Time Until Reaching HRRmax (s) | Sample Remnants (wt.%) | Proper Emission of CO (kg/kg) | Proper Emission of CO2 (kg/kg) |
---|---|---|---|---|---|---|---|---|---|---|---|
1. | Ep5 | 1318 | 603 | 130 | 849 | 40.7 | 16 | 132 | 1.85 | 2.1 | 11.3 |
2. | 5B | 900 | 595 | 114 | 316 | 21.3 | 10 | 84 | 3.87 | 2.2 | 10.4 |
3. | 5A | 748 | 435 | 136 | 197 | 17.0 | 16 | 148 | 5.64 | 1.9 | 10.5 |
4. | 5M | 892 | 364 | 117 | 158 | 15.6 | 36 | 100 | 3.25 | 2.0 | 10.6 |
5. | 5F | 1011 | 446 | 77 | 655 | 33.6 | 38 | 82 | 5.74 | 2.9 | 10.6 |
6. | 10F + 5M | 962 | 475 | 101 | 701 | 35.3 | 34 | 120 | 7.60 | 2.4 | 10.4 |
7. | 10F + 5A | 539 | 353 | 84 | 693 | 35.0 | 16 | 118 | 16.47 | 2.3 | 10.1 |
8. | 10B + 5M | 1162 | 584 | 121 | 476 | 27.1 | 30 | 104 | 5.57 | 2.2 | 11.6 |
9. | 10B + 5A | 740 | 310 | 105 | 327 | 21.7 | 10 | 96 | 10.22 | 2.3 | 10.5 |
10. | 5F + 10M | 1199 | 530 | 107 | 278 | 19.9 | 10 | 114 | 6.97 | 2.2 | 11.6 |
11. | 5F + 10A | 570 | 369 | 104 | 926 | 43.5 | 36 | 190 | 9.28 | 2.1 | 10.0 |
12. | 5B + 10M | 988 | 470 | 96 | 754 | 37.2 | 38 | 118 | 11.01 | 2.4 | 11.9 |
13. | 5B + 10A | 693 | 405 | 87 | 547 | 29.7 | 30 | 136 | 9.80 | 2.7 | 11.3 |
Item | Sample name | Temperature of Onset of Thermal Decomposition of the First Transformation Phase (°C) | Temperature of the Maximum Rate of Weight Loss of the Sample in Phase I/II of the Transformation (°C) | Maximum Rate of Mass Loss in Phase I/II Transformation (%/min) | Temperature of 50% Sample Weight Loss (°C) | Mass of Sample after Thermal Decomposition (mg); (%) |
---|---|---|---|---|---|---|
1. | Ep5 | 330 | 343/514 | 6.71/2.99 | 395 | 0.05; 1.56 |
2. | 5B | 317 | 335/510 | 6.70/2.36 | 368 | 0.14; 4.44 |
3. | 5A | 335 | 337/511 | 9.77/2.50 | 399 | 0.19; 5.31 |
4. | 5M | 337 | 365/487 | 6.99/21.36 | 376 | 0.25; 7.30 |
5. | 5F | 318 | 330/512 | 7.53/1.99 | 361 | 0.06; 1.52 |
6. | 10F + 5M | 316 | 338/512 | 7.18/2.53 | 380 | 0.19; 5.59 |
7. | 10F + 5A | 310 | 333/519 | 5.99/2.01 | 360 | 0.22; 6.71 |
8. | 10B + 5M | 320 | 338/522 | 7.46/2.06 | 374 | 0.22; 5.82 |
9. | 10B + 5A | 311 | 328/513 | 7.50/1.97 | 355 | 0.27; 6.99 |
10. | 5F + 10M | 335 | 346/510 | 6.85/3.38 | 346 | 0.27; 7.02 |
11. | 5F + 10A | 320 | 336/513 | 7.61/2.15 | 366 | 0.26; 7.00 |
12. | 5B + 10M | 340 | 353/508 | 7.41/3.08 | 388 | 0.27; 7.85 |
13. | 5B + 10A | 319 | 337/515 | 6.94/2.13 | 372 | 0.34; 8.77 |
Item | Sample Name | Maximum CO Concentration (ppm) | Maximum CO2 Concentration (ppm) | Time to Reach Maximum Concentration Value (s) |
---|---|---|---|---|
1. | Ep5 | 3705 | 47,271 | 405 |
2. | 5M | 1721 | 30,751 | 355 |
3. | 5A | 2963 | 37,170 | 325 |
4. | 5B | 2707 | 32,725 | 345 |
5. | 5F | 2453 | 35,389 | 600 |
6. | 5B + 10A | 2561 | 22,931 | 300 |
7. | 5B + 10M | 2091 | 40,824 | 475 |
8. | 10B + 5A | 2348 | 31,989 | 595 |
9. | 10B + 5M | 3183 | 37,338 | 380 |
10. | 5F + 10A | 1830 | 30,212 | 510 |
11. | 5F + 10M | 3656 | 36,875 | 285 |
12. | 10F + 5A | 3083 | 29,224 | 380 |
13. | 10F + 5M | 4673 | 34,783 | 275 |
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Staszko, S.; Półka, M. Analysis of Selected Organophosphorus Compounds and Nano-Additives on Thermal, Smoke Properties and Quantities of CO and CO2 of Epoxy Materials. Materials 2023, 16, 3369. https://doi.org/10.3390/ma16093369
Staszko S, Półka M. Analysis of Selected Organophosphorus Compounds and Nano-Additives on Thermal, Smoke Properties and Quantities of CO and CO2 of Epoxy Materials. Materials. 2023; 16(9):3369. https://doi.org/10.3390/ma16093369
Chicago/Turabian StyleStaszko, Sebastian, and Marzena Półka. 2023. "Analysis of Selected Organophosphorus Compounds and Nano-Additives on Thermal, Smoke Properties and Quantities of CO and CO2 of Epoxy Materials" Materials 16, no. 9: 3369. https://doi.org/10.3390/ma16093369