Influence of Modified Epoxy Dian Resin on Properties of Nitrile-Butadiene Rubber (NBR)
Abstract
:1. Introduction
2. Materials and Methods
2.1. Sample Composition
- -
- ED-20: molecular weight 340 g/mol; epoxy groups content 20%;
- -
- ED-24 AK: molecular weight 970 g/mol; epoxy groups content 4.9%; carboxyl groups content 1.5%;
- -
- ED-24 (Epidian 6) modified with adipic acid (ED-24AK) of the formula is presented in Figure 1.
2.2. Sample Preparation
- Mastication of rubber—2 min;
- Admixing of resin—2 min;
- Addition and mixing of crosslinking system—1 min, making the total time of mixing ca. 5 min.
2.3. Kinetics of Crosslinking
2.4. Crosslink Density
2.5. FT-IR Analysis
- -
- 2950, 2850, 1450, 1000, 900 cm−1 originated from C-H groups;
- -
- 1550 cm−1 -C=C- from butadiene;
- -
- 750 cm−1 C-H bonds in -CH=CH- butadiene monomer units;
- -
- 2250 cm−1 -CN groups from acrylonitrile monomer units.
- -
- 1050 cm−1 originating from C-O bonds;
- -
- 900 cm−1 typical for the presence of an epoxy ring;
- -
- 1700, 1450 and 750 cm−1 characteristic for adipic acid;
- -
- 550 cm−1 derived both from a functional group X in the para position in C6H4X2 of Epidian and from adipic acid were assigned and changes to their intensity and position discussed.
2.6. Mechanical Properties
2.7. Surface Energy
2.8. Adhesion Measurements
2.9. Friction Measurement
3. Results and Discussion
3.1. Kinetics of Crosslinking
3.2. Crosslink Density
3.3. FT-IR (Fourier-Transform Infrared Spectroscopy) Analysis
3.4. Mechanism of Crosslinking
3.5. Mechanical Properties
3.6. Contact Angle and Surface Energy
3.7. Adhesion Measurements
3.8. Friction Characteristics
4. Summary and Conclusions
- FTIR analysis reveals that absorption peaks originated from both resins and rubber; however, characteristic peaks of ED-20 are more visible in comparison to ED-24 AK, which can be associated with the active participation in crosslinking of rubber only for the latter.
- The addition of adipic acid modified dian resin increases the crosslink density of NBR (of both covalent and ionic characters).
- The effect of NBR modification by epoxy dian resins is likely to be related to the morphology of the system. Too little or too much resin content has a negative effect on the degree of its dispersion in the rubber matrix. The aggregated resin particles do not interfere with the crosslinking of rubber phase. The observed effect of lowering the density of the rubber matrix is lower in the case of the addition of ED-24 AK, which shows a much greater tendency for internal and external crosslinking, contributing to the total crosslinking of the system.
- The above conclusions explain the findings that the addition of ED-20 is more efficient in terms of rubber adhesion to glass fibers, whereas ED-24AK is better according to its mechanical properties (TS, moduli in extension and hardness).
- The addition of ED-20 results in a higher surface energy of NBR in comparison to ED-24 AK resin. Despite higher polarity of the modified epoxy resin, due to its participation in rubber crosslinking, the NBR vulcanizates modified with ED-24 AK show lower surface polarity than those for which ED-20 was used. This better explains the adhesion of NBR modified with unmodified epoxy resin to glass fibers.
- The resin addition in the amount of 5 phr has the greatest influence on the friction force of NBR vulcanizates (increasing for ED-20; decreasing for ED-24AK), due to different mechanism of their action involved, i.e., plastification for the former and hardening for the latter. The optimal amount of the tested resin modifiers from the point of view of reducing NBR friction, regardless of their type, is 10 phr. In the case of ED-20, this can be explained by the best lubricating effect, with moderate plasticization of vulcanizates. On the other hand, in the case of the ED-24 AK, we deal with an optimal combination of a greater stiffness of the vulcanizate with a reduced polarity of its surface.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Carraher, C.E., Jr.; Moore, J.A. (Eds.) Modification of Polymers: Polymer Science and Technology; Plenum Press: New York, NY, USA, 1983; Volume 21. [Google Scholar] [CrossRef]
- Hiltner, A. (Ed.) Structure—Property Relationships of Polymer Solids; Springer: Berlin/Heidelberg, Germany, 1983; ISBN 978-1468446159. [Google Scholar]
- Thomas, S.; Grohens, Y.; Jyotishkumar, P. (Eds.) Characterization of Polymer Blends: Miscibility, Morphology, and Interfaces; Wiley: Hoboken, NJ, USA, 2015; ISBN 978-3-527-33153-6. [Google Scholar]
- Nemani, S.K.; Annavarapu, R.K.; Mohammadian, B.; Raiyan, A.; Heil, J.; Haque, A.; Abdelaal, A.; Sojoudi, H. Surface Modification of Polymers: Methods and Applications. Adv. Mater. Interf. 2018, 5, 1801247. [Google Scholar] [CrossRef]
- Pinson, J.; Thiry, D. (Eds.) Surface Modification of Polymers: Methods and Applications; Wiley: Hoboken, NJ, USA, 2019; ISBN 978-3-527-81923-2. [Google Scholar]
- Jing, S.; Sumio, A.; Katsuya, M.; Hidetoshi, H.; Oravec, J.; Preto, J.; Melus, P. Adhesion of carbon steel and natural rubber by functionalized silane coupling agents. Int. J. Adhes. 2017, 72, 70–74. [Google Scholar] [CrossRef]
- Deepalekshmi, P.; Visakh, P.M.; Mathew, A.P.; Chandra, A.K.; Thomas, S. Advances in Elastomers: Their Composites and Nanocomposites: State of Art, New Challenges and Opportunities. In Advances in Elastomers II; Springer: Berlin/Heidelberg, Germany, 2013; pp. 1–9. [Google Scholar] [CrossRef]
- Hesse, W.; Leicht, E.; Sattelmeyer, R. Rubber Compositions and Vulcanisates Obtained Therefrom Having an Improved Adhesion to Reinforcing Materials. European Patent 0440036A1, 7 August 1991. [Google Scholar]
- Swarts, J.M.; Lee, Z.S. Composition for Rubberizing Steel Cords. U.S. Patent 4148769A, 10 April 1979. [Google Scholar]
- Ziegler, S.P. Układ Zwiększający Przyczepność Dla Wyrobów Gumowych. Polski Patent 2432810T3, 31 July 2014. [Google Scholar]
- Davis, J.A. Rubber Compositions and Articles Thereof Having Improved Metal Adhesion and Metal Adhesion Retention. U.S. Patent 4435477A, 6 March 1984. [Google Scholar]
- Motawie, A.M.; Sadek, E.M. Curing of Natural Rubber/Epoxy Adhesive Pak. J. Sci. Ind. Res. 2001, 44, 142–147. [Google Scholar]
- Singh, B.; Sedlak, J.A. Additives for improving tire cord adhesion and toughness of vulcanized rubber compositions. European Patent 0473948, 11 March 1992. [Google Scholar]
- Matykiewicz, D. Hybrid Epoxy Composites with Both Powder and Fiber Filler: A Review of Mechanical and Thermomechanical Properties. Materials 2020, 13, 1802. [Google Scholar] [CrossRef] [PubMed] [Green Version]
- Luginsland, H.-D.; Froöhlich, J.; Wehmeier, A. Influence of Different Silanes on the Reinforcement of Silica-Filled Rubber Compounds. Rubber Chem. Technol. 2002, 75, 563–579. [Google Scholar] [CrossRef]
- Chudzik, J.; Bieliński, D.M.; Bratychak, M.; Demchuk, Y.; Astakhova, O.; Jędrzejczyk, M.; Celichowski, G. Influence of Modified Epoxy Resins on Peroxide Curing, Mechanical Properties and Adhesion of SBR, NBR and XNBR to Silver Wires—Part I: Application of Monoperoxy Derivative of Epoxy Resin (PO). Materials 2021, 14, 1320. [Google Scholar] [CrossRef]
- Chudzik, J.; Bieliński, D.M.; Bratychak, M.; Demchuk, Y.; Astakhova, O.; Jędrzejczyk, M.; Celichowski, G. Influence of Modified Epoxy Resins on Peroxide Curing, Mechanical Properties and Adhesion of SBR, NBR and XNBR to Silver Wires—Part II: Application of Carboxy-Containing Peroxy Oligomer (CPO). Materials 2021, 14, 1285. [Google Scholar] [CrossRef]
- Immergut, E.H.; Mark, H.F. Principles of Plasticization. In Platzer; Plasticization and Plasticizer Processes; Advances in Chemistry; American Chemical Society: Washington, DC, USA, 1965; pp. 1–26. [Google Scholar]
- Kruželák, J.; Sýkora, R.; Hudec, I. Peroxide vulcanization of natural rubber. Part II: Effect of peroxides and co-agents. J. Polym. Eng. 2015, 35, 21–29. [Google Scholar] [CrossRef]
- Bratychak, M.; Astakhova, O.; Mykhailiv, O.; Stryzhachuk, A.; Shyshchak, O. Chemical Modification of ED-24 Epoxy Resin by Adipic Acid. Chem. Chem. Technol. 2012, 6, 51–57. [Google Scholar] [CrossRef]
- Ellis, B. Chemistry and Technology of Epoxy Resins; Blackie Academic and Professional: London, UK, 1993; ISBN 978-9401053020. [Google Scholar]
- Blagonravova, A.; Nepomnyashiy, A. Lakovye Epoksidnye Smoly; Khimiya: Moscow, Russia, 1970. [Google Scholar]
- Sapronov, O.; Maruschak, P.; Sotsenko, V.; Buketova, N.B.; De Deus, A.B.D.G.; Sapronova, A.; Prentkovskis, O. Development and Use of New Polymer Adhesives for the Restoration of Marine Equipment Units. J. Mar. Sci. Eng. 2020, 8, 527. [Google Scholar] [CrossRef]
- Habib, F.; Bajpai, M. Synthesis and Characterization of Acrylated Epoxidized Soybean Oil for UV-Cured Coatings. Chem. Chem. Technol. 2011, 5, 317–326. [Google Scholar] [CrossRef]
- Zhyltsova, S.; Mykhalchuk, V.; Platonova, O.; Biloshenko, V. Epoxy-Silica Nanocomposites Based on Ethoxysilanes and Diglycidyl Ether of Dicyclohexylpropane. Chem. Chem. Technol. 2011, 5, 49–54. [Google Scholar] [CrossRef]
- Bashta, B.; Astakhova, O.; Shyshchak, O.; Bratychak, M. Epoxy Resins Chemical Modification by Dibasic Acids. Chem. Chem. Technol. 2014, 8, 309–316. [Google Scholar] [CrossRef]
- Habib, F.; Bajpai, M. UV Curable Heat Resistant Epoxy Acrylate Coatings. Chem. Chem. Technol. 2010, 4, 205–216. [Google Scholar] [CrossRef]
- Esmizadeh, E.; Naderi, G.; Barmar, M. Effect of Organo-clay on Properties and Mechanical Behavior of Fluorosilicone Rubber. Fiber Polym. 2014, 15, 2376–2385. [Google Scholar] [CrossRef]
- Vahidifar, A.; Esmizadeh, E.; Rodrigue, D. Effect of the simultaneous curing and foaming kinetics on the morphology de-velopment of polyisoprene closed cell foams. Elastomery 2018, 22, 3–18. [Google Scholar]
- Bieliński, D.M.; Głąb, P.; Chruściel, J. Modification of styrene-butadiene rubber with polymethylsiloxanes. Part I: Interactions between modifier and rubber. Polimery 2007, 52, 195–202. [Google Scholar] [CrossRef] [Green Version]
- Sheehan, C.J.; Bisio, A.L. Polymer/Solvent Interaction Parameters. Rubber Chem. Technol. 1966, 39, 149–192. [Google Scholar] [CrossRef]
- Flory, P.J.; Rehner, J. Statistical mechanics of cross-linked polymer networks. I. Rubberlike Elasticity. J. Chem. Phys. 1943, 11, 512–520. [Google Scholar] [CrossRef]
- Mandal, U.K.; Tripathy, D.K.; De, S.K. Effect of silica filler on dynamic mechanical properties of lonic elastomer based on carboxylated nitrile rubber. J. Appl. Polym. Sci. 1995, 55, 1185–1191. [Google Scholar] [CrossRef]
- Vondracek, P.; Pouchaleon, A. Ammonia-induced tensile set and swelling in silica-filled silicone rubber. Rubber. Chem. Technol. 1990, 63, 202–214. [Google Scholar] [CrossRef]
- Zaborski, M.; Lipińska, M. Właściwości kauczuku butadienowo-akrylonitrylowego zawierającego jako napełniacz strącaną kredę modyfikowaną różnymi aminokwasami. Polimery 2002, 47, 6, 428–434. [Google Scholar]
- Lipińska, M. Elastomers Chapter 3: Nitrile Elastomer/LDH Composites with Varying Mg/Al Ratio, Curing, Nanoparticles Dispersion and Mechanical Properties; Intech Open: London, UK, 2017; pp. 39–74. [Google Scholar] [CrossRef] [Green Version]
- Owens, D.K.; Wendt, R.C. Estimation of the surface free energy of polymers. J. Appl. Polym. Sci. 1969, 13, 1741–1747. [Google Scholar] [CrossRef]
- Płaza, S. Fizykochemia Procesów Trybologicznych; Wydawnictwo Uniwersytetu Łódzkiego: Łódź, Poland, 1997; p. 37. (In Polish) [Google Scholar]
Components | 5% of Resin | 10% of Resin | 15% of Resin | |||
---|---|---|---|---|---|---|
(phr) | (g) | (phr) | (g) | (phr) | (g) | |
Nancar 2865 (NBR) | 100.0 | 60.0 | 100.0 | 55.0 | 100.0 | 50.0 |
Stearic acid | 1.0 | 0.6 | 1.0 | 0.55 | 1.0 | 0.5 |
ZnO | 5.0 | 3.0 | 5.0 | 2.75 | 5.0 | 2.5 |
DM (MBTS) | 1.0 | 0.6 | 1.0 | 0.55 | 1.0 | 0.5 |
Sulfur | 1.5 | 0.9 | 1.5 | 0.83 | 1.5 | 0.75 |
ED-20/ED-24AK | 5.0 | 3.0 | 10.0 | 5.5 | 15.0 | 7.5 |
Ref. | ED-20 5% | ED-20 10% | ED-20 15% | ED-24AK 5% | ED-24AK 10% | ED-24AK 15% | |
---|---|---|---|---|---|---|---|
ML (dNM) | 0.5 | 0.7 | 0.6 | 0.6 | 0.8 | 0.8 | 0.7 |
MH (dNM) | 4.9 | 6.2 | 5.5 | 4.2 | 5.9 | 5.6 | 5.4 |
ΔM (dNM) | 4.4 | 5. 4 | 4.9 | 3.6 | 5.1 | 4.8 | 4.7 |
t05 (min) | 6.1 | 3.2 | 4.0 | 4.9 | 0.7 | 0.6 | 0.5 |
t90 (min) | 38.4 | 47.4 | 42.4 | 40.7 | 34.2 | 27.1 | 30.9 |
CRI (100%/min) | 3.1 | 2.3 | 2.6 | 2.8 | 3.0 | 3.8 | 3.3 |
Parameter | Ref. | ED-20 | ED-24 AK | ||||
---|---|---|---|---|---|---|---|
- | 5% | 10% | 15% | 5% | 10% | 15% | |
TS (MPa) | 2.09 | 3.31 | 2.61 | 3.21 | 4.91 | 4.41 | 7.13 |
Eb (%) | 646 | 270 | 695 | 560 | 513 | 526 | 339 |
SE100 (MPa) | 0.85 | 0.81 | 0.63 | 0.69 | 0.76 | 0.91 | 0.86 |
SE200 (MPa) | 1.06 | 1.03 | 0.93 | 1.01 | 1.08 | 1.6 | 1.5 |
SE300 (MPa) | 1.22 | 1.34 | 1.24 | 1.33 | 1.51 | 2.4 | 2.4 |
Hardness (°ShA) | 38.1 | 37.2 | 35.5 | 32.1 | 38.5 | 41.6 | 40.4 |
Parameter | Ref. | ED-20 | ED-24 AK | ||||
---|---|---|---|---|---|---|---|
5% | 10% | 15% | 5% | 10% | 15% | ||
Adhesion (N): | |||||||
Average | 18.5 | 27.7 | 24.5 | 26.5 | 22.1 | 15.6 | 23 |
Std deviation | 3.8 | 4.5 | 4.1 | 5.3 | 5.4 | 3.7 | 3.7 |
Sample | ED-20 5% | ED-20 10% | ED-20 15% | ED-24 AK 5% | ED-24 AK 10% | ED-24 AK 15% | |
---|---|---|---|---|---|---|---|
Property Tested | |||||||
Curing time (min) | ↑ (+23%) | ↑ (+10%) | ↑ (+6%) | ↓ (−16%) | ↓ (−29%) | ↓ (−20%) | |
Crosslink density (mol/cm3) | ↑ (+25%) | ↓ (−14%) | ↑ (+30%) | ↑ (+27%) | ↑ (+12%) | ↑ (+28%) | |
Tensile Strength (MPa) | ↑ (+58%) | ↑ (+25%) | ↑ (+54%) | ↑ (+135%) | ↑ (+111%) | ↑ (+241%) | |
Elongation at break (%) | ↓ (−58%) | ↑ (+8%) | ↓ (−13%) | ↓ (−21%) | ↓ (−19%) | ↓ (−48%) | |
Hardness (°Sh A) | ↓ (−2%) | ↓ (−7%) | ↓ (−16%) | ↑ (+1%) | ↑ (+9%) | ↑ (+6%) | |
Surface energy (mJ/m2) | ↑ (+19%) | ↑ (+32%) | ↑ (+16%) | ↓ (−3%) | ↓ (+3%) | ↑ (+35%) | |
Adhesion (N) | ↑ (+50%) | ↑ (+32%) | ↑ (+43%) | ↑ (+19%) | ↓ (−16%) | ↑ (+24%) | |
Friction (N) | ↑ (+113%) | ↓ (−25%) | ↓ (+25%) | ↓ (−12%) | ↓ (0%) | ↓ (−12%) |
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Chudzik, J.; Bieliński, D.M.; Demchuk, Y.; Bratychak, M.; Astakhova, O. Influence of Modified Epoxy Dian Resin on Properties of Nitrile-Butadiene Rubber (NBR). Materials 2022, 15, 2766. https://doi.org/10.3390/ma15082766
Chudzik J, Bieliński DM, Demchuk Y, Bratychak M, Astakhova O. Influence of Modified Epoxy Dian Resin on Properties of Nitrile-Butadiene Rubber (NBR). Materials. 2022; 15(8):2766. https://doi.org/10.3390/ma15082766
Chicago/Turabian StyleChudzik, Joanna, Dariusz M. Bieliński, Yuriy Demchuk, Michael Bratychak, and Olena Astakhova. 2022. "Influence of Modified Epoxy Dian Resin on Properties of Nitrile-Butadiene Rubber (NBR)" Materials 15, no. 8: 2766. https://doi.org/10.3390/ma15082766