Mechanical Properties of Polytetrafluoroethylene-Based Composites with Modified Silicon Dioxide: a Temperature-Dependent Study

Abstract

The article provides a comprehensive study of the effect of modified silicon dioxide on the physical, mechanical, and thermodynamic properties of polytetrafluoroethylene-based polymer composites on in a wide range of temperatures, including cryogenic conditions typical of the Arctic. It was demonstrated that modifying the filler surface with aluminum chloride improves interfacial interaction with the polymer matrix, promotes the formation of a more ordered supramolecular structure, and increases the degree of crystallinity of the composite. X-ray diffraction analysis, scanning electron microscopy, and differential scanning calorimetry revealed that the introduction of the modified filler leads to a decrease in the coefficient of linear thermal expansion and an increase in the enthalpy of fusion. Mechanical testing revealed increased tensile and compressive strength, compressive modulus, and stability of properties at subzero temperatures for composites with modified silica compared to pure polytetrafluoroethylene and a composite with an unmodified filler. It was established that the key factor in improving performance is effective reinforcement of the polymer matrix through uniform distribution of filler particles and enhanced adhesion at the phase interface due to aluminum cations adsorbed on the SiO₂ surface. The obtained results demonstrate the potential of using modified silicon oxide to create polymer composites resistant to extreme Arctic climatic conditions

The work was carried out as part of the State Assignment of the Ministry of Science and Higher Education of the Russian Federation "Fundamental Principles of Creating New Polymer Materials for Technical and Medical Applications with Controlled and Self-Organizing Properties" (FSRG-2024-0004)

Please cite this article in English as:

Sivtseva-Gladkina N.P., Spiridonov A.M., Danilova S.N., et al. Mechanical properties of polytetrafluoroethylene-based composites with modified silicon dioxide: a temperature-dependent study. Herald of the Bauman Moscow State Technical University, Series Natural Sciences, 2026, no. 4 (127), pp. 97--117 (in Russ.). EDN: QWEVFX

References

[1] Pudovkina O.I., Redkina T.M., Solomonova V.N. The development strategy of the Arctic zone of Russia. Perspektivy nauki [Science Prospects], 2018, no. 3, pp. 70--73 (in Russ.).

[2] Pogostinskaya N.N., Pogostinskiy Yu.A., Vlasova M.S. Measuring the strategy for socio-economic development of the Russian Arctic zone. Arktika: ekologiya i ekonomika [Arctic: Ecology and Economy], 2019, no. 33, pp. 21--33 (in Russ.). DOI: https://doi.org/10.25283/2223-4594-2019-1-21-33

[3] Krutikov A.V., Smirnova O.O., Bocharova L.K. Strategy for the development of the Russian Arctic. Results and prospects. Arktika i Sever [Arctic and North], 2020, no. 40, pp. 254--269 (in Russ.). DOI: https://doi.org/10.37482/issn2221-2698.2020.40.254

[4] Kondratov N.A. Development of transport infrastructure in the Arctic zone of Russia. Geograficheskiy vestnik [Geographical Bulletin], 2017, no. 4, pp. 68--80 (in Russ.). DOI: https://doi.org/10.17072/2079-7877-2017-4-68-80

[5] Ulchenko M.V., Bashmakova E.P. Problems of development of transport infrastructure in regions of the Arctic zone of the Russian Federation. Ekonomika i upravlenie: problemy, resheniya, 2018, no. 11, pp. 45--52 (in Russ.). EDN: YUVQQX

[6] Алексеева М.Б., Богачев В.Ф., Горенбургов М.А. Системная диагностика стратегии развития промышленности Арктики. Записки горного института, 2019, т. 238, с. 450--458. DOI: https://doi.org/10.31897/PMI.2019.4.450

[7] Zhukov M.A. An optimal set of criteria for the allocation of territories within the Arctic zone of the Russian Federation. Prirodnye resursy Arktiki i Subarktiki [Arctic and Subarctic Natural Resources], 2024, no. 3, pp. 462--469 (in Russ.). DOI: https://doi.org/10.31242/2618-9712-2024-29-3-462-469

[8] Makhutov N.A., Moskvichev V.V., Fomin V.M. Designing machinery for the Arctic: a problem of socioeconomic development of Russia’s Eastern regions. Her. Russ. Acad. Sci., 2015, vol. 1, pp. 79--86. DOI: https://doi.org/10.1134/S1019331615010104

[9] Apsosimova E., Tarasov N. On the issue of application of mining machines in the arctic conditions. IOP Conf. Ser.: Earth Environ. Sci., 2019, vol. 272, no. 3, art. 032066. DOI: https://doi.org/10.1088/1755-1315/272/3/032066

[10] Rae P.J., Dattelbaum D.M. The properties of poly(tetrafluoroethylene) (PTFE) in compression. Polymer, 2004, vol. 45, no. 22, pp. 7615--7625. DOI: https://doi.org/10.1016/j.polymer.2004.08.064

[11] Speerschneider C.J., Li C.H. A correlation of mechanical properties and microstructure of polytetrafluoroethylene at various temperatures. J. Appl. Phys., 1963, vol. 34, no. 10, pp. 3004--3007. DOI: https://doi.org/10.1063/1.1729110

[12] Deshwal D., Belgamwar S.U., Bekinal S.I., et al. Role of reinforcement on the tribological properties of polytetrafluoroethylene composites: a comprehensive review. Polym. Compos., 2024, vol. 45, no. 16, pp. 14475--14497. DOI: https://doi.org/10.1002/pc.28802

[13] Madhan K., Padmanaban R., Venkatesh G. Formulation and numerical investigation of PTFE-based composites for piston rings of oil free air compressors. In: Rajkumar K., Jayamani E., Ramkumar P. (eds). Recent Advances in Materials Technologies. Lecture Notes in Mechanical Engineering. Singapore, Springer, 2022, pp. 87--98. DOI: https://doi.org/10.1007/978-981-19-3895-5_7

[14] Yin M.H., Zhang Y.C., Zhou R.M., et al. Friction mechanism and application of PTFE coating in finger seals. Tribol. Trans., 2022, vol. 65, no. 2, pp. 260--269. DOI: https://doi.org/10.1080/10402004.2021.1949512

[15] Dhanumalayan E., Joshi G.M. Performance properties and applications of polytetrafluoroethylene (PTFE) --- a review. Adv. Compos. Hybrid Mater., 2018, vol. 1, no. 2, pp. 247--268. DOI: https://doi.org/10.1007/s42114-018-0023-8

[16] Guo Q., Huang Y., Xu M., et al. PTFE porous membrane technology: a comprehensive review. J. Membr. Sci., 2022, vol. 664, art. 121115. DOI: https://doi.org/10.1016/j.memsci.2022.121115

[17] Kornopoltsev V.N., Mognonov D.M., Ayurova O.Z., et al. New tribological composites based on polytetrafluoroethylene. Inorg. Mater. Appl. Res., 2017, vol. 8, no. 1, pp. 108--111. DOI: https://doi.org/10.1134/S2075113317010208

[18] Vishal K., Rajkumar K., Sabarinathan P. Effect of recovered silicon filler inclusion on mechanical and tribological properties of polytetrafluoroethylene (PTFE) composite. Silicon, 2022, vol. 14, no. 9, pp. 4601--4610. DOI: https://doi.org/10.1007/s12633-021-01250-w

[19] Qu M., Yao Y., He J., et al. Tribological study of polytetrafluoroethylene lubricant additives filled with Cu microparticles or SiO₂ nanoparticles. Tribol. Int., 2017, vol. 110, pp. 57--65. DOI: https://doi.org/10.1016/j.triboint.2017.02.010

[20] Shi X., Wu C., Rong M., et al. Improvement of creep resistance of polytetrafluoroethylene films by nano-inclusions. Chin. J. Polym. Sci., 2013, vol. 31, no. 3, pp. 377--387. DOI: https://doi.org/10.1007/s10118-013-1225-8

[21] Xie H., Jiang B., He J., et al. Lubrication performance of MoS₂ and SiO₂ nano-particles as lubricant additives in magnesium alloy-steel contacts. Tribol. Int., 2016, vol. 93-A, pp. 63--70. DOI: https://doi.org/10.1016/j.triboint.2015.08.009

[22] Ge X., Xia Y., Cao Z. Tribological properties and insulation effect of nanometer TiO₂ and nanometer SiO₂ as additives in grease. Tribol. Int., 2015, vol. 92, pp. 454--461. DOI: https://doi.org/10.1016/j.triboint.2015.07.031

[23] Shen J.T., Top M., Pei Y.T., et al. Wear and friction performance of PTFE filled epoxy composites with a high concentration of SiO₂ particles. Wear, 2015, vol. 322-323, pp. 171--180. DOI: https://doi.org/10.1016/j.wear.2014.11.015

[24] Peng D.X., Kang Y., Hwang R.M., et al. Tribological properties of diamond and SiO₂ nanoparticles added in paraffin. Tribol. Int., 2009, vol. 42, no. 6, pp. 911--917. DOI: https://doi.org/10.1016/j.triboint.2008.12.015

[25] Liu F., Jin Y., Jiang W., et al. Improved coefficient thermal expansion and mechanical properties of PTFE composites for high-frequency communication. Compos. Sci. Technol., 2023, vol. 241, art. 110142. DOI: https://doi.org/10.1016/j.compscitech.2023.110142

[26] Lin J., Chen H., Yao L. Surface tailoring of SiO₂ nanoparticles by mechanochemical method based on simple milling. Appl. Surf. Sci., 2010, vol. 256, no. 20, pp. 5978--5984. DOI: https://doi.org/10.1016/j.apsusc.2010.03.105

[27] Hua D., Tang J., Jiang J., et al. Controlled grafting modification of silica gel via RAFT polymerization under ultrasonic irradiation. Mater. Chem. Phys., 2009, vol. 114, no. 1, pp. 402--406. DOI: https://doi.org/10.1016/j.matchemphys.2008.09.046

[28] Thissen P., Seitz O., Chabal Y.J. Wet chemical surface functionalization of oxide-free silicon. Prog. Surf. Sci., 2012, vol. 87, no. 9-12, pp. 272--290. DOI: https://doi.org/10.1016/j.progsurf.2012.10.003

[29] Lipatov Yu.S. Fizicheskaya khimiya napolnennykh polimerov [Physical chemistry of filled polymers]. Moscow, Khimiya Publ., 1977.

[30] Solomko V.P. Napolnennye kristallizuyushchiesya polimery [Filled crystallizable polymers]. Kiev, Naukova dumka Publ., 1980.

[31] Smolyanskii A.S., Arsentyev M.A., Rashkovskii A.Y., et al. Radiation-induced changes in the degree of crystallinity of powdered polytetrafluoroethylene. Crystallogr. Rep., 2019, vol. 64, no. 4, pp. 553--558. DOI: https://doi.org/10.1134/S1063774519040205

[32] Loginov B.A. Udivitelnyy mir ftorpolimerov [Amazing world of fluoropolymers]. Moscow, Devyatyy element Publ., 2009.

[33] Shelestova V.A., Koval I.V., Bashlakova A.L. Effect of the anisotropy of fluoroplastic composites and the filler concentration on the coefficient of linear thermal expansion. Polimernye materialy i tekhnologii [Polymer Materials and Technologies], 2019, no. 3, pp. 64--68. EDN: IWBQDA

[34] Jiang Z., Yuan Y. Effects of particle size distribution of silica on properties of PTFE/SiO₂ composites. Mater. Res. Express, 2018, vol. 5, no. 6, art. 066306. DOI: https://doi.org/10.1088/2053-1591/aac99f

[35] Chen Y.C., Lin H.C., Lee Y.D. The effects of filler content and size on the properties of PTFE/SiO₂ composites. J. Polym. Res., 2003, vol. 10, no. 4, pp. 247--258. DOI: https://doi.org/10.1023/B:JPOL.0000004620.71900.16

[36] Rae P.J., Brown E.N. The properties of poly(tetrafluoroethylene) (PTFE) in tension. Polymer, 2005, vol. 46, no. 19, pp. 8128--8140. DOI: https://doi.org/10.1016/j.polymer.2005.06.120

[37] Brown E.N., Rae P.J., Orler E.B., et al. The effect of crystallinity on the fracture of polytetrafluoroethylene (PTFE). Mater. Sci. Eng. C, 2006, vol. 26, no. 8, pp. 1338--1343. DOI: https://doi.org/10.1016/j.msec.2005.08.009

[38] Mashkov Yu.K. Kompozitsionnye materialy na osnove politetraftoretilena. Strukturnaya modifikatsiya [Composite materials based on polytetrafluoroethylene. Structural modification]. Moscow, Mashinostroenie Publ., 2005.

[39] Brown E.N., Rae P.J., Gray G.T. The influence of temperature and strain rate on the tensile and compressive constitutive response of four fluoropolymers. J. Phys. IV, 2006, vol. 134, pp. 935--940. DOI: https://doi.org/10.1051/jp4:2006134143

[40] Chen C., Guo Z., Tang E. Determination of elastic modulus, stress relaxation time and thermal softening index in ZWT constitutive model for reinforced Al/PTFE. Polymers, 2023, vol. 15, no. 3, art. 702. DOI: https://doi.org/10.3390/polym15030702

[41] Negrov D.A., Eremin E.N. The influence of ultrasonic exposure on polytetrafluoroethylene structure modified with boron nitride. J. Phys.: Conf. Ser., 2017, vol. 858, art. 012021. DOI: https://doi.org/10.1088/1742-6596/858/1/012021

[42] Bosq N., Guigo N., Persello J., et al. Crystallization of polytetrafluoroethylene in a wide range of cooling rates: nucleation and diffusion in the presence of nanosilica clusters. Molecules, 2019, vol. 24, no. 9, art. 1797. DOI: https://doi.org/10.3390/molecules24091797

[43] Orman S., Dogu M., Ozbek B. Optimization of the filament winding process for glass fiber-reinforced PPS and PP composites using Box --- Behnken design. Polymers, 2024, vol. 16, no. 24, art. 3488. DOI: https://doi.org/10.3390/polym16243488

[44] Feng B., Fang X., Wang H.X., et al. The effect of crystallinity on compressive properties of Al--PTFE. Polymers, 2016, vol. 8, no. 10, art. 356. DOI: https://doi.org/10.3390/polym8100356