# Aluminum Composites With Small Nanoparticles Additions: Corrosion Resistance

L.E. Agureev, V.I. Kostikov, Zh.V. Eremeeva, A.A. Barmin, S.V. Savushkina, B.S. Ivanov

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L.E. Agureev, V.I. Kostikov, Zh.V. Eremeeva, A.A. Barmin, S.V. Savushkina, et al., Aluminum Composites With Small Nanoparticles Additions: Corrosion Resistance. Mechanics, Materials Science & Engineering Journal, 2016, 10.13140/RG.2.1.3617.6400. hal-01305957

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# Aluminum Composites With Small Nanoparticles Additions: Corrosion Resistance

L.E. Agureev¹ᵃ, V.I. Kostikov², Zh.V. Eremeeva², A.A. Barmin³, S.V.Savushkina⁴, B.S. Ivanov⁵

1. Researcher, Department of Nanotechnology, Keldysh Research Center, Russia

2. Doctor of Science, Associate Professor, Moscow State University of Steel and Alloys, Russia

3. Ph.D., Leading Researcher, Department of Nanotechnology, Keldysh Research Center, Russia

4. Ph. D., Senior Researcher, Department of Nanotechnology, Keldysh Research Center, Russia

5. Engineer, Department of Nanotechnology, Keldysh Research Center, Russia

a. trynano@gmail.com

**Keywords:** nanometric particles, aluminum composites, PM method, corrosion resistance, corrosion rate

**Abstract.** Research of corrosion resistance of the aluminum powder composites containing microadditives (0.01 – 0.15% is executed about.) zirconium oxide nanoparticles. Extreme dependence of speed of corrosion of aluminum composites in 10-% solutions of sulfuric and nitric acid from the maintenance of nanoadditives is shown. It has been shown the dynamics of mass loss of aluminum composites with nanoparticles of ZrO₂ during corrosion tests in acids solutions. The lowest corrosion rate of 3.36 mm/a of nitric acid was observed in the sample containing ZrO₂ 0.01 vol.% nanoparticles. For the case of sulfuric acid with the best result of 2.21 mm/a showed the material with 0.05 vol.% nano-additive.

**Introduction.** Nanotechnologies allow to create the strong and lightweight materials steady against various aggressive influences. Influence of nanoparticles on structure of material is caused by high superficial energy. There is a huge number of the works devoted to creation of composite materials, both with metal, and with a ceramic matrix, the nanoparticles strengthened by various concentration [1-7]. The light and strong materials, like aluminum alloys, for creation of various bearing designs of spacecraft have high value For astronautics [8-11]. In many works, the researchers conducted the development of aluminum composites containing nanoparticles of different nature in concentrations of more than 5 vol.%. It is rarely possible to find work devoted to low concentrations of nano-additives in aluminum [12-18]. This work is dedicated to the creation of aluminum composites with small amounts (0.01-0.15 %vol.) of nano-oxide ZrO₂ by powder metallurgy techniques.

Attention to small concentrations of the nanoparticles was based on the following provisions:

- high surface energy of nanoparticles;

- ease of uniform distribution of small amounts of nanoparticles and their disaggregation within the matrix;

- high impact of nanoparticles on the structure and properties of interfacial layers (matrix-MFS-nanoparticle).

The theory of irreversible processes and catastrophe theory say that small changes of operating parameters can jump the most important characteristics of the system [19,20]. Nanoparticles possessing high superficial energy, brings it in material and to interphase layer, influencing functional characteristics of composite in one direction or another. In this regard, a researcher separate issue is the determination of threshold effects of nanoparticles on the material and the search for the optimal technology of its receipt, depending on performance requirements.
The objective of the work was creation of aluminum composites, hardened with small additions of metal oxide nanoparticles like ZrO₂, and determination of its corrosion resistance in acids solutions. According to ideas of a number of famous scientists on the structure and properties of an interphase layer in solids nanoparticles having a high surface energy and making changes to structure of a matrix, even at very small concentration at the level of 0.001-0., about. % can cardinally change characteristics of material [21-24]. In tab. 1 influence of nanoparticles on properties of materials is briefly explained.

**1. Experimental procedure.** The charge used: as a matrix - aluminum powder with mean diameter of 4 µm (ASD-4, "SUAL", Russia), as reinforcer - nanopowder of zirconia (d<sub>av</sub> = 50 nm, S<sub>sp</sub> = 32 m²/g), Keldysh Research Center, Russia). The technology of preparation of composites consisted in the following. At the beginning aluminum powder was sieved through a sieve with a cell of 14 microns, then mixed with alcohol in a ratio of 1:4. Then, placed in an ultrasonic bath while stirring the mixture by rotary stirrer. Nanoparticles dispersed in ultrasound, after which the dispersion was added to the stirred alumina powder in alcohol. Quantity of nanoadditives varied from 0.01 to 1.5 vol.% Mixing lasted for 20-40 min. Drying of suspensions took place on air at a temperature of 60 ° C within 24 hours. The resulting blend compressed into a cylindrical mold with a pressure of 400 MPa. Next, sintering was performed in forevacuum at 640 ° C during 120-180 minutes.

The corrosion resistance was measured as follows. The total exposure time of samples was 15 hours. Samples were weighed prior to the experiment and during the measurements on scales up to 4-th sign. Samples were immersed in 10% solution acid (nitric acid or sulfuric acid). The difference in mass (primary - to experiment and obtained by checkweighing) was determined by mass loss of samples and plotted on it. At each check weighing and date recorded.

By results of tests of samples of aluminum composites for corrosion resistance values of speed of corrosion (γ) on a formula were calculated [25]:

$$ \gamma = \frac{x \cdot 365 \cdot 24}{\rho \cdot 1000}, \text{mm/a,} $$

where x₁ – mass loss rate, g/(m²·h);

ρ – density of material, g/cm³.

**2. Results and discussions.** The results are shown in Fig. 1-4. Particularly interesting is the results on corrosion resistance in a solution of nitric acid. The lowest rate of mass loss of 3.36 mm/a was observed in the sample containing nanoparticles of ZrO₂ 0.01 vol.% . For the case of sulfuric acid with the best result of 2.21 mm/a showed the material with 0.05 vol.% of the nano-additive.

The worst level of resistance in H₂SO₄ showed a sample with 0.15 vol.% of nanoparticles. Perhaps this is due to the number and size of the brought defects (cavities) by mixing aluminum powder with nano-additives . Nevertheless, it should be noted that all of the samples in comparison with pure aluminum sintered showed considerably greater resistance to corrosion in both acid solutions. While first (pure aluminum) at all dissolved in nitric acid after 15 hours and in sulfuric through 10.
<figure><img src="image_2.png" /><figcaption>Fig. 1. The dependence of the aluminum composites corrosion rate of the content nanoparticles ZrO₂ (test in a 10%-nitric acid solution).</figcaption></figure>

<figure><img src="image_3.png" /><figcaption>Fig. 2. Composites mass loss over time in a solution of nitric acid.</figcaption></figure>
<figure><img src="image_4.png" /><figcaption>Fig. 3. The dependence of the aluminum composites corrosion rate of the content nanoparticles ZrO₂ (test in a 10-% sulfuric acid solution)</figcaption></figure>

<figure><img src="image_5.png" /><figcaption>Fig. 4. Composites mass loss over time in a solution of sulfuric acid.</figcaption></figure>

**Summary.** Samples of aluminum composites with ZrO₂ nanoparticles were examined for corrosion resistance in 10-% solutions of nitric acid and sulfuric acid. The lowest corrosion rate of 3.36 mm/a of nitric acid was observed in the sample containing ZrO₂ 0.01 vol.% nanoparticles. For the case of sulfuric acid with the best result of 2.21 mm/a showed the material with 0.05 vol.% nano-additive.

**Acknowledgements.** Authors thank collectives NITU "MISIS" and Keldysh Research Center for the help in development of aluminum composites.

**References**

[1] Berestenko V.I., Torbov V.I., Torbova O.D. Poluchenie ul'tradispersnyh poroshkov dioksida cirkonija v plazme SVCh razrjada. Tezisy dokladov IV Vsesojuznogo simpoziuma po plazmohimii, g. Dnepropetrovsk, 1984 g., s. 59-60. - Berestenko V.I., Torbay V.I., Torbova O.D. Getting
ultrafine powders of zirconia in microwave plasma discharge. Abstracts of IV All-Union Symposium on Plasma Chemistry, Dnepropetrovsk, 1984, p. 59-60. [In Russian]

[2] Kevorkijan, V.M. Aluminum composites for automotive applications: a global perspective / VJVL Kevorkijan // JOM; -19991- №11.- P. 54- 58.

[3] Tang, F. The microstructure-processing-property relationships in an Al matrix composite system reinforced by Al-Cu-Fe alloy particles / Thesis D.Ph. -Iowa State University. - Ames, Iowa. - 2004.

[4] Kang Y.C., Chan S.L.-I. Tensile properties of nanometric Al2O3 particulate-reinforced aluminum matrix composites // Materials chemistry and physics, 85, 2004. P. 438-443.

[5] Ma Z.Y., Tjong S.C., Li Y.L. et al. High temperature creep behavior of nanometric Si3N4 particulate reinforced aluminium composite. // Materials Science and Engineering, A225, 1997. -P. 125-134.

[6] Mazahery A., Osfadshabani M. Investigation on mechanical properties of nano-Al2O3-reinforced aluminum matrix composites. // Journal of Composite Materials, 45 (24), 2011. -P. 2579-2586.

[7] Roduner Je. Razmernye jeffekty v nanomaterialah. -M.: Tehnosfera, 2010. -252 s.- E. Roduner size effects in nanomaterials. -M.: Technosphere, 2010. -252 p. [In Russian]

[8] Kostikov V.I., Varenkov A.N. Sverhvysokotemperaturnye kompozicionnye materialy. -M.: Intermet Inzhiniring, 2003. -560 s. - Kostikov V.I., Varenko A.N. Ultra high temperature composites. -M.: Intermet Engineering, 2003. -560 p. [In Russian]

[9] Tehnologija proizvodstva izdelij i integral'nyh konstrukcij iz kompozicionnyh materialov v mashinostroenii./ Nauchnye redaktory A.G.Bratuhin, V.S.Bogoljubov, O.S.Sirotkin. -M.: Gotika, 2003. -516 s.- The production technology and integrated manufacturing of composite structures in mechanical engineering. / Scientific Editors A.G.Bratuhin, V.S.Bogolyubov, O.S.Sirotkin. -M.: Gothic, 2003. -516 p. [In Russian]

[10] Pilotiruemaja jekspedicija na Mars./ Pod red. A.S.Koroteeva. -M.: Rossijskaja akademija kosmonavtiki imeni K.Je.Ciolkovskogo, 2006. -320 s. - Manned expedition to Mars. / Ed. A.S.Koroteeva. -M.: Russian Academy of Cosmonautics Tsiolkovsky, 2006. -320 p. [In Russian]

[11] Alifanov O.M., Andreev A.N., Gushhin V.N. i dr. Ballisticheskie rakety i rakety-nositeli. -M.: Drofa, 2004. -512 s. - Alifanov OM, Andreev AN, VN Gushchin and others. Ballistic missiles and launchers. -M.: Bustard, 2004. -512 p. [In Russian]

[12] Kalashnikov, I.E. Razvitie metodov armirovanija i modificirovanija struktury aljumomatrichnyh kompozicionnyh materialov [Tekst]: avtoref. dis. na soisk. uchjon. step. dokt.tehn.nauk (05.16.06)/ Kalashnikov Igor' Evgen'evich; IMET RAN. -Moskva, 2011. -26 s. - Kalashnikov IE Development of methods of reinforcement and modification of the structure of aluminum-matrix composite materials [Text]: Author. Dis. on soisk. Kazan. step. dokt.tehn.nauk (05.16.06) / Kalashnikov Tamm; IMET RAS. -Moscow, 2011. -26 p. [In Russian]

[13] Kurganova, Ju.A. Razrabotka i primenenie dispersnooprochnjonnyh aljumomatrichnyh kompozicionnyh materialov v mashinostroenii [Tekst]: avtoref. dis. na soisk. uchjon. step. dokt.tehn.nauk (05.16.06)/ Kurganova Julija Anatol'evna; IMET RAN. -Moskva, 2008. -26 s.- Kurganova, Y. Development and application of dispersion hardened aluminum-matrix composite materials in engineering [Text]: Author. Dis. on soisk. Kazan. step. dokt.tehn.nauk (05.16.06) / Kurganova Juliya; IMET RAS. -Moscow, 2008. -26 p. [In Russian]

[14] Grigorovich V.K., Sheftel' E.N. Dispersionnoeoprochnenie tugoplavkih metallov. -M.: Nauka, 1980. -302 s.- Grigorovich V.K., Sheftel' E.N. Precipitation hardening refractory metals. -M.: Nauka, 1980. -302 p. [In Russian]
[15] Sliney N.E. Kompozicionnye materialy dlja podshipnikov i uplotnitelej gazovyh turbin // Sovremennoe mashinostroenie, 1991, №3, s. 175-201. - Sliney N.E. Composite materials for bearings and seals of gas turbines // Modern Machinery, 1991, №3, p. 175-201. [In Russian]

[16] Sliding, wear response of an Al - Cu alloy the influence of SiC particle reinforcement and test parameters / Prasad B.K., Jha A.K., Modi O.P., Das S., Dasgupta R., Yegneswaran A.N. // J.Mater. Sci. Lett.- 1998.-17, № 13, p. 1121-1123.

[17] Hosking F.M., Portillo F., Wunderlin R., Mehrabian R. Composites of aluminum alloys; fabrication and wear behaviour // J.Mater.Sci. -1982.- 17, №2. P.477-498.

[18] Rohatgi P. Cast aluminum - matrix composites for automotive applications // JOM. -1991. - 43, №4.- P.10-16.

[19] Prigozhin I., Nikolis G. Samoorganizacija v neravnovesnyh sistemah: Ot dissipativnyh struktur k uporjadochennosti cherez fluktuacii. -M.: Mir, 1979. -512 s.- Prigogine I., Nikolis G. Self-organization in nonequilibrium systems: From dissipative structures for ordering through fluctuations. -M.: Mir, 1979. -512 p. [In Russian]

[20] Arnol'd V.I. Teorija katastrof. Teorija katastrof. «Sovremennye problemy matematiki. Fundamental'nye napravlenija. T. 5(Itogi nauki i tehniki VINITI AN SSSR». -M., 1988, s. 5-218. - Arnold V.I. Catastrophe Theory. Catastrophe Theory. "Contemporary Mathematics. Fundamental Directions. T. 5 (Results of Science and Technology VINITI. "-M., 1988, pp. 5-218. [In Russian]

[21] Obrazcov I.F., Lur'e S.A., Belov P.A. i dr. Osnovy teorii mezhfaznogo sloja. Mehanika kompozicionnyh materialov i konstrukcij, 2004, t. 10, №3, s. 596-612.- Samples IF, Lurie SA, Belov PA et al. Basic theory of the interfacial layer. Mechanics of Composite Materials and Structures, 2004, v. 10, №3, p. 596-612. [In Russian]

[22] Tajra S., Otani R. Teorija vysokotemperaturnoj prochnosti materialov. -M.: Metallurgija, 1986. -280 s.- Taira S., R. Otani theory of high-strength materials. -M.: Metallurgy, 1986. -280 p. [In Russian]

[23] Chuvil'deev V.N. Neravnovesnye granicy zjoren v metallah. Teorija i prilozhenija. -M.: FIZMATLIT, 2004. -304 s.- Chuvildeev VN Non-equilibrium grain boundaries in metals. Theory and Applications. -M.: FIZMATLIT, 2004. -304 p. [In Russian]

[24] Ohji T., Jeong Y.-K., Choa Y.-H., Niihara K. Strengtheing and toughening mechanisms of ceramic nanocomposites // Journal of American Ceramic Society. - 1998. - №81. - P. 1453-1460.

[25] Handbook of Corrosion Data / Ed. by B.D.Craig, D.S.Anderson. – Ohio: ASM International, 998 p.