Abstract
Aluminum metal matrix composites are increasingly popular nowadays because of their wide range of uses. The low weight and excellent mechanical qualities, such as strength and hardness, of Al-Al2O3 composites make them useful in many fields, including automotive, aerospace, electronics, aeronautics, and military. Most of the engine components are made of aluminum-silicon alloys because of their excellent casting and forming properties. In engine components wear is a crucial parameter to be considered therefore in this investigation Al-Si alloy with varying percentages of V2O5 has been considered to develop the Al-Al2O3 composite and evaluate its tribological aspect. For composite development, a novel in-situ approach has been used with the help of the stir-casting method. The tribological behavior of the different composites was examined experimentally and studied with sliding distance, applied load, and the amount of reinforcement. Composites show a significant increase in hardness relative to the base alloy because of the generation of hard alumina particles within the melt. The wear behavior of in-situ Al-Al2O3 composites was studied using a pin-on-disc setup. In terms of COF and wear rate, the composite with a 1% addition of V2O5 performed better in the trial.
Introduction
A wide variety of industries around the world use aluminum alloys because of their exceptional qualities, including electronics, automobiles, aeronautics, and the packaging industry.1–3 As compared to other nonferrous materials, aluminum alloys have a better specific strength, greater ductility, and are more cost-effective. 4 In order to reduce the weight of automobiles, composite materials are being employed to replace steel in various areas of the vehicle. Aluminum-silicon alloys find extensive use in the automotive industry, particularly in engine components due to their excellent castability.
Al-Si is one of the most used aluminum alloys because of its excellent mechanical strength and ease of casting. Hypoeutectic and hypereutectic type Al-Si are commercially available. 5 Ceramic or oxide particles can greatly improve the mechanical and tribological properties of aluminum alloys, despite the alloys’ inherent weak tribological characteristics. These composites with embedded aluminum alloys go by the designation “Aluminum matrix composites” (AMCs). Due to these features, AMCs have attracted the attention of scientists across disciplines.6,7
AMCs can be prepared in a wide variety of techniques, including mechanical alloying, stir casting, squeeze casting, etc. 8 Among these many approaches, in-situ fabrication and ex-situ procedure stand out as particularly noteworthy. The former method involves the production of alumina particles within the melt by the chemical interaction of oxide and nitride with the molten metal. Particles are added to the metal from the outside in the latter method. The in-situ composites have potential advantages over ex-situ composites like higher interfacial strength, better wettability, better particle size, uniform distribution, and improved mechanical properties at an economic cost of production. The major challenge of the fabrication of in-situ composites includes a limited choice of reinforcements. The reinforcements should be thermodynamically feasible as the nucleation and growth processes govern their size and shape. 9 Liquid metallurgy route, especially the stir casting is a widely preferred technique for processing. It is simple, cost-effective, and the most commercially viable technique at present. 10
In view of the current demand for lightweight materials with excellent strength and stiffness, techniques for developing metal-matrix composites have received a lot of attention. Aluminum alloys have unfavorable wear properties however, the addition of ceramic or oxide particles significantly supports eliminating this drawback. In this context, numerous ceramic particles like SiC, TiB2, MoO3, ZnO, ZrB2, TiO2, etc., are incorporated into aluminum alloys to enhance their mechanical and tribological properties. Great improvements have been reported in the properties by the addition of non-metallic phases (like borides, nitrides, oxides, carbides, etc.) to aluminum alloys.11,12 Many oxides such as MnO2, ZnO, MoO3, CuO, SO3, and CeO2 have been used to fabricate in-situ Al2O3/Al composites. These metal/nonmetal oxides are added externally and get reduced by liquid aluminum to form an in-situ Al2O3/Al composite. Alumina and other useful materials generate within the melt due to the reduction reaction and contribute to the enhancement of properties. Among numerous dispersoids, Al2O3 particles are most favored for Al-based alloy due to good chemical compatibility and the absence of unwanted reactions among the matrix and reinforcing particles. In-situ generated fine Al2O3 particles impart better properties due to uniform distribution and intrinsic and extrinsic effects.
A study was conducted to determine the wear rate of AA6351 with a ZrB2 in-situ composite ranging from 0 to 9 percent. The wear rate was decreased by both the heat treatment and the addition of ceramic particles. 13 TiB2 was utilized as a grain refiner in an Al-7Si matrix, and the resulting alteration in Si morphology was found to increase the wear rate. 14 The wear and friction behavior of cast in-situ Al-Al2O3 composite was reported by a researcher. The composite was developed by the addition of MnO2 particles to the melt, which reduced it to Al2O3 particles. The investigation shows a decrement in wear rate as well as in volume loss over the base matrix. The effect of porosity on the wear rate has been analyzed. A higher wear rate has been reported with growing porosity content. 15
TiO2 and MoO3 particles have been used to develop different composites. The oxide particles were added in the melt of Al-5wt%Mg alloy for reduction to form alumina particles. By increasing the particle content, the wear rate decreases for the same testing conditions. Wear debris produced during dry sliding wear forms a transfer layer that helps in improving the wear resistance at low loads but not for high loads. 16 The wear properties of A356 with 10wt% TiB2 have been investigated. The composites were prepared using K2TiF6 and KBF4 salts. The resultant TiB2 produced from the reaction between salts was added to the A356 alloy melt. Al-2 wt. % Sc alloy was added in A356 alloy and A356-10wt. % TiB2 melt. The morphology of Si particles changes from a needle-like shape to a fine spheroidal shape due to the presence of Sc. The addition of Sc helps in reducing the secondary dendrite arm spacing by 50%. Both hardness as well as wear resistance increase due to Sc and TiB2 addition. 17 Another work for the same composite reveals that the wear rate strongly depends upon the amount of TiB2 content in the composite instead of the overall hardness of the composite. 18
Several oxide materials such as MnO2, ZnO, CuO, MnO2, and MoO3 are well-known fillers for high-performance Al-Al2O3 composites. However, other alternate oxide materials such as V2O5 have not been explored up to the full extent. Despite being cost-effective, ease of processing, and uniform distribution, liquid processing based in-situ method, using V2O5 has not been used to fabricate Al-Al2O3 composites. The influence of V2O5 filler on the mechanical and tribological properties of Al-Al2O3 composite has not been investigated. Nanoparticles of V2O5 increase antiwear properties when mixed in oil and the lowest wear rate has been reported by adding 0.2 wt. % in oil. 19 Vanadium acts as a grain refiner and it has been used by many researchers but not in the oxide form. A powder metallurgy route has been used by a researcher to form an Al-(Al3V-Al2O3) composite. 20
Within the scope of this study, an in-situ approach was used to develop a particulate composite by incorporating nano-sized Al2O3 into an aluminum-silicon alloy. Detailed research was conducted on the mechanical and wear properties of the composite material. The purpose of this study is to investigate the factors that have an impact on wear rate, specifically the normal load, the sliding distance, and the reinforcement.
Experimental procedure
Development of composite
In this research first, the composite was produced utilizing Al-7Si alloy as a matrix with the chemical composition of 6.94% Si, 0.22% Fe, 0.17% Cu, 0.41% Mg, 0.11% Mn, and Al balance (all in wt. %). V2O5 particles extra pure with 99.3% purity and a particle size of 250 nm were used as a reinforcement. An optical emission spectrometer (OES; AMETEK Germany) was used to find out the composition of the procured material. Figure 1 shows a furnace with a bottom pouring facility that was used for casting. In the stir-casting method, stirring contributes to transferring particles into the molten alloy and helps to disperse and suspend the particles in the melt. For this purpose, a stainless steel stirring blade with three bents was used for stirring. To prevent steel from dissolving in molten aluminum, the blade was coated with a fine graphite paste. 21 The parameters used are mentioned in Table 1.

Bottom pouring furnace and the samples obtained. 21
Process parameters used for the composite development.
The melting temperature parameter has been selected based on differential thermal analysis.
DTA was performed utilizing the EXSTAR TG/DTA 6300. The experiment was carried out using Al-7Si and vanadium pentoxide powder. The sample was heated in an Al2O3 pan at 10°C min−1 in the presence of a nitrogen environment. Figure 2 depicts an endothermic peak at 583°C, corresponding to the melting of Al-7Si alloy. Another observation at 673°C showed the melting of vanadium pentoxide. The decline in peak has been observed between 800°C and 850°C, this might be the formation of another phase. In the current study, the casting has been done considering the parameters according to DTA analysis. A small amount of magnesium is added to the Al-7Si melt in the presence of argon gas. CaF2 is used as flux while mixing V2O5 in aluminum melt. This increases the fluidity of the slag and does not react chemically with V2O5. Magnesium helps to improve the wettability of in-situ formed particles, allowing them to stay inside the melt. To disseminate the preheated particles of V2O5, the stirrer's position was kept constant in the melt. The melt was poured into a preheated steel mould after 15–20 minutes of mixing. At this point, the melt was degassed in preparation for vacuum casting.

Differential thermal analysis curve carried out at 10°C per minute.
Designation of the developed composite
Three different composites were developed by adding 1, 3, and 5% V2O5, and all the composites have been designated by sample name. The nomenclature given to the composites is based on material composition and is shown in Table 2.
Nomenclature of samples.
Where A represents the aluminum-7% silicon alloy, V followed by the number represents the wt. % of V2O5 added.
Pin on disc test setup
A pin-on-disc tribometer was used to study the tribological properties of different composites shown in Figure 3. All tests were carried out in accordance with standard protocols (ASTM G99-95). A personal computer was connected with a pin-on-disc setup for data acquisition. LVDT was employed for the wear determination in micrometers and the mounted sensor sensed the changes in terms of frictional forces. For each sample, pin weight was measured before and after the test. A highly sensitive weighing scale was used to assess the weight loss of a pin under various loads and at various sliding distances (Shimadzu AX 200).

Pin on disc tribotester.
The height and the diameter of flat cylindrical pins used for the test were 30 mm and 10 mm respectively. The counterface disc of EN-31 steel (60HRC) of 165mm diameter and 8mm thickness was used with 145 mm as the maximum track diameter. The chemical composition of EN31 steel measured with the OES was found C1, Mn 0.5, Si 0.35, S 0.05, P 0.05, Cr 1.3, and Fe balanced. To make sure that the surfaces are clean ethyl alcohol was used before each experiment. All experiments were conducted at ambient temperature and for each experiment; a 40 mm track diameter was used. The normal loads of 10, 20 and 30 N were applied at 0.83 m/s sliding velocity for a 1000m sliding distance for all the experiments.
The pin samples were properly cleaned and then polished with different grit-size paper ranging from 400 to 1000. The disc was cleaned with A350 Emery paper after each test. The pins were first cleaned with C2H5OH and an ultrasonicator and then kept in a vacuum to prevent them from corrosion. After the test, worn surfaces were examined with a trinocular stereo zoom microscope. To obtain accurate results an average of three readings have been reported.
Results and discussion
XRD analysis
From the thermodynamic aspect, alumina is formed by the reduction of V2O5 according to the following reaction.

XRD pattern of base alloy and its composites.
α-Al2O3 and Al-Si peaks were the major components of the composites because alumina was so stable, that no further reaction products were discovered in the compositions. When we looked at Al2O3, we did not see all the predicted diffraction peaks, even though the matrix peaks were clearly visible. There were distinct differences between the diffraction patterns because of the low volume fraction of Al2O3 in the Al-Si matrix and the fine powder size in mixtures. A very small variation in the peaks was observed, which may be due to the lesser addition of particles. 23 Another reason for the small difference in the peaks could be the masking of the strong peaks of Al on the weaker peaks of other phases identified as Al3V and Al2O3 in the composite, confirming the occurrence of in-situ reaction. 23 Moderate peaks of Al3V and Al2O3 were present in the case of Al-1% V2O5 as compared to Al-3% V2O5 and Al-5% V2O5 composites. This may be due to the occurrence of a nearly complete reaction between Al-Si alloy and V2O5 particles for Al-1% V2O5 composites. The reduction of aluminum can be easily identified by a decrement of aluminum peaks up to 3% V2O5 particle addition.
SEM analysis
Figure 5(a), (b), and (c) shows the SEM images of Al-7Si with 1, 3 and 5% addition of V2O5 respectively. From the images, it is clear that alumina content increases with the increasing content of V2O5 particles. A uniform distribution of nanoparticles is depicted in composites with a lower percentage of Al2O3. For composites with more percent of nanoparticles in the case of AV5, the agglomeration generated by the clustering effect of particles can be shown in Figure 5 (c).

SEM images of (a) AV1 (b) AV3 (c) AV5.
The EDAX analysis shown in Figure 6 confirms the formation of nearly stoichiometric Al2O3 in the composite as the atomic percentage of aluminum and oxygen are nearly 40:60. This is attributed to the proper mixing of reinforcement. Further addition increases the agglomeration of nanoparticles and lowers the O2 element and the results are well aligned with other researchers. 24 The size of alumina has been estimated with the help of image J software uniform dispersion of fine Al2O3 particles of 126 nm average size generated through in-situ reaction.

EDAX of AV1 composite.
Mechanical properties
Alloy Al-7Si and its composites are listed in Table 3 of this document. The hardness of the material was assessed from a variety of different viewpoints, with an average value taken into account. A 1% increase in oxide particle concentration increases hardness by 28% to 30%. Figure 7 depicts the relationship between hardness variation and the amount of V2O5 addition. At 100 gf load, the graph displays the highest hardness value for AV1, and it then begins to decrease. The improvement in the properties attributed to the hard alumina particles, the refinement of alpha aluminum (α–Al), and the change in the size of eutectic silicon particles as reported in the previous report. 25 The hardness of composites increases linearly with the weight fraction of the particles till 1% addition. This is due to the fact that Al2O3 has a substantially higher hardness than the matrix and the uniform distribution of Al2O3 and the smaller grain size of the matrix. After that due to more alumina particle generation, agglomeration occurs and properties start deteriorating. 26

Microhardness variation concerning V2O5 addition.
Mechanical properties of base alloy and its cast composites.
# Standard deviations are shown within parentheses.
Coefficient of friction analysis
An experimental study has been carried out to estimate the effect of normal load and the weight percentage of V2O5 particles, on the wear rate of Al-Al2O3 composites. The coefficient of friction is measured for different composites at different sliding distances ranging from 200 to 1000 at 10, 20, and 30 N loads under constant 0.83 m/s sliding velocity. Figure 8 shows the behavior of COF with varying sliding distances at different loads for all the composites.

Coefficient of friction at (a) 10 N (b) 20 N and (c) 30 N load at a constant sliding velocity of 0.83 m/s.
It is revealed from Figure 8(a), (b), and (c) that at low load, COF increases continuously with sliding distance with one or two exceptions. At intermediate loads, the maximum COF is observed at a small sliding distance (200 m) and decreases afterward with some exceptions. At higher loads, the coefficient of friction increases continuously up to a sliding distance of 600 m and decreases afterward. Among all the in-situ composites and the matrix alloy, Al-7Si base alloy exhibits the highest coefficient of friction due to the non-presence of hard alumina particles, whereas AV1 in-situ composite displays the lowest COF due to the homogeneous distribution of lower amounts of nanoparticles in the aluminum alloy. Beyond 1% addition in the case of AV3 and AV5, the coefficient of friction increases due to an increase in agglomeration and clustering effect 27–29 Figure 9 shows the average COF with load for the base aluminum-silicon alloy and its cast composites under constant sliding velocity and sliding distance. The figure reveals that the COF varies with load and decreases for the composite with high microhardness which conforms to Archard's law of wear.30,31 The base alloy matrix reveals the highest COF and the in-situ composite having 1% V2O5 shows the lowest COF at all loads.

Coefficient of friction vs load at 1000 m for 0.83 m/s sliding velocity.
The reduction in the COF at 1000 m for 10 N load is about 30%, 21%, and 6.5% for AV1, AV3, and AV5 respectively over the base aluminum-silicon alloy. A similar trend of reduction in the COF is obtained at 20 and 30 N loads. The significant reduction in the COF may be ascribed to the decrease in the contacting area of two mating surfaces owing to the existence of uniformly distributed fine Al2O3 (alumina) particles in the Al-Si matrix. With increases in the weight percentage of V2O5 particles, more alumina particles are generated which agglomerate to form clusters of the particles. This clustering of agglomerated particles affects the size and dispersion of alumina particles which eventually leads to an upturn in the coefficient of friction. 29
Volume loss
Figure 10 indicates the volume loss of pins made by base alloy and different composites with load for 1000 m sliding distance (steady state regime). This figure reveals that with the increase in load the volume loss for base Al-Si alloy and its cast composites increases.

Volume loss vs load for 1000 m sliding distance.
Volume loss for all the composite decreases as compared to pure Al-Si alloy. Volume loss also increases with an increase in V2O5 addition, as the in-situ composite with 1% V2O5 particle addition exhibits lower volume loss as compared to other in-situ composites having more wt. % of V2O5. This reduction is attributed to the presence of hard alumina particles in the matrix. Less addition of V2O5 leads to the uniform dispersion of the optimum quantity of fine coherent Al2O3 particles in the matrix. Higher addition leads to the agglomeration of Al2O3 particles causing incoherency with the matrix. These incoherent particles may detach easily during wear testing as reported by others. 32 The average reduction in volume loss is determined to be 47.3%, 36.3%, and 27.5% for composites with 1%, 3%, and 5% V2O5 addition respectively as compared to base Al-Si alloy.
Wear
Figure 11 clearly describes the wear pattern of aluminum-silicon and its different composites under dry sliding conditions. Bulk wear increases with load for the base alloy and the composites. It is generally known that increasing the amount of reinforcing particles reduces the wear of in-situ composites because hard particles act as a load bearer and in the case of in-situ, it produces pure interfaces which in turn enhance the interfacial bonding strength. 33 However, other researchers believe that the porosity content of cast in-situ composites increases as the particle content increases, resulting in a deterioration in their wear resistance. Porosity generation in composites can be attributed to the dismal wetting of reinforced particles in molten aluminum alloy. 34

Wear rate of different composites at different loads.
At low loading conditions, the addition of particles creates a compressed protective layer, which leads to a decreasing wear rate. 35 However, the formation of new oxide debris during the dry sliding test at high loads locks the previously created debris, resulting in surge wear. The specific wear rate tends to rise as additional nanoparticles are added, e.g. AV5. This increase is due to the presence of porosity in the cast in-situ composite. Higher porosity increases the effective area of contact, which finally raises the wear rate. 33 As a result, porosity not only softens the material but also fosters delamination and subsurface cracks.
Increase in applied load results in the worn-out surface of the material. Because of the micromachining action at low loads, a portion of the counterface material separates and oxidizes. Between the mating surfaces, this oxidized material (Fe2O3) forms a tribo layer. Wear tests have shown that the creation of this tribo layer, which serves as a solid lubricant between the mating surfaces, is responsible for the temporary reduction in wear rate. When large loads are applied, the tribo layer is dismantled, resulting in delamination. High load causes high temperatures near surfaces and lowers the shear strength in the materials’ subsurface layers, promoting excessive material transfer. Similar kind of transfer layers has been perceived by various investigators specifically in the case of aluminum-based composites.32,36,37
Effect of reinforcement
It is evident that nanoparticle generation ameliorates the hardness of composites, which resulted in a lower wear rate in comparison to base matrix alloy. According to researchers, excessive adhesive wear is determined largely by the material's hardness. 29 Further evidence and support from the practical work suggested that, scuff and seizure, the onset of adhesive process stunting when the hardness of mating parts increased. 38
There is a pure and clean interface between the Al-7Si matrix and Al2O3 particles leading to the better load-bearing capacity of the composite which in turn brings down the rate of wear with the addition of V2O5 particles. The presence of dislocations surrounding the Al2O3 particles due to the difference in coefficient of linear thermal expansion between matrix and reinforcement also increases the resistance to wear.
Effect of sliding velocity
High sliding velocity and high load lead to comparatively more heat generation between the mating surfaces. The heat generation results in mellowing down surfaces, which in turn increases the penetration of the counter surface into the pin (composite) surface. Different thermal expansion of Al2O3 particles and the matrix is vital in wearing down the composites. This incongruity in terms of thermal expansion causes the development of stresses at the interface. As the sliding velocity increases, the heat generation also surges to a high value, leading to an increase in interfacial stress. When this interface stress surpasses the interface bond strength, cracks may develop in the matrix region or particles may leave their place to create a cavity. 32 The presence of Al2O3 particles, secondary hard phases, and intermetallic phases restricts the metal flow during the dry sliding wear as these hard particles/phases decrease the area of contact between the mating surfaces and decrease material removal during dry sliding wear.14,39
As there is limited work available with the V2O5 in aluminum-based composite especially fabricated by stir casting method therefore it is compared with other oxide particles and externally added Al2O3 nanoparticle based composites. The properties of as-cast Al- Al2O3 composites fabricated under the present investigation are compared with those of the composites fabricated by Sajjadi and Ezatpour. In their research, they have taken A356 as a matrix and Al2O3 as reinforcement. Two different types of composites were made by adding Al2O3 in nano and micro sizes. Two different methods of fabrication; stir casting and compo casting have been used for both types of composites. The results obtained by them for the micro size Al2O3 composites, fabricated by stir casting are considered for comparison. The present work shows better results in terms of mechanical properties when compared with an equal volume fraction of alumina used. 40
Conclusion
Al-Al2O3 composite was successfully fabricated. The Al2O3 particles in the matrix were clearly visible in the SEM images. However, a high percentage of Al2O3 shows agglomeration.
Developed MMC exhibits a significant improvement in mechanical properties due to the presence of nano size alumina formation within the matrix, which significantly contributes to strength as per the Orowan mechanism. AV1 composite showed the highest hardness and tensile strength among other composites including the base alloy.
A significant improvement in the coefficient of friction was observed at low loads. A decrease in COF at 1000 m for 10 N load was about 30%, 21%, and 6.5% for AV1, AV3, and AV5 respectively over the base aluminum-silicon alloy.AV1 shows the lowest COF and highest hardness which conforms to Archard's law of wear.
A great improvement in the wear behavior was observed in all composites as compared to the base alloy. The amount of reinforcement, size, and method of fabrication plays a significant role in the mechanical and tribological properties.
The present work provides a cost-effective route for the development of in-situ composite. It opens the emerging area of research in the lightweight aluminum-based composite. As per the tribological results, the developed composite can have applications in automotive components especially the piston, valves, and other components having the dynamic pair. The work also enriched the knowledge base in the field of stir-cast aluminum-based composites.
Footnotes
Declaration of conflicting interests
The authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.
Funding
The authors received no financial support for the research, authorship, and/or publication of this article.
