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Effect of Al Element on the Microstructure and Properties of Cu-Ni-Fe-Mn Alloys

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Effect of Al Element on the Microstructure and Properties of Cu-Ni-Fe-Mn Alloys materials Article Effect of Al Element on the Microstructure and Properties of Cu-Ni-Fe-Mn Alloys Ran Yang 1, Jiuba Wen 1,2,*, Yanjun Zhou 1,2, Kexing Song 1,2,* and Zhengcheng Song 1 1 School of Materials Science and Engineering, Henan University of Science and Technology, Luoyang 471023, China; [email protected] (R.Y.); [email protected] (Y.Z.); [email protected] (Z.S.) 2 Collaborative Innovation Center of Nonferrous Metals, Henan University of Science and Technology, Luoyang 471023, China * Correspondence: [email protected] (J.W.); [email protected] (K.S.) Received: 28 August 2018; Accepted: 14 September 2018; Published: 19 September 2018 Abstract: The effects of aluminum on the mechanical properties and corrosion behavior in artificial seawater of Cu-Ni-Fe-Mn alloys were investigated. Cu-7Ni-xAl-1Fe-1Mn samples, consisting of 0, 1, 3, 5, and 7 wt % aluminum along with the same contents of other alloying elements (Ni, Fe, and Mn), were prepared. The microstructure of Cu-7Ni-xAl-1Fe-1Mn alloy was analyzed by Transmission Electron Microscopy (TEM), and its corrosion property was tested by an electrochemical system. The results show that the mechanical and corrosion properties of Cu-7Ni-xAl-1Fe-1Mn alloy have an obvious change with the aluminum content. The tensile strength has a peak value of 395 MPa by adding 3 wt % aluminum in the alloy. Moreover, the corrosion rate in artificial seawater of Cu-7Ni-3Al-1Fe-1Mn alloy is 0.0215 mm/a which exhibits a better corrosion resistance than the commercially used UNS C70600. It is confirmed that the second-phase transformation of Cu-7Ni-xAl-1Fe-1Mn alloy follows the sequence of α solid solution ! Ni3Al ! Ni3Al + NiAl ! Ni3Al + NiAl3. The electrochemical impedance spectroscopy (EIS) shows that the adding element aluminum in the Cupronickel can improve the corrosion resistance of Cu-7Ni-xAl-1Fe-1Mn alloy. Keywords: Cu-Ni-Al alloy; microstructure; mechanical property; corrosion resistance 1. Introduction Due to their high resistance to biofouling, heat transfer ability, and favorable resistance to the ravages of the marine environment, copper-based alloys are being offered as solutions to a range of industries requiring reliability in seawater to meet today’s exacting engineering challenges. It is well known that the addition of nickel to copper matrix can usually improve the comprehensive properties of the alloy, including corrosion and mechanical properties [1–3]. For instance, H. Nady et al. [4] investigated the stability of Cu-Al-Ni alloy in neutral chloride solutions with different nickel contents. It is confirmed that the corrosion rate of the alloy decreases as the content of nickel increases. However, its cost is quite high due to its high nickel content. In the 1930s, it was found that adding appropriate amounts of iron and manganese to copper–nickel alloys could improve corrosion–erosion resistance [5–7]. The most commonly used for seawater pipelines is the UNS C70600. The desired properties, including corrosion and mechanical properties, can be achieved by alloying elements aluminum [8–11]. One of the copper-based alloys Cu-14.5Ni-3Al-1.3Fe-0.3Mn has found increasing use in recent years. In previous studies [12–14], the good corrosion resistance of Cu-Ni-Al alloy in chloride solution was found to be attributed to the formation of a duplex oxide film. However, the effect of aluminum on the combination property of special Cupronickel alloys Cu-7Ni-xAl-1Fe-1Mn has not been in-depth studied. Thus, a study of aluminum effect of Cu-7Ni-xAl-1Fe-1Mn on the mechanical properties and corrosion resistance is necessary. Materials 2018, 11, 1777; doi:10.3390/ma11091777 www.mdpi.com/journal/materials Materials 2018, 11, x FOR PEER REVIEW 2 of 11 Materials 2018, 11, 1777 2 of 11 xAl-1Fe-1Mn has not been in-depth studied. Thus, a study of aluminum effect of Cu-7Ni-xAl-1Fe- 1Mn on the mechanical properties and corrosion resistance is necessary. For copper–nickel alloys, its ability of both mechanical strength and corrosion resistance in For copper–nickel alloys, its ability of both mechanical strength and corrosion resistance in seawater is crucial for engineering application. Therefore, we tried to reduce nickel content by adding seawater is crucial for engineering application. Therefore, we tried to reduce nickel content by adding aluminumaluminum and and expected expected better better results results with with the the CupronickelCupronickel alloy of of Cu-7Ni- Cu-7Ni-xxAl-1Fe-1MnAl-1Fe-1Mn alloy alloy (wt.%, (wt.%, usedused throughout throughout the the whole whole paper). paper). WeWe preparedprepared Cu-7Ni-Cu-7Ni-xAl-1Fe-1Mn with with different different aluminum aluminum contentscontents and and carried carried out out tensile tensile tests tests and and immersionimmersion test.test. The The experimental experimental results results will will provide provide guidanceguidance for for the the research research and and industrial industrial application application ofof Cu-7Ni-Cu-7Ni-xAl-1Fe-1Mn alloy. alloy. 2. Experimental2. Experimental 2.1.2.1. Materials Materials TheThe nominal nominal compositions compositions of theof designedthe designed Cu-Ni-Al Cu-N alloysi-Al alloys are listed are listed in Table in1 .Table The raw1. The materials raw werematerials electrolytic were copper,electrolytic nickel copper, block, nickel electrolytic block, electrolytic aluminum, aluminum, Cu-10 mass% Cu-10 iron mass% master iron alloy, master and Cu-22alloy, mass% and manganeseCu-22 mass% master manganese alloy. The master raw materialsalloy. The were raw smeltedmaterials in were medium smelted frequency in medium vacuum inductionfrequency furnace vacuum by feedinginduction sequence furnace by of copper,feeding nickel,sequence Cu-Fe of copper, master nickel, alloy, Cu-Fe Cu-Mn master master alloy, alloy, Cu- and electrolyticMn master aluminum. alloy, and The electrolytic raw materials aluminum. were The melted raw inmaterials proper were ratios melted at 1170–1200 in proper◦C ratios and deoxidized at 1170– by1200 magnesium °C and deoxidized alloy. by magnesium alloy. TableTable 1. 1.The The nominal nominal chemical chemical compositions compositions ofof the designed copper copper alloys alloys (wt (wt %). %). Number NumberCu CuNi Ni FeFe MnMn Al Al 1 Bal1 Bal7.0 7.0 1.01.0 1.01.0 0 0 2 Bal2 Bal7.0 7.0 1.01.0 1.01.0 1.0 1.0 3 Bal3 Bal7.0 7.0 1.01.0 1.01.0 3.0 3.0 4 Bal4 Bal7.0 7.0 1.01.0 1.01.0 5.0 5.0 5 Bal5 Bal7.0 7.0 1.01.0 1.01.0 7.0 7.0 2.2.2.2. Experimental Experimental Method Method MechanicalMechanical properties properties of of Cu-7Ni- Cu-7Ni-xxAl-1Fe-1MnAl-1Fe-1Mn alloy were were measured measured in in accordance accordance with with the the uniaxialuniaxial tensile tensile test. test. TensileTensile samplessamples were were prepared prepared according according to the tothe GB/T GB/T 228.1-2010 228.1-2010 method method of test of testat at room room temperature. temperature. Figure Figure 1 shows1 shows the tensile the tensile specimens specimens for room for temperatur room temperaturee tests. Tensile tests. testing Tensile testingwas performed was performed using a using SHIMADZU a SHIMADZU AG-I250KN AG-I250KN precision precisionuniversal testing universal machine testing with machine a constant with a constantstrain rate strain of 1 rate mm/min. of 1 mm/min. For transmission For transmission electron microscopy electron microscopy (TEM), thin (TEM), foil specimens thin foil specimens with a withdiameter a diameter 3 mm 3 mmwere were prepared prepared by means by means of both of both a double-jet a double-jet electropolisher electropolisher and and an anion ion thinner. thinner. MicrostructuresMicrostructures of of alloys alloys were were observed observed by by JEOL JEOLJEM-2100. JEM-2100. FigureFigure 1. 1.Drawing Drawingof of tensiletensile specimensspecimens (unit: mm). mm). TheThe corrosion corrosion resistance resistance of of Cu-7Ni-Cu-7Ni-xxAl-1Fe-1MnAl-1Fe-1Mn alloy was was measured measured by by static static immersion immersion corrosioncorrosion test test based based on on JB/T JB/T 7901-1999, 7901-1999, andand the corro corrosionsion rate rate was was calculated calculated by by weight weight loss loss method. method. TheThe sample sample size size was wasF30 Φ mm30 mm× 2.5 × 2.5 mm, mm, and and each each group group had had three three parallel parallel specimens. specimens. The The surface surface area of the sample was measured before immersion corrosion, and the quality was accurately determined by an analytical balance. The corrosion medium was artificial seawater; the artificial seawater composition is shown in Table2[ 15]. The test was carried out at room temperature for 10 days, and the corrosion medium was Materials 2018, 11, x FOR PEER REVIEW 3 of 11 area of the sample was measured before immersion corrosion, and the quality was accurately determined by an analytical balance. MaterialsThe2018 corrosion, 11, 1777 medium was artificial seawater; the artificial seawater composition is shown3 of 11in Table 2 [15]. The test was carried out at room temperature for 10 days, and the corrosion medium was replaced every seventh day. After completion of the test, with the volume ratio of 1:2 replacedhydrochloric every acid seventh solution, day. on After the corrosion completion after of cleaning, the test, the with corrosion the volume products ratio were of 1:2 removed hydrochloric after acidcleaning solution, with onalcohol, the corrosion and then after the cleaning, sample was the corrosionput in a drying products oven were drying removed to calculate after cleaning the quality with alcohol,loss of samples and then before the sample and after was putcorrosion. in a drying The ovencorrosion drying rate to calculateR was calculated the quality by loss the ofchange samples of beforesample and quality after corrosion.before and The after corrosion corrosion.
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