UDK 669.715:669.3:620.18 Izvirni znanstveni članek ISSN 1580-2949 MTAEC 9, 36(1-2)49(2002) B. ZLATIČANIN ET AL.: THE EFFECT OF COPPER CONTENT ON THE MICROSTRUCTURE OF ... THE EFFECT OF COPPER CONTENTS ON THE MICROSTRUCTURE OF THE ALUMINIUM-COPPER ALLOY VPLIV VSEBNOSTI BAKRA NA MIKROSTRUKTURO ZLITIN ALUMINIJ - BAKER Biljana Zlatičanin1, Stevan \uri}2, Branka Jordovi}3, Biljana Stojanovi}4, Branislav Radonji}1 1University of Montenegro, The Faculty of Metallurgy and Technology, Cetinjski put bb, 81000 Podgorica, Yugoslavia 2University of Belgrade, 11000 Belgrade 3The Faculty of Technical, Cacak, Yugoslavia 4CMS - Belgrade, 11000 Belgrade biljanaŽl.cis.cg.ac.yu Prejem rokopisa - received: 2001-04-02; sprejem za objavo - accepted for publication: 2001-10-05 The effect of copper content, in the interval range from 0% to 33%, on the microstructure of aluminium-copper alloys was examined. Using X-ray powder diffraction we established that the tetragonal intermetallic compound Al2Cu with the lattice parameters: a = 6,076 Ĺ, c = 4,886Ĺ and V = 180,4 Ĺ3, is formed across the whole range of copper additions. The effect of the copper content on the microstructure was monitored quantitatively. Using automatic image analysis we were able to measure the linear intercept grain size, the secondary dendrite arm spacing (DAS), the size of eutectic cells (Le), as well as the size distribution and volume fractions of the a-solid solution and the eutectic. In alloys containing more copper the average value of the DAS was found to decrease. Key words: copper-aluminium alloy, intermetallic compound, Al2Cu, lattice parameters, solidification structure Raziskan je bil vpliv bakra v razponu od 0 % do 33 % na mikrostrukturo zlitin aluminij-baker. Z uklonom rentgenskih žarkov je bilo potrjeno, da v vsem razponu vsebnosti bakra nastaja intermetalna faza Al2Cu s parametri kristalne mreže a = 0,6076 nm, c = 0,4886 nm in V = 18,04 nm3. Vpliv bakra na mikrostrukturo je bil določen s kvantitativnimi meritvami. Z avtomatsko analizo slike so bile določene linearne intercepcijske dolžine, širina sekundarnih dendritnih vej (DAS) in velikost evtektskih celic (Le). Določeni so bili tudi velikostna porazdelitev in delež trdne a-raztopine in evtektika; širina sekundarnih dendritnih mej se zmanjšuje pri naraščanju vsebnosti bakra. Ključne besede: zlitine aluminij-baker, intermetalna spojina Al2Cu, parametri kristalne mreže, strjevalna struktura 1 INTRODUCTION Standard industrial aluminium-copper alloys solidify with the formation of a dendritic structure, however, a tendency to form with a globular structure at higher copper contents was reported1,2 and confirmed in our earlier unpublished work. We have examined the solidification structure in the aluminium-copper system over a wide range of copper content. The experimental work consisted of melting and casting alloys with different compositions representing the range of copper contents in standard aluminium alloys, as well as alloys with higher copper contents for an investigation of alloys with X-ray powder diffraction and quantitative microstructure analysis. The hardness and compression strength of the alloys were also determined. The solidification structure was modified by the addition of the AlTi5B1 alloy in the range of 0.02 to 0.25 % Ti. 2 EXPERIMENTAL The X-ray diffraction analysis was performed on pure aluminium and pure copper, as well as on the aluminium-copper alloys: AlCu5, AlCu8, AlCu15, AlCu15Mg3, AlCu23, AlCu33, using a wide range of angles (29) from 5 to 100° with a step of 0,02° and a holding time of 0,4 s. A diffractometer with a graphite monochromator and a constant divergence slit (D) of 1mm was used. The current and the voltage of the X-ray tube during the analysis were 32mA and 40kV, respectively. The width of the receiving slit (R) was 0,1mm, corresponding to fine focussed X-ray tubes. The radiation was the Cu Koc1/a2, doublet (Ŕoc1= 1,54051 Ĺ and Xa2 = 1,54433 Ĺ). Special attention was given to an assessment of the different structural parameters by quantitative microstructure analysis, which was considered as more reliable, accurate and faster than conventional manual methods of microstructure analysis. 3 RESULTS AND DISCUSSION 3.1 Results of the X-ray analysis From the X-ray diffractograms the microstructural parameters have been calculated: the average sub-grain size (Table 1), the microvoltage (Table 2) and the dislocation density (Table 3). MATERIALI IN TEHNOLOGIJE 36 (2002) 1-2 49 B. ZLATIČANIN ET AL.: THE EFFECT OF COPPER CONTENT ON THE MICROSTRUCTURE OF Table 1: Average crystallite size in the crystallographic direction Š110] for different copper contents in aluminium-copper alloys Tabela 1: Povprečna velikost kristalitov v kristalni smeri Š110] pri različni vsebnosti bakra v zlitinah aluminij-baker Type of sample Average crystalite size, Ĺ AlCu5 (0,08% Ti) 641 AlCu8 (0,08% Ti) 561 AlCu15 (0% Ti) 748 AlCu15Mg3 (0,08% Ti) 374 AlCu23 (0,08% Ti) 897 AlCu33 (0,08% Ti) 748 Table 2: The microvoltage in the crystallographic direction Š110] for different copper contents in aluminium-copper alloy Tabela 2: Mikronapetosti v kristalni smeri Š110] pri različni vsebnosti bakra v zlitinah aluminij-baker Type of sample Microvoltage (mV) AlCu5 (0,08% Ti) 0,1920 AlCu8 (0,08% Ti) 0,2194 AlCu15 (0% Ti) 0,1644 AlCu15Mg3 (0,08% Ti) 0,3305 AlCu23 (0,08% Ti) 0,1371 AlCu33 (0,08% Ti) 0,1644 Table 3: Dislocation density in the direction Š110] for different copper contents in aluminium-copper alloys Tabela 3: Gostota dislokacij v kristalni smeri Š110] pri različni vsebnosti bakra v zlitinah aluminij-baker Type of sample Dislocation density, cm-2 AlCu5 (0,08% Ti) 7,3 x 1010 AlCu8 (0,08% Ti) 9,5 x 1010 AlCu15 (0% Ti) 5,4 x 1010 AlCu15Mg3 (0,08% Ti) 21,4 x 1010 AlCu23 (0,08% Ti) 3,7 x 1010 AlCu33 (0,08% Ti) 5,4 x 1010 Table 4: Grain size for different copper contents in aluminium-copper alloys Tabela 4: Velikost zrn pri različi vsebnosti bakra v zlitinah aluminij-baker Type of sample average, µm min, µm max, µm RSE, % Al (0%Ti) 537,69559 78,94737 2210,52632 6,53767 Al (0,08%Ti) 101,31646 18,98734 303,79747 3,45954 AlCu5 (0,08%Ti) 85,72152 18,98734 215,18987 2,59978 AlCu8 (0,08%Ti) 74,49620 12,65823 189,87342 2,81358 AlCu15 (0%Ti) 810,48387 193,54839 2709,67742 5,06863 AlCu15 (0,02%Ti) 230,63492 47,61905 777,77778 3,78064 AlCu15 (0,08%Ti) 53,00000 9,37500 162,50000 2,94158 AlCu15 (0,15%Ti) 49,71717 15,15152 121,21212 2,99332 AlCu15 (0,25%Ti) 48,39966 10,10101 126,26263 2,76879 AlCu15Mg3 (0,08%Ti) 87,31313 30,30303 212,12121 2,42991 AlCu23 (0,08%Ti) 57,71717 20,20202 151,51515 2,91693 AlCu33 (0,08%Ti) 366,78722 113,92405 721,51899 9,03907 The sub-grain is the range of the lattice of the crystal grain from which the X-rays are coherently diffracted. The sub-grains are separated by dislocation walls and have a space orientation which is different by several 50 angle minutes. Using X-ray diffraction of polycrystals, the sub-grain is defined as a range of quantitative values, starting from the average length in a definite crystallo-graphic direction, through the average volume, to their dimensional distributions. Microvoltages are the most-often used parameter of crystal-lattice deficiency and represent the deviations in the distance d between twocrystal planes having identical šhkl} indices in a determined crystallographic direction. This kind of a crystal-lattice deficiency is the result of the distribution of dislocations or the difference in the chemical composition of the alloy. The dislocation density is alsoa parameter of the lattice defectiveness. It is most often defined as the minimum density of dislocation-free areas compared to the number of dislocations on the crystallite edges. The X-ray examination of the different aluminium-copper alloys showed very high microvoltage values (Table 2), which were expected because of the way the alloys were manufactured and the method used to investigate them. 3.2 Quantitative microstructure analysis The grain size (minimum, maximum and average values), the relative standard measuring errors (RSEs) (see Table 4), the dendrite arm spacing3 (DAS) (see Table 5), the eutectic cell length (Le) (see Table 6), as well as the size distribution and the volume share of the a-solid solution and eutectic were measured. Table 5: Dendrite arm spacing (DAS) for different copper contents in aluminium-copper alloys Tabela 5: Širina sekudarnih dendritnih vej pri različni vsebnosti bakra v zlitinah aluminij-baker Type of sample average, µm min, µm max, µm RSE, % Vv,ah.s. % AlCu5 (0,08%Ti) 30,19837 1,63 134,69 2,9381 84,75599 AlCu8 (0,08%Ti) 26,88980 1,63 102,04 2,3774 83,48839 AlCu15 (0%Ti) 20,22536 1,63 123,27 2,1228 75,14505 AlCu15 (0,02%Ti) 23,13044 1,63 112,65 2,2226 76,67941 AlCu15 (0,08%Ti) 23,30254 1,22 90,61 2,3228 74,38530 AlCu15 (0,15%Ti) 20,66491 1,22 102,86 2,1645 74,28727 AlCu15 (0,25%Ti) 18,98537 1,63 92,24 2,0971 71,12862 AlCu15Mg3 (0,08%Ti) 19,65894 1,63 102,86 2,0845 76,84319 AlCu23 (0,08%Ti) 17,37533 1,63 79,18 2,0074 54,49193 The copper content in the standard aluminium alloys was up to about 5%, slightly below the value of 5,65% that represents the maximum solid solubility of copper in aluminium at the eutectic temperature of 548 °C. Since alloys with as much as 33% copper were tested, a considerable amount of eutectic is found in the microstructure. With standard alloys the primary phase of the a-solid solution solidifies in a dendritic form. With higher copper contents the eutectic appears in the inter-dendritic space. The grain size and the distribution of dendrites and eutectic depend on the casting parameters4, the melt MATERIALI IN TEHNOLOGIJE 36 (2002) 1-2 B. ZLATIČANIN ET AL.: THE EFFECT OF COPPER CONTENT ON THE MICROSTRUCTURE OF Table 6: The linear intercept size of eutectic cells (Le) for different copper contents in aluminium-copper alloys Tabela 6: Linearna intercepcijska dolžina evtektičnih celic (Le) pri različni vsebnosti bakra v zlitinah aluminij-baker Type of sample min, µm max, µm average, µm RSE, % Vv,e.% AlCu5 (0,08%Ti) 1,63 44,90 5,65236 3,35377 14,59140 AlCu8 (0,08%Ti) 1,63 34,29 5,55443 3,00760 16,34898 AlCu15 (0%Ti) 1,63 46,53 7,05516 2,74649 24,58736 AlCu15 (0,02%Ti) 1,63 51,43 7,38373 3,24170 22,81881 AlCu15 (0,08%Ti) 1,63 63,67 8,34064 3,50108 25,01952 AlCu15 (0,15%Ti) 1,22 42,86 6,67921 3,04908 23,15246 AlCu15 (0,25%Ti) 1,22 55,10 7,30999 2,93505 26,14938 AlCu15Mg3 (0,08%Ti) 1,63 48,98 6,20416 2,80237 23,07952 AlCu23 (0,08%Ti) 1,63 165,71 14,56085 3,91495 44,43566 Table 7: Hardness and compression strength of aluminium-copper alloys with different amounts of copper Tabela 7: Trdota in tlačna trdnost zlitin AlCu z različno vsebnostjo bakra Type of sample HBaverage (N/mm2) (N/mm2) Al (0%Ti) 25,025 38,22 119,74 Al (0,08%Ti) 27,000 49,94 141,66 AlCu5 (0,08%Ti) 64,350 101,92 471,34 AlCu8 (0,08%Ti) 76,725 147,77 478,98 AlCu15 (0%Ti) 90,000 214,01 491,72 AlCu15 (0,02%Ti) 91,250 221,66 491,72 AlCu15 (0,08%Ti) 96,625 229,30 557,96 AlCu15 (0,15%Ti) 102,400 230,83 558,98 AlCu15 (0,25%Ti) 103,375 239,49 558,98 AlCu15Mg3 (0,08%Ti) 142,500 371,97 675,16 AlCu23 (0,08%Ti) 110,000 292,99 563,45 AlCu33 (0,08%Ti) 197,500 501,91 672,61 temperature and the solidification rate, which also affect the properties of the alloys. The microstructure can be influenced by controlling the casting parameters and by the addition of titanium and boron in form of the alloy AlTi5B1 to produce particles of TiB2 in the melt. These particles are then the nuclei for the TiAl3 phase that affects the solidification. Titanium and aluminium produce a peritectic reaction with the TiAl3 and the solid peritectic acts as a solidification nucleus for pure aluminium and its solid solutions. 3.3 Mechanical properties The Brinell hardness and the compression strength are shown in Table 7. The changes in chemical composition of the alloy cause changes in the structure that are reflected in the Brinell hardness and the compression strength. The hardness of the modified alloy is higher than the hardness of the alloy without any modification treatment. By increasing the content of copper and titanium the hardness and compression strength alsoincrease. 4 CONCLUSIONS Based on our findings we can draw the following conclusions about the effect of the content of copper on aluminium-copper alloys: – With increased amounts of copper in the alloy5 the average value of the DAS is decreased (see Table 5). – With the same chemical composition but increased titanium content, the average value of the grain size is decreased (see Table 4). With the addition of AlTi5B1 a modification to the solidification structure and smaller solidification grains are obtained. We confirmed that titanium is a very effective grain refiner. The resulting dispersion of insoluble components as well as a smaller porosity and fewer non-metal inclusions improved the mechanical properties. – Compression strength and hardness increase with the content of copper and titanium (Table 7). The compression strength and hardness of the magnesium alloy are also greater; compared to the copper alloy it has a smaller grain size for the same content of titanium. Across the whole range of copper content tested the lattice parameters of the tetragonal intermetallic compound remained constant. 5 REFERENCES 1 L. F. Mondolfo, Aluminium Alloys: Structure and Properties, Butterworth and Co (Publishers) Ltd, London 1976, 253 2 X. Yang, J. D. Hunt and D. V. Edmonds, A quantitative study of grain structures in twin-roll cast aluminium alloys, part II: AA 3004, Aluminium, 69 (1993) 2, 158-162 3 AM. Samuel, FH. Samuel, Effect of Alloying Elements and Dendrite Arm Spacing on the Microstructure and Hardness of an Al-Si-Cu-Mg-Fe-Mn (380), Journal of Materials Science, 7 (1995) 4, 1698-1708 4 B. Radonjic, Directionality of Cast Aluminium Structure, Aluminium, 58 (1982) 11, 646-649 5 WQ. Jie, W. Reif, Effect of Cu Content on Grain - Refinement of an Al-Cu Alloy with AlTi6 and AlTi5B1 Refiners, Zeitschrift fur Metallkunde, 84 (1993) 7, 445-450 MATERIALI IN TEHNOLOGIJE 36 (2002) 1-2 51 B. ZLATIČANIN ET AL.: THE EFFECT OF COPPER CONTENT ON THE MICROSTRUCTURE OF 52 MATERIALI IN TEHNOLOGIJE 36 (2002) 1-2