Treatment of aluminium alloy

Abstract: The invention provides a method of heat treating high strength aluminium alloy. The method comprises the steps of; solution heat treating of an aluminium alloy of from 3 to 9 wt.% Zn, 1 to 6 wt.% Mg, 1 to 3 wt.% Cu, at least one of 0.1 to 0.5 wt.% Cr, 0.1 to 0.5 wt.% Zr, 0.2 to 1.0 wt.% Mn, the balance being Al, heating the alloy to a temperature within a lower temperature zone of from 100 to 140°C for a duration of time, reheating the alloy to a temperature within an upper temperature zone of from 160 to 200°C for a second duration of time, cooling the alloy to a temperature within the lower temperature zone, and repeating the steps (2), (3), and (4) at least twice.

Description: The invention relates to the field of metallurgy and particularly to the field of Al-Zn-Mg-Cu alloy having high strength and high corrosion resistance. Aluminium alloys are widely used in the structures wherein low weight and high strength properties are required as those of aeroplanes. Among them the 7000 series Al-Zn-Mg-Cu aluminium alloys represented by 7075 and 7050 aluminium alloys of Japanese Industrial Standard (JIS) are widely utilized. These alloys obtain high strength by fine precipitates resulted from solution heat treatments and aging treatments. Generally speaking in the aging treatment, alloys are heat-treated under isothermal condition for from several hours to a duration of time lower than 100 hours in the temperature range of from 100 to 200 °C at single or dual temperature level. For example, in the recommended aging condition of JIS-W-1103, the temperature range is from 116 to 127 °C and the aging time is 24 hours for the 7075 alloys, whereas for the 7075 alloys with T 73 treatment, the temperature range is from 102 to 113°C and the aging time is from 6 to 8 hours for the first step treatment and from 102 to 113 °C , from 6 to 8 hours for the second step treatment. In the aging treatment, the temperatures should be kept constant in the recommended range for the duration of comparatively long time, which leads to the prescribed material properties of the alloys. In the 7000 series aluminium alloys, the high strength property is obtained by the formation of the fine precipitates of the aforementioned solution treatment and the aging treatment. However the dimensions, shape, and distribution of the precipitates varies with the aging condition. For example, in case of the 7075 T 6 alloy, the tensile strength of 58 kgf/mm² is obtained, whereas the susceptibility of the stress corrosion cracking is enhanced. In case of the 7075 alloys forging, the threshold stress in the ST direction wherein the stress corrosion cracking does not occur in the material, is 6 kgf/mm² for 7075 T 6, and 31 kgf/mm² for 7075 T 73 condition. The resistance to the stress corrosion cracking of the material is enhanced at the sacrifice of the strength of alloys. Accordingly, it is difficult to have both the corrosion resistance and the high strength property of material in the 7000 series aluminium alloys. The cause lies in the state of the precipitates which is determined by the aging treatment. When the aging is carried out under a comparatively low temperature such as 120°C, a very fine precipitate of the size of 5 nanometer is formed, and high strength is obtained. When the aging is carried out under a comparatively high temperature such as 170°C as in the case of 7075 T 73, the size of the precipitate grows to from 10 to 20 nanometer, and the strength is lowered, but the corrosion resistance such as the susceptibility for the stress corrosion cracking is lowered. Treatment of this type is known from US-A-3 198 676, US-A-2 248 185, CH-A-429198 and EP-A-0 081 441. In each of these the alloy is subjected to a two step "low-high" temperature aging. As mentioned above, to produce aluminium alloys having both the corrosion resistance and the high strength property, it is necessary to change the state of the precipitates. However, it is difficult to change the state of the precipitate in the prior art. It is an object of the invention to provide a heat treating method for high strength aluminium alloy. According to the invention a heat treating method for high strength aluminium alloy is provided comprising the steps of; (1) solution heat treating an aluminium alloy consisting of 3 to 9 wt.% Zn, 1 to 6 wt.% Mg, 1 to 3 wt.% Cu, at least one of 0.1 to 0.5 wt.% Cr, 0.1 to 0.5 wt.% Zr, 0.2 to 1.0 wt.% Mn, and the balance being Al, plus unavoidable impurities, (2) heating the alloy to a temperature within a lower temperature zone of from 100 to 140°C for a duration of time, (3) reheating the alloy to a temperature within an upper temperature zone of from 160 to 200°C for a second duration of time, (4) cooling the alloy to a temperature within the lower temperature zone, and (5) repeating the steps (2), (3), and (4) at least twice. The duration of time in the lower temperature zone and/or that in the upper temperature zone may be null. The temperature of the lower temperature zone may be more preferably from 105 to 125°C, and the temperature of the upper temperature zone may be from 160 to 180°C. Figures 1, 2(A), 2(B), and 2(C) are graphs showing the patterns of the heat treatment of the inventions. As mentioned before, the resistance to the stress corrosion cracking of the material was enhanced at the sacrifice of the strengths of alloys. To compromise the two properties aging treatment is an effective means. To obtain aluminium alloys having both the corrosion resistance and the high strength, the following conditions of chemical composition and heat treatment are required: The chemical composition is; Zn being from 3 to 9 wt.%, Mg being from 1 to 6 wt.%, Cu being from 1 to 3 wt.% at least one of; Cr being from 0.1 to 0.5 wt.%, Zr being from 0.1 to 0.5 wt.%, and Mn being from 0.2 to 1.0 wt.% and the balance aluminium. The heat treatment condition is: (1) the above mentioned material is solution heat treated, (2) the material is heated to the lower temperature zone of from 100 to 140°C for a duration of time, (3) the material is reheated to the upper temperature zone of from 160 to 200 °C for a duration of time, (4) the material is cooled down to the temperature range specified in (2), and (5) the steps (2), (3), and (4) are repeated at least twice. The reason of the specification of the above conditions is explaned as follows: 1. Zn is necessary for the enhancement of the strength. However when the Zn content is below 3 wt.%, sufficient practical strength cannnot be obtained. When the Zn content exceeds 9 wt.%, the hot workability is lowered. Accordingly, the Zn content is determined to be from 3 to 9 wt.%. 2. Mg is necessary for the enhancement of the strength. However when the Mg content is below 1 wt.%, sufficient practical strength cannnot be obtained. When the Mg content exceeds 6 wt.%, the hot workability and the corrosion resistance are lowered. Accordingly, the Mg content is determined to be from 1 to 6 wt.%. 3. Cu is necessary for the enhancement of the strength and the corrosion resistance. However the effect is saturated when the Cu content exceeds 3 wt.%. When the Cu content is below 1 wt.%, enough strength cannot be obtained. Accordingly, the Cu content is determined to be from 1 to 3 wt.%. 4. Cr, Zr, and Mn retards the recryztallization and promote the resistance to the stress corrosion cracking (hereinafter SCC). At least one of these element can be added to the alloy. However when the Cr content is below 0.1 wt.%, Zr, below 0.1 wt.%, and Mn, below 0.2 wt.%, the above mentioned effect cannnot be obtained. When the Cr content exceeds 0.5 wt.%, Zr content, 0.5 wt.%, and Mn, 1.0 wt.%, the effect is saturated. Accordingly the Cr content is determined to be from 0.1 to 0.5 wt.%, Zr, from 0.1 to 0.5 wt.%, and Mn, from 0.2 to 1.0 wt.% 5. The reason of the heat treatment conditions is explained as follows; Figures 1, 2(A), 2(B), and 2(C) are graphs showing the patterns of the heat treatment of the inventions. As shown in Figure 1, the aluminium alloy as solution heat treated is heated from room temperature, denoted as O, to the temperature, denoted as A, of the lower temperature zone and kept isothermally at the temperature for a duration of time t₁, denoted as AB. The alloy is reheated to the temperature, denoted as C, of the upper temperature zone and kept isothermally at the temperature for a duration of time t₂, denoted as CD, and cooled down to the temperature, denoted as E, of the lower temperature zone. This is the cycle of the aging treatmant and the cycle is repeated at least twice as shown by the points E, F, G, H, I, J, K, L, and M. The point M denotes room temperature. 5.1. When the temperature of the lower temperature zone is lower than 100 °C, t₁ becomes large to obtain a sufficient strength which is uneconomical, since the rate of growth of the precipitate is small at the temperature. When the temperature of the lower temperature zone is higher than 140 °C, sufficient strength cannnot be obtained. Accordingly the temperature of the lower temperature zone is determined to be from 100 to 140°C, and more preferably from 105 to 125 °C. 5.2. When the temperature of the upper temperature zone is lower than 160°C, the precipitate effective to the corrosion resistance cannot be obtained. When the temperature of the upper tempeature zone is higher than 200 °C, the sufficient strength cannot be obtained, even though the first step of the heat treatment is carried out in appropriate temperature range, since a rapid growth of the precipitate occurs. Accordingly the temperature of the upper temperature zone is determined to be from 160 to 200°C, and more preferably from 160 to 180 °C. 5.3. When the number of the cycle of the aging treatment is more than twice, the property having the strength and the corrosion resistance can be obtained, whereas this cannnot be obtained when the number of the cycle is single. The upper limit of the number of the cycle should be determined according to the chemical composition of the alloy and the dimension of the heat treated manufacture, since the excessive number of the cycle leads to the decrease of the strength in spite of the increase of the corrosion resistance. 6. When the number of the cycle is more than twice, the alloy can be cooled down from the temperature of the upper temperature zone down to the room temperature, denoted as N, or can be cooled down from the temperature of the lower temperature zone down to the room temperature, denoted as P, after a duration of time t₂, denoted as IJ as shown in Figure 1. 7. As for the duration time t₁ and t₂, t₁ can be zero as shown in Figure 2(A), t₂ can be zero as shown in Figure 2(C), and t₁ and t₂ can be zero as shown in Figure 2(B) with no influence on the properties of the alloy. 8. The temperatures except ambient one can be different among the heat cycle when the temperatures are in the range prescribed above with no influence on the properties of the alloy. 9. The rates of heating and cooling between the zones can be chosen with no influence on the properties of the alloy. EXAMPLES The invention is explained by examples described below: The samples for test are prepared as follows: The samples are of a 7050 series Al-6.3Zn-2.5Cu-0.12Zr alloy and a 7075 series Al-5.6Zn-2.3Mg-1.6Cu-0.1Cr-0.2Mn alloy. The samples are hot forged or hot rolled into plate with the thickness of 13mm, solution heat treated at 480 °C, and aging treated as described below: EXAMPLE 1 The aging treatment is carried out according to the patterns shown in Figures 1, 2(A), 2(B), and 2(C), and the temperatures, the duration of time, and the number of cycle are varied according to Table 1a. As for Table 1a, T₁ and T₂ denote the aging temperatures of the lower temperature zone and the upper temperature zone, respectively, and, t₁ and t₂ denote the duration of time at the aging temperature T₁,T₂ respectively. The heating and cooling rates are 0.5 °C/min. Two kinds of aging, namely, the peak aging and the over aging are carried out by conventional methods of aging for the purpose of comparison. Various tests are carried out as for the samples treated by the invented method and the conventional method. The tensile test is carried out to obtain the strength and the elongation. The fracture toughness test is carried out for a part of the samples. The exfoliation corrosion test prescribed by ASTM G 34 is carried out for all the samples. The stress corrosion cracking (SCC) test prescribed by JIS-H-8711 is carried out for a part of the samples. In the SCC test, the samples are stressed by a three point bending method and under the applied stress, the immersion of the samples into 3.5% NaCl aqueous solution and the drying thereof in air, is repeated for twenty days. As the result of the test the maximum stress wherein the crack is not generated, is defined as the threshold stress value of the SCC. Table 1a and 1b report the aging treatment conditions and the test results. The evaluating index of the exfoliation corrosion test, Exco rating, is P, EA, EB, EC, ED in the order of the superiority of the evaluation, wherein the Exco rating of P and EA are allowable value in the practical use of the alloy. As shown in Table 1b, the samples of the invention have the tensile strength of from 52 to 62 kgf/mm² and the value of the Exco rating is P or EA and the threshold stress value of the SCC test is more than 50 kgf/mm² which is a high value. In case of No. 12 and 13 of the peak aging, the same level of strength with those of the invented ones is obtained, but the corrosion resistance is inferior to those of the invented ones. In case of No 14 and 15 of the over aging, the good corrosion resistance is obtained, but the strength is lower by from 3 to 8 kgf/ mm² compared to those of the invented ones. As for the fracture toughness test, the test value of the invented ones is superior to or equal to those of the conventional ones. This superiority is also recognized in the 7050 series alloy, which proves the effectiveness of the invention. As shown in Table 1, the patterns of the aging treatment are triangular in Nos. 1, 2, 7, and 8, and trapezoidal in Nos. 3 to 6 and 9 to 11. The test results reveal that essentially no difference is found between those of the two patterns. No. Kind of Alloy Aging Treatment Pattern No. of Cycle T₁ (°C) t₁ (min.) T₂ (°C) t₂ (min.) 1 7050 120 0 170 0 5 2 7050 110 0 180 0 5 3 7050 120 100 170 20 3 4 7050 120 100 170 20 8 5 7050 120 60 170 60 25 6 7050 130 90 190 30 5 7 7075 120 0 170 0 5 8 7075 110 0 180 0 5 9 7075 120 100 170 20 3 10 7075 120 100 170 20 8 11 7075 120 60 170 60 5 12 7050 120 °C x 24 h - 13 7075 - 14 7050 170 °C x 6 h - 15 7075 - No. 0.2% PS (kgf/mm²) TS (kgf/mm²) E ℓ (%) K IC (kgf/mm 3/2 ) Exco Rating Threshold Stress SCC Remarks 1 58.8 61.9 13.6 95.3 EA 53.0 Invention Examples 2 56.0 60.2 12.8 - EA 52.0 3 58.0 61.8 14.0 - EA - 4 54.7 57.5 14.6 - P - 5 53.6 55.5 16.0 - P - 6 55.8 58.7 14.0 - P - 7 49.7 54.9 13.2 97.6 EA - 8 50.1 54.0 14.0 - EA - 9 53.9 57.3 12.5 - EA - 10 50.0 52.6 16.8 - P - 11 52.1 55.8 13.1 - EA - 12 54.1 59.0 16.4 88.9 EC 39.5 Conventional Examples 13 52.0 57.3 15.2 92.7 ED - 14 49.0 54.1 16.8 97.5 P 45.0 Conventional Examples 15 44.8 50.2 14.5 100.3 EA - EXAMPLE 2 Tables 2(A) and 2(B) report the aging treatment condition and the test results on the 7050 alloy wherein T₁ and T₂ are varied and the number of the cycle is set to be 5. When T₁ is low and out of the scope of the invention such as in Nos. 4 and 5, the strength is comparable but the corrosion resistance is inferior to those of the invented ones. When T₁ is high and out of the scope of the invention such as in No. 6, the corrosion resistance is comparable but the strength is inferior to those of the invented ones. When T₂ is low and out of the scope of the invention such as in No. 9, the corrosion resistance is inferior to those of the invemnted ones. When T₂ is high and out of the scope of the invention such as in Nos. 10 and 11, the strength is inferior to those of the invented ones. No. Kind of Alloy Aging Treatment Pattern No. of Cycle T₁(°C ) t₁ (min.) T₂ (°C) t₂(min.) 1 7050 120 0 170 0 5 2 7050 110 0 170 0 5 3 7050 135 0 170 0 5 4 7050 75 0 170 0 5 5 7050 90 0 170 0 5 6 7050 150 0 170 0 5 7 7050 110 0 180 0 5 8 7050 110 0 195 0 5 9 7050 110 0 150 0 5 10 7050 110 0 210 0 5 11 7050 110 0 220 0 5 No. 0.2 % PS (kgf/mm²) TS (kgf/mm²) E ℓ (%) Exco Rating Remarks 1 58.8 61.9 13.6 EA Invention Examples 2 57.5 61.0 13.0 EA 3 55.9 59.8 16.1 P 4 52.6 59.1 12.5 ED Comparison Examples 5 54.8 60.0 13.4 ED 6 47.5 52.1 14.0 P 7 56.8 62.1 13.8 EA Invention Examples 8 56.0 61.5 14.1 P 9 59.5 63.4 11.5 ED Comparison Examples 10 45.0 50.5 15.8 P 11 42.6 49.1 17.0 P EXAMPLE 3 Table 3a and 3b report the aging condition and the test results on the 7050 alloy wherein T₁ is fixed to 120°C and T₂ ,170 °C, and the number of the cycle is varied. When the number of the cycle is single such as in Nos. 4 and 5, the strength is sufficient but the corrosion resistance is deteriorated. Even when the number of the cycle is at least two such as in No. 3, wherein the test is interrupted during the cycle, the corrosion resistance is not inferior to those of Nos. 1 and 2. EXAMPLE 4 Tables 4a, 4b and 4c reports the aging treatment condition and the test results on the 7050 alloy wherein T₁ and T₂ is varied , cycle by cycle, and the number of the cycle is 5. As far as T₁ and T₂ stays in the temperature zone in the scope of the invention, both high strength and corrosion resistance are obtained. Even when the pattern of the cycle is a combination of triangle and trapezoid as in the case of No 2 and 3, high strength and corrosion resistance are obtained. No. Kind of Alloy Aging Treatment Pattern No. of Cycle T₁ (°C) t₁ (min.) T₂ (°C) t₂ (min.) 1 7050 120 0 170 0 5 2 7050 120 60 170 60 5 3 7050 120 60 170 60 2.5 4 7050 120 0 170 0 1 5 7050 120 0 170 0 1 No. Heating and Cooling Rates ( °C/min.) 0.2 % PS (kgf/mm²) TS (kgf/mm²) E ℓ (%) Exco Rating Remarks 1 0.5 58.8 61.9 13.6 EA Invention Examples 2 0.5 54.3 56.6 15.3 P 3 0.5 59.1 62.3 13.0 EA 4 0.5 56.4 59.7 14.5 ED Comparison Examples 5 0.1 58.9 62.0 13.5 ED No. Kind of Alloy Aging Treatment Condition st Cycle 2nd Cycle T₁ t₁ T₂ t₂ T₁ t₁ T₂ t₂ 1 7050 120 0 170 0 120 0 170 0 2 7050 120 0 170 0 110 0 190 0 3 7050 120 0 170 0 110 0 190 30 No. Aging Treatment Condition 3rd Cycle 4th Cycle 5th Cycle T₁ t₁ T₂ t₂ T₁ t₁ T₂ t₂ T₁ t₁ T₂ t₂ 1 120 0 170 0 120 0 170 0 120 0 170 0 2 135 0 160 0 120 0 170 0 130 0 180 0 3 135 30 160 60 120 60 170 60 120 0 170 0 No. 0.2 % PS (kgf/mm²) TS (kgf/mm² ) E ℓ (%) Exco Rating Remarks 1 58.8 61.9 13.6 EA Invention Example 2 57.1 60.8 14.5 EA Invention Example 3 56.6 60.1 15.5 P Invention Example

Claims: A method of heat treating an aluminium alloy characterized by the steps of: (1) solution heat treating an aluminium alloy comprising from 3 to 9 wt.% Zn, 1 to 6 wt.% Mg, 1 to 3 wt.% Cu, at least one of 0.1 to 0.5 wt.% Cr, 0.1 to 0.5 wt.% Zr, 0.2 to 1.0 wt.% Mn, the balance being Al; (2) heating the alloy to a temperature within a lower temperature zone of from 100 to 140°C for a first period of time; (3) reheating the alloy to a temperature within an upper temperature zone of from 160 to 200°C for a second period of time; (4) cooling the alloy to a temperature within the lower temperature zone; and (5) repeating the steps (2), (3), and (4) at least twice. A method according to claim 1, characterized in that the duration of the first period of time is zero. A method according to claim 1 or 2, characterized in that the duration of time of the second period of time is zero. A method according to any one of the preceding claims, wherein the temperature within the lower temperature zone is from 105 to 125°C. A method according to any one of the preceding claims, wherein the temperature within the upper temperature zone is from 160 to 180°C.

Inventors: MINAKAWA KUNINORI C O PATENT L, SAKIYAMA TETSUO C O PATENT LIC, TSUYAMA SEISHI C O PATENT LICE, MINAKAWA, KUNINORI, C/O PATENT & LICENSE DEPART., SAKIYAMA, TETSUO, C/O PATENT & LICENSE DEPARTMENT, TSUYAMA, SEISHI, C/O PATENT & LICENSE DEPARTMENT, Minakawa, Kuninori, C/o Patent &amp; License Depart., Sakiyama, Tetsuo, C/o Patent &amp; License Department, Tsuyama, Seishi, C/o Patent &amp; License Department
Applicants: NIPPON KOKAN KK, NKK CORPORATION
Application year: 1990
Main classification: C22F1
IPC codes: C22C21, C22F1