| (19) |
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(11) |
EP 1 831 415 B2 |
| (12) |
NEW EUROPEAN PATENT SPECIFICATION |
|
After opposition procedure |
| (45) |
Date of publication and mentionof the opposition decision: |
|
15.10.2014 Bulletin 2014/42 |
| (45) |
Mention of the grant of the patent: |
|
18.03.2009 Bulletin 2009/12 |
| (22) |
Date of filing: 04.10.2005 |
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| (51) |
International Patent Classification (IPC):
|
| (86) |
International application number: |
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PCT/EP2005/010809 |
| (87) |
International publication number: |
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WO 2006/037648 (13.04.2006 Gazette 2006/15) |
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| (54) |
METHOD FOR PRODUCING A HIGH STRENGTH, HIGH TOUGHNESS A1-Zn ALLOY PRODUCT
HERSTELLUNGSVERFAHREN FÜR EIN HOCHFESTES, HOCHZÄHES A1-ZINNLEGIERUNGSPRODUKT
PROCÉDÉ DE FABRICATION D'UN ALLIAGE DE AL-ZN À HAUTE RÉSISTANCE ET DE GRANDE DURETE
|
| (84) |
Designated Contracting States: |
|
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC NL PL PT RO SE
SI SK TR |
| (30) |
Priority: |
05.10.2004 EP 04077721
|
| (43) |
Date of publication of application: |
|
12.09.2007 Bulletin 2007/37 |
| (73) |
Proprietor: Aleris Aluminum Koblenz GmbH |
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56070 Koblenz (DE) |
|
| (72) |
Inventors: |
|
- BENEDICTUS, Rinze
NL-2612 PJ Delft (NL)
- KEIDEL, Christian, Joachim
56410 Montabaur (DE)
- HEINZ, Alfred, Ludwig
56414 Niederahr (DE)
|
| (74) |
Representative: Müller Schupfner & Partner
Patent- und Rechtsanwaltspartnerschaft mbB |
|
Bavariaring 11 80336 München 80336 München (DE) |
| (56) |
References cited: :
EP-A- 0 368 005 US-A- 4 305 763 US-A1- 2002 162 609
|
EP-A- 0 829 552 US-A- 5 496 426 US-A1- 2003 219 353
|
|
| |
|
|
- 'International Alloy Designations and Chemical Composition Limits for Wrought Aluminum
and Wrought Aluminum Alloys', 1998, THE ALUMINUM ASSOCIATION, WASHINGTON pages 7 -
9
|
|
| |
|
FIELD OF THE INVENTION
[0001] The present invention relates to a high-strength high-toughness AI-Zn alloy wrought
product with elevated amounts of Zn for maintaining good corrosion resistance, and
to a method for producing such a high-strength high-toughness AI-Zn alloy product
and to a plate product of such alloy. More specifically, the present invention relates
to a high strength, high toughness AI-Zn alloy designated by the AA7000-series of
the international nomenclature of the Aluminum Association for structural aeronautical
applications. Even more specifically, the present invention relates to a new chemistry
window for an AI-Zn alloy having improved combinations of strength and toughness by
maintaining good corrosion resistance, which does not need specific ageing or temper
treatments.
BACKGROUND OF THE INVENTION
[0002] It is known in the art to use heat treatable aluminium alloys in a number of applications
involving relatively high strength, high toughness and corrosion resistance such as
aircraft fuselages, vehicular members and other applications. Aluminium alloys AA7050
and AA7150 exhibit high strength in T6-type tempers. Also precipitation-hardened AA7x75,
AA7x55 alloy products exhibit high strength values in the T6 temper. The T6 temper
is known to enhance the strength of the alloy, wherein the aforementioned AA7x50,
AA7x75 and AA7x55 alloy products which contain high amounts of zinc, copper and magnesium
are known for their high strength-to-weight ratios and, therefore, find application
in particular in the aerospace industry. However, these applications result in exposure
to a wide variety of climatic conditions necessitating careful control of working
and ageing conditions to provide adequate strength and resistance to corrosion, including
both stress corrosion and exfoliation.
[0003] In order to enhance resistance against stress corrosion and exfoliation as well as
fracture toughness it is known to artificially over-age these AA7000-series alloys.
When artificially aged to a T79, T76, T74 or T73-type temper their resistance to stress
corrosion, exfoliation corrosion and fracture toughness improve in the order stated
(T73 being best and T79 being close to T6) but at the cost of strength compared to
the T6 temper condition. A more acceptable temper condition is the T74-type temper
which is a limited over-aged condition, between T73 and T76, in order to obtain an
acceptable level of tensile strength, stress corrosion resistance, exfoliation corrosion
resistance and fracture toughness. Such T74 temper is performed by over-ageing the
aluminium alloy product at temperatures of 121°C for 6 to 24 hours and followed by
171°C for about 14 hours.
[0004] Depending on the design criteria for a particular aircraft component even small improvements
in strength, toughness or corrosion resistance result in weight savings, which translate
amongst others to fuel economy over the life time of the aircraft. To meet these demands
several other 7000-serie alloys have been developed.
[0005] For example each of
EP-0377779,
EP 0 368 005 ,
US-5,221,377 and
US-5,496,426 disclose alloy products and an improved process for producing an 7055 alloy for sheet
or thin plate applications in the field of aerospace such as upper-wing members with
high toughness and good corrosion properties which comprises the steps of working
a body having a composition consisting of, about in wt.%: Zn 7.6 to 8.4, Cu 2.2 to
2.6, Mg 1.8 to 2.1 or 2.2, and one or more elements selected from Zr, Mn V and Hf,
the total of the elements not exceeding 0.6 wt.%, the balance aluminium plus incidental
impurities, solution heat treating and quenching the product and artificially ageing
the product by either heating the product three times in a row to one or more temperatures
from 79°C to 163°C or heating such product first to one or more temperatures from
79°C to 141°C for two hours or more and heating the product to one or more temperatures
from 148°C to 174°C. These products are reported to have an improved exfoliation corrosion
resistance of "EB" or better with about 15% greater yield strength than similar sized
7x50 counter- parts in the T76-temper condition. They still have at least about 5%
higher strength than their similarsized 7x50-T77 counterpart (7150-T77 will be used
herein below as a reference alloy). Document
US 6, 562, 154 discloses a rolled aluminium alloy sheet product and the production of such sheet
products, which exhibit improved strength and fatigue crack growth resistance. The
production method includes casting, scalping, preheating, initial hot rolling, reheating,
finish hot rolling and optional cold rolling. Some suitable alloy compositions include
AA2xxx, AA5xxx, AA6xxx and AA7xxx alloys.
SUMMARY OF THE INVENTION
[0006] It is an object of the present invention to provide an improved AI-Zn alloy preferably
for plate products with high (compressive) strength and high toughness. Corrosion
resistance should not deteriorate.
[0007] More specifically, it is an object of the present invention to provide an alloy product
which can be used for upper wing applications in aerospace with an improved compression
yield strength and a high unit propagation energy with properties which are better
than the properties of a conventional AA7055-alloy in the T77 temper.
[0008] It is another object of the invention to obtain an AA7000-series aluminium alloy
which exhibits strength in the range of T6-type tempers and toughness and corrosion
resistance properties in the range of T73-type tempers.
[0009] It is another object of the invention to provide a method of manufacturing the aluminium
alloy product according to this invention.
[0010] The present invention meets one or more of these objects by the characterizing features
of the independent claims. Further preferred embodiments are described and specified
within the dependent claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0011] As will be appreciated hereinbelow, except otherwise indicated, alloy designations
and temper designations refer to the Aluminum Association designations in Aluminum
Standards and Data and the Registration Records, all published by the US Aluminum
Association.
[0012] One or more of the above mentioned objects of the invention are achieved by using
an AI-Zn alloy product with an improved combination of high toughness and high strength
by maintaining good corrosion resistance, said alloy comprising, and preferably consisting
of, (in weight percent):
| Zn |
6.0 to 11.0 |
| Cu |
1.4 to 2.2 |
| Mg |
1.4 to 2.4 |
| Zr |
0.05 to 0.15 |
| Ti |
< 0.05, |
| Hf and/or V < 0.25, |
optionally Sc and/or Ce 0.05 to 0.25, and
optionally Mn 0.05 to 0.12,
and inevitable impurities and balance aluminium, preferably other elements each less
than 0.05 and less than 0.50 in total, and wherein the alloy product has a substantially
fully unrecrystallized microstructure at the position T/10 of the finished product.
[0013] Such chemistry window for an AA7000-series alloy exhibits excellent properties when
produced to relatively thin plate products, and which is preferably useable in aerospace
upper-wing applications having gauges in the range of 20 mm to 60 mm.
[0014] The above defined chemistry has properties which are comparable or better than existing
alloys of the AA7x50 or AA7x55 series in the T77-temper, without using the above described
cumbersome and complicated T77 three-step ageing cycles. The chemistry leads to an
aluminium product which is more cost effective and is also simpler to produce since
less processing steps are necessary. Additionally, the chemistry allows new manufacturing
techniques like age forming or age creep forming which is not feasible when a T77-temper
alloy is applied. Even better, the chemistry as defined above can also be aged to
the T77-temper whereby the corrosion resistance further improves.
[0015] According to the invention it has been found that a selected range of elements, using
a higher amount of Zn and a specific combination of a particular range of Mg and Cu,
exhibit substantially better combinations of strength and toughness and maintaining
a good corrosion performance such as exfoliation corrosion resistance and stress corrosion
cracking resistance.
[0016] The present invention uses the chemistry in combination with a method to produce
a rolled product from such chemistry, as explained herein below, to obtain a substantially
fully unrecrystallized microstructure at least at the position T/10 of the finished
product. More preferably the product is unrecystallized across the whole thickness.
With unrecystallized we mean that more than 80%, preferably more than 90% of the gauge
of the finished rolled product is substantially unrecrystallized. Hence, the present
invention is disclosing an alloy product which is in particular suitable for upper
wing skin applications for aircrafts and having a thickness in the range of 20 to
60 mm, preferably 30 to 50 mm.
[0017] It has been found that is not necessary to slowly quench the rolled product or to
increase the gauge of the rolled product to obtain superior compression yield strength
and toughness properties.
[0018] Copper and magnesium are important elements for adding strength to the alloy. Too
low amounts of magnesium and copper result in a decrease of strength while too high
amounts of magnesium and copper result in a lower corrosion performance and problems
with the weldability of the alloy product. Prior art techniques used special ageing
procedures to ameliorate the strength while low amounts of magnesium and copper are
used in order to achieve a good corrosion performance. In order to achieve a compromise
in strength, toughness and corrosion performance copper and magnesium amounts (in
wt.%) of between 1.7 and 2.2%, preferably between 1.7 and 2.1% for Mg and 1.8 and
2.1% for Cu have been found to give a good balance for thin plate products. Throughout
the claimed chemistry of the present invention it is now possible to achieve strength
levels in the region of a T6-temper alloy while maintaining corrosion performance
characteristics similar to those of T74-temper alloys.
[0019] Apart from the amounts of magnesium and copper the invention discloses a balance
of magnesium and copper amounts to zinc, especially the balance of magnesium to zinc,
which gives the alloy these performance characteristics. The improved corrosion resistance
of the alloy according to the invention has exfoliation properties ("EXCO") of EB
or better, preferably EA or better.
[0020] The amount (in weight%) of zinc is preferably in a range of 7.4 to 9.6%, more preferably
in a range of 8.0 to 9.6%, most preferably in a range of 8.4 to 8.9%. Testing has
found an optimum zinc level of about 8.6%. Further details are given in the examples
as described in more details hereinbelow.
[0021] It has furthermore been shown that, according to a preferred embodiment of the present
invention, a Sc-containing alloy is an excellent candidate for obtaining high strength
versus high notch toughness levels. By adding Sc to an alloy comprising copper, magnesium,
zinc, zirconium and titanium it has been found that the microstructure remains unrecrystallized,
thereby showing superior properties with regard to strength and toughness. Hence,
preferred amounts of Sc (in weight%) are in a range of [Zr] + 1.5 [Sc] <0.15%. Preferred
amounts (in weight%) of Sc or Ce are in a range of 0.03 to 0.06% when the amount of
Zn is about 8.70% and Mg and Cu are about 2.10%. The levels of the unit propagation
energy are considerably good for an alloy with additional Sc, Ce or Mn alloying elements.
[0022] A method for producing a high strength, high toughness AI-Zn alloy product with good
corrosion resistance according to the present invention comprises the steps of claim
1.
[0023] It has been found that the microstructure of the alloy product remains substantially
fully unrecrystallized underneath its surface when the inventive method step of pre-working
the product and hot rolling and cold rolling the pre-worked product are applied.
[0024] In accordance with an embodiment of the present invention the method includes a first
hot rolling of the ingot which has been homogenised into a pre-worked product, hot
rolling the re-heated product to about 150 to 250 (in final-gauge%) and then cold
rolling the hot rolled product to the final gauge or hot rolling the re-heated product
to about 105 to 140 (in final-gauge%) and then cold rolling the hot rolled product
to the final gauge. "Final-gauge%" means a percentage in thickness compared to the
thickness of the final product. 200 final-gauge% means a thickness which is twice
as much as the thickness of the finally worked product. That means that it has been
found that it is advantageous to first hot roll the pre-heated product to a thickness
which is about twice as high as the thickness of the final product and then cold rolling
the hot rolled product to the final thickness or to hot roll the pre-heated product
to a thickness which is about 20% higher than the thickness of the final product and
then cold rolling the product, thereby obtaining another about 20% reduction of the
gauge of the hot rolled product.
[0025] According to another embodiment of the present invention it is advantageous to hot
roll the re-heated product at low temperatures in the range of 300°C to 420°C so that
the alloy does not recrystallise. Optionally, it is possible to artificially ageing
the worked and heat-treated product with a two-step T79 or T76 temper or to use a
T77-three step temper if SCC performance shall be improved.
[0026] The present invention is useful for hot-working the ingot after casting and cold-working
into a worked product with a gauge in the range of 20 to 60 mm.
[0027] The present invention also concerns a plate product of high strength, high toughness
AI-Zn alloy of the aforementioned composition which plate product is preferably a
thin aircraft member, even more preferably an elongate structural shape member such
as an upper-wing member, a thin skin member of an upper-wing or of a stringer of an
aircraft.
[0028] The properties of the claimed alloy may further be enhanced by an artificial ageing
step comprising a first heat treatment at a temperature in a range of 105°C to 135°C,
preferably around 120°C for 2 to 20 hours, preferably around 8 hours and a second
heat treatment at a higher temperature then 135°C but below 210°C, preferably around
155°C for 4 to 12 hours, preferably 8 to 10 hours.
[0029] The foregoing and other features and advantages of the alloys according to the present
invention will become readily apparent from the following detailed description of
preferred embodiments.
Example 1
[0030] On a laboratory scale 14 different aluminium alloys have been cast into ingots, homogenised,
pre-heated for more than 6 hours at about 410°C and hot rolled to 4 mm plates. Solution
heat treatment was done at 475°C and thereafter water quenched. Thereafter, the quenched
product was aged by a two-step T76 ageing procedure. The chemical compositions are
set out in Table 1.
Table 1. Chemical compositions of alloys in thin plate form, in weight%, balance aluminium
and inevitable impurities, Fe 0.06, Si 0.05, Ti 0.04 and Zr 0.12.
| Alloy |
Cu |
Mg |
Zn |
Others |
| 1 |
2.0 |
2.1 |
8.0 |
0.08 Mn |
| 2 |
2.1 |
2.1 |
8.1 |
- |
| 3 |
1.7 |
1.75 |
8.7 |
- |
| 4 |
2.1 |
1.7 |
8.6 |
- |
| 5* |
2.4 |
1.7 |
8.6 |
- |
| 6 |
1.7 |
2.2 |
8.7 |
- |
| 7 |
2.1 |
2.1 |
8.6 |
- |
| 8* |
2.4 |
2.1 |
8.7 |
- |
| 9* |
1.7 |
2.5 |
8.7 |
- |
| 10 |
2.1 |
2.4 |
8.6 |
- |
| 11 |
2.5 |
2.5 |
8.7 |
- |
| 12 |
2.1 |
2.1 |
9.2 |
- |
| 13* |
2.1 |
2.1 |
8.7 |
0.03 Ce |
| 14 |
2.1 |
2.1 |
8.7 |
0.06 Sc |
| *Alloy composition outside claim 1. |
[0031] The alloys of Table 1 were processed using three processing variants (see step 5
variant 1 being comparative examples and variants 2 and 3 being examples of the invention)
:
- 1. Homogenisation was performed by heating at a temperature rate of 40°C/h to a temperature
of 460°C, then soaking for 12 hours at 460°C and another increase with 25°C/h to a
temperature of 475°C with another soaking for 24 hours at 475°C, and air cooling to
room temperature.
- 2. Pre-heating was done at 420°C for 6 hours with a heating rate of 40°C/h.
- 3. The lab scale ingots were hot rolled from 80 to 25 mm, thereby reducing the gauge
by about 6 to 8 mm per pass.
- 4. The 25 mm thick products were reheated to 420°C for about 30 min.
- 5.
Variant 1: The reheated product was hot rolled to 4.0 mm (comparative).
Variant 2: The reheated product was hot rolled to 8.0 mm and thereafter cold rolled
to 4.0 mm (comparative).
Variant 3: The reheated product was hot rolled to 5.0 mm and then cold rolled to 4.0
mm, in accordance with the invention.
- 6. Solution heat treatment was done for 1 hour at 475°C, thereafter water quenched.
- 7. Stretching was done by 1.5 to 2.0% within about 1 hour after quenching.
- 8. Thereafter, the stretched products were aged in accordance with a T76 ageing procedure,
thereby raising the temperature to 120°C at a rate of 30°C/h and maintaining the temperature
at 120°C for 5 hours, raising the temperature at a rate of 15°C/h to a temperature
of 160°C and soaking for 6 hours, and air cooling the aged product to room temperature.
[0032] Strength was measured using small Euronorm and toughness were measured in accordance
with ASTM B-871(1996). The results of the three above-mentioned variants are shown
in Table 2a to 2c.
Table 2a. Strength and toughness properties of the alloys as shown in Table 1 in MPa and notch
toughness (TYR) in accordance with Variant 1.
| Alloy |
Rp |
UPE |
TYR |
| 1 |
582 |
211 |
1.31 |
| 2 |
564 |
215 |
1.48 |
| 3 |
534 |
243 |
1.49 |
| 4 |
550 |
214 |
1.48 |
| 5 |
579 |
208 |
1.44 |
| 6 |
592 |
84 |
1.34 |
| 7 |
595 |
120 |
1.32 |
| 8 |
605 |
98 |
1.32 |
| 9 |
612 |
30 |
1.31 |
| 10 |
613 |
54 |
1.12 |
| 11 |
603 |
33 |
1.11 |
| 12 |
- |
- |
- |
| 13 |
597 |
163 |
1.27 |
| 14 |
587 |
121 |
1.35 |
Table 2b. Strength and toughness properties of the alloys as shown in Table 1 in MPa and notch
toughness (TYR) in accordance with Variant 2:
| Alloy |
Rp |
UPE |
TYR |
| 1 |
599 |
125 |
1.30 |
| 2 |
567 |
268 |
1.45 |
| 3 |
533 |
143 |
1.53 |
| 4 |
587 |
205 |
1.38 |
| 5 |
563 |
178 |
1.45 |
| 6 |
569 |
134 |
1.35 |
| 7 |
- |
- |
- |
| 8 |
616 |
72 |
1.10 |
| 9 |
- |
- |
- |
| 10 |
601 |
22 |
1.00 |
| 11 |
612 |
5 |
1.05 |
| 12 |
- |
- |
- |
| 13 |
595 |
88 |
1.16 |
| 14 |
626 |
71 |
1.26 |
Table 2c. Strength and toughness properties of the alloys as shown in Table 1 in MPa and notch
toughness (TYR) in accordance with Variant 3.
| Alloy |
Rp |
UPE |
TYR |
| 1 |
600 |
170 |
1.35 |
| 2 |
575 |
211 |
1.47 |
| 3 |
535 |
232 |
1.59 |
| 4 |
573 |
260 |
1.46 |
| 5 |
604 |
252 |
1.39 |
| 6 |
587 |
185 |
1.43 |
| 7 |
613 |
199 |
1.26 |
| 8 |
627 |
185 |
1.18 |
| 9 |
- |
- |
- |
| 10 |
607 |
31 |
1.09 |
| 11 |
614 |
26 |
0.92 |
| 12 |
606 |
58 |
1.11 |
| 13 |
601 |
148 |
1.26 |
| 14 |
616 |
122 |
1.35 |
[0033] From the results presented in Tables 2a to 2c it is clear that a minor degree (10
to 20%) of cold rolling is beneficial for an optimum toughness versus strength balance.
The purely hot rolled material in accordance with Variant 1 (Table 2a) is close to
the optimum but in general the Variant 3-alloys are better.
[0034] Furthermore, it can be seen that Sc-containing alloy 14 is advantageous if high strength
versus high notch toughness is needed. Small amounts of manganese do increase the
strength but at the cost of some toughness.
Example 2
[0035] Additional chemistries have been processed in accordance with the above-mentioned
processing steps 1 to 8, thereby using the variant 3 of step 5 of example 1 above
and a T76 ageing.
Table 3. Chemical compositions of thin plate alloys, in weight%, for all alloys balance aluminium
and inevitable impurities, Fe 0.06, Si 0.05.
| Alloy |
Cu |
Mg |
Zn |
Zr |
Ti |
Others |
| 1 |
2.0 |
2.1 |
8.0 |
0.11 |
0.03 |
0.08 Mn |
| 2 |
2.1 |
2.1 |
8.1 |
0.12 |
0.03 |
- |
| 3 |
1.7 |
2.2 |
8.7 |
0.12 |
0.03 |
- |
| 4 |
2.1 |
2.1 |
8.6 |
0.12 |
0.03 |
- |
| 5* |
2.4 |
2.1 |
8.7 |
0.12 |
0.03 |
- |
| 6 |
2.1 |
2.1 |
9.2 |
0.12 |
0.03 |
- |
| 7* |
2.1 |
2.1 |
8.7 |
0.12 |
0.04 |
0.04 Ce |
| 8 |
2.1 |
2.1 |
8.7 |
0.10 |
0.04 |
0.06 Sc |
| 9 |
1.7 |
2.1 |
9.3 |
0.12 |
0.03 |
- |
| 10* |
1.6 |
2.5 |
9.2 |
0.12 |
0.04 |
- |
| 11 |
2.1 |
2.4 |
9.2 |
0.12 |
0.04 |
- |
| *alloy compostion outside claim 1 |
[0036] The properties of the alloys mentioned in Table 3 have been tested in the L-direction
for the strength and in the L-T-direction for the toughness.
Table 4. Strength and toughness properties of the alloys as shown in Table 3 in MPa and notch
toughness (TS/Rp) in accordance with Variant 3.
| Alloy |
Rp |
Rm |
UPE |
TS/Rp |
| |
(MPa) |
(MPa) |
(kJ/m2) |
|
| 1 |
601 |
637 |
177 |
1.35 |
| 2 |
575 |
603 |
221 |
1.48 |
| 3 |
591 |
610 |
194 |
1.45 |
| 4 |
613 |
647 |
199 |
1.34 |
| 5 |
624 |
645 |
178 |
1.18 |
| 6 |
608 |
638 |
63 |
1.13 |
| 7 |
601 |
639 |
163 |
1.27 |
| 8 |
618 |
652 |
132 |
1.35 |
| 9 |
613 |
632 |
75 |
1.25 |
| 10 |
618 |
650 |
5 |
1.29 |
| 11 |
619 |
654 |
26 |
1.18 |
[0037] The toughness versus tensile yield strength (Rp) shown in Table 4 clearly shows that
the best toughness versus tensile yield strength value is obtained for alloys having
around 8.6 to 8.7 weight% zinc. Alloys with lower levels of zinc will show similar
toughness values but the tensile strength is -generally speaking- lower whereas high
levels of zinc result in higher strength levels but lower toughness levels. Small
amounts of manganese do increase the strength at the cost of toughness.
Example 3
[0038] Further tests were done with zinc levels of 8.6 and 8.7 thereby varying copper and
magnesium levels. It can be shown that toughness levels can be elevated at the same
strength levels. Some additional alloys were processed similar as to the ones in Example
2, thereby using the processing steps 1 to 8 as described above and Variant 3 of step
5 of Example 1.
Table 5. Chemical compositions of thin plate alloys, in weight%, for all alloys balance aluminium
and inevitable impurities, Fe 0.06, Si 0.05.
| Alloy |
Cu |
Mg |
Zn |
Zr |
Ti |
Others |
| 3 |
1.7 |
2.2 |
8.7 |
0.12 |
0.03 |
- |
| 4 |
2.1 |
2.1 |
8.6 |
0.12 |
0.03 |
- |
| 5* |
2.4 |
2.1 |
8.7 |
0.12 |
0.03 |
- |
| 12* |
2.5 |
2.5 |
8.7 |
0.11 |
0.03 |
0.08 Mn |
| 13 |
2.1 |
2.4 |
8.6 |
0.12 |
0.03 |
- |
| 14* |
1.7 |
2.5 |
8.7 |
0.12 |
0.03 |
- |
| 15 |
1.7 |
1.7 |
8.7 |
0.12 |
0.03 |
- |
| 16* |
2.4 |
1.7 |
8.6 |
0.12 |
0.03 |
- |
| 17 |
2.1 |
1.7 |
8.6 |
0.12 |
0.04 |
- |
| *alloy composition outside claim 1 |
Table 6. Strength and toughness properties of the alloys as shown in Table 5 in MPa and notch
toughness (TS/Rp) in accordance with Variant 3.
| Alloy |
Rp |
UPE |
TS/Rp |
| |
(MPa) |
(kJ/m2) |
|
| 3 |
591 |
194 |
1.45 |
| 4 |
613 |
199 |
1.34 |
| 5 |
624 |
178 |
1.18 |
| 12 |
614 |
26 |
0.92 |
| 13 |
607 |
31 |
1.09 |
| 14 |
621 |
55 |
1.01 |
| 15 |
535 |
232 |
1.59 |
| 16 |
604 |
252 |
1.39 |
| 17 |
573 |
260 |
1.46 |
[0039] As shown in Table 6 it is advantageous to have magnesium levels of less than 2.4%
with an optimum of about 1.7%. When magnesium levels are at about 1.7%, excellent
toughness properties are obtained but the strength levels decrease. With magnesium
levels of about 2.1% the best strength levels are obtained. Hence, magnesium is best
in between 1.7 and 2.1%.
[0040] All above mentioned alloys have been tested on exfoliation corrosion according to
ASTM G-34. They all showed a performance of EB or better.
[0041] Furthermore, it has been shown that the addition of Ce or Sc enhances the microstructure
of the alloy thereby reducing recovery processes. Since the recovery within the alloy
material is low, nearly no recrystallization takes place even though a solution heat
treatment is used in accordance with the standard route. Sc represses recrystallization
so that usually more than 90% of the thickness of the thin plate products remains
unrecrystallized.
1. Method for producing a high strength, high toughness AI-Zn alloy product with good
corrosion resistance, comprising the steps of:
a.) casting an ingot with the following composition, in weight percent:
| Zn |
6.0 to 11.0% |
| Cu |
1.4 to 2.2% |
| Mg |
1.4 to 2.4% |
| Zr |
0.05 to 0.15% |
| Ti |
< 0.05% |
| Hf and/or V < 0.25%, |
optionally Sc and/or Ce 0.05 to 0.25%,
optionally Mn 0.05 to 0.12%, and
inevitable impurities and balance aluminium,
b.) homogenising and/or pre-heating the ingot after casting,
c.) hot working the ingot into a pre-worked product,
d.) reheating the pre-worked product and hot rolling the reheated product,
cold rolling the hot-rolled, product by a degree of 10 to 20% to the final gauge,
e.) solution heat treating and quenching the solution heat treated product,
f.) optionally stretching or compressing of the quenched alloy product, and
g.) optionally ageing the quenched and optionally stretched or compressed product
to achieve a desired temper,
and wherein the product in its final temper has a substantially fully unrecrystallized
microstructure at least at the position T/10 of the finished product.
2. Method according to claim 1, wherein hot rolling the reheated product to about 150
to 250 (in final-gauge%) and then cold rolling the hot rolled product to the final
gauge.
3. Method according to claim 1 or 2, wherein hot rolling the reheated product to about
105 to 140 (in final-gauge%) and then cold rolling the hot rolled product to the final
gauge.
4. Method according to any one of claims 1 to 3, comprising hot rolling the reheated
product at low temperatures in the range of 300°C to 420°C to prevent the alloy product
from recrystallising.
5. Method according to any one of claims 1 to 4, wherein the artificial ageing during
step g.) is to temper selected from the group consisting of T79, and T76, and preferably
by means of a two step ageing treatment.
6. Method according to any one of claims 1 to 5, wherein the artificial ageing during
step g.) consists of a first ageing step at a temperature in a range of 105 to 135°C
for 2 to 20 hours and a second ageing step at a temperature higher than 135°C but
less than 210°C for 4 to 12 hours to a temper selected from T79 and T76 temper.
7. Method according to claim 6, wherein the artificial ageing during step g.) consists
of a first ageing step at a temperature around 120°C for 2 to 20 hours and a second
ageing step at a temperature higher than 135°C but less than 210°C for 4 to 12 hours
to a temper selected from T79 and T76 temper.
8. Method according to claim 6 or 7, wherein the artificial ageing during step g.) consists
of a first ageing step at a temperature around 120°C for 2 to 20 hours and a second
ageing step at a temperature around 155°C for 4 to 12 hours to a temper selected from
T79 and T76 temper.
9. Method according to any one of claims 1 to 8, wherein the amount of Zn is in a range
of 7.4 to 9.6 wt.%.
10. Method according to claim 9, wherein the amount of Zn is in a range of 8.0 to 9.6
wt.%, and preferably in a range of 8.4 to 8.9 wt.%.
11. Method according to any one of claims 1 to 10, wherein the amount of Cu is in a range
of 1.7 to 2.2 wt.%, and preferably in a range of 1.8 to 2.1 wt.%.
12. Method according to claim 11, wherein the amount of Mg is in a range of 1.7 to 2.2
wt.%, and preferably in a range of 1.7 to 2.1 wt.%.
13. Method according to any one of claims 1 to 12, wherein the amount of Sc is in a range
of [Zr]+1.5 [Sc]<0.15 wt.%.
14. Method according to any one of claims 1 to 13, wherein the amount of Sc is in a range
of 0.03 to 0.06%, and wherein the amount of Ce is in a range of 0.03 to 0.06%.
15. Method according to any one of claims 1 to 14, wherein the amount of inevitable impurities
are < 0.05 wt.% each, and total < 0.5 wt.%.
16. Method according to any one of claims 1 to 15, wherein of the finished rolled product
more than 80%, and preferably more than 90%, of the gauge has a substantially unrecrystallized
microstructure.
17. Method according to any one of claims 1 to 16, wherein the AI-Zn product is a thin
plate having a gauge in the range of 20 to 60 mm, and preferably 30 to 50 mm.
18. Method according to any one of claims 1 to 17, wherein the AI-Zn product is a product
selected from the group consisting of thin aircraft member, an upper-wing member,
a thin skin member of an upper-wing, or a stringer of an aircraft.
1. Verfahren zur Herstellung eines hochfesten, hochzähen Al-Zn-Legierungsprodukts mit
guter Korrosionsbeständigkeit, umfassend die Schritte:
a.) (Guss)Formen eines Barrens mit der folgenden Zusammensetzung, in Gewichtsprozent:
Zn 6,0 bis 11,0%
Cu 1,4 bis 2,2%
Mg 1,4 bis 2,4%
Zr 0,05 bis 0,15%
Ti < 0,05%
Hf und/oder V < 0,25%,
wahlweise Sc und/oder Ce 0,05 bis 0,25%,
wahlweise Mn 0,05 bis 0,12%, und
unvermeidbare Verunreinigungen und Rest Aluminium,
b.) Homogenisieren und/oder Vorwärmen des Barrens nach dem Formen,
c.) Warmbearbeiten des Barrens zu einem vorbearbeiteten Produkt,
d.) Wiedererwärmen des vorbearbeiteten Produkts und Warmwalzen des nacherwärmten Produkts,
Kaltwalzen des warmgewalzten Produkts um ein Maß von 10 bis 20% auf Enddicke,
e.) Lösungsglühen und Abschrecken des lösungsgeglühten Produkts,
f.) optional Recken oder Komprimieren des abgeschreckten Legierungsprodukts, und
g.) optional Altern des abgeschreckten und ggf. gereckten oder komprimierten Produkts,
um einen gewünschten Zustand bzw. Temper zu erzielen,
und wobei das Produkt in seinem Endzustand eine im Wesentlichen vollständig nicht
rekristallisierte Mikrostruktur zumindest an der Position T/10 des fertigen Produkts
aufweist.
2. Verfahren nach Anspruch 1, wobei das Warmwalzen des nacherwärmten Produkts auf etwa
150 bis 250 (in Prozent der Enddicke) und dann das Kaltwalzen des warmgewalzten Produkts
auf die Enddicke erfolgen.
3. Verfahren nach Anspruch 1 oder 2, wobei das Warmwalzen des nacherwärmten Produkts
auf etwa 105 bis 140 (in Prozent des Endmaßes) und dann das Kaltwalzen des warmgewalzten
Produkts auf die Enddicke erfolgen.
4. Verfahren nach einem der Ansprüche 1 bis 3, umfassend das Warmwalzen des nacherwärmten
Produkts bei niedrigen Temperaturen im Bereich von 300°C bis 420°C, um das Legierungsprodukt
am Rekristallisieren zu hindern.
5. Verfahren nach einem der Ansprüche 1 bis 4, wobei das künstliche Altern während Schritt
g.) im Tempern besteht, ausgewählt aus der Gruppe bestehend aus T79 und T76, und bevorzugt
mithilfe einer zweistufigen Alterungsbehandlung.
6. Verfahren nach einem der Ansprüche 1 bis 5, wobei das künstliche Altern während Schritt
g.) aus einem ersten Alterungsschritt besteht bei einer Temperatur in einem Bereich
von 105 bis 135°C während 2 bis 20 Stunden und einem zweiten Alterungsschritt bei
einer Temperatur über 135°C, aber unter 210°C während 4 bis 12 Stunden bis zu einem
Zustand bzw. Temper ausgewählt aus T79- und T76-Temper.
7. Verfahren nach Anspruch 6, wobei das künstliche Altern während Schritt g.) aus einem
ersten Alterungsschritt besteht bei einer Temperatur um 120°C während 2 bis 20 Stunden
und aus einem zweiten Alterungsschritt bei einer Temperatur über 135°C, aber unter
210°C während 4 bis 12 Stunden bis zu einem Temper ausgewählt aus T79- und T76-Temper.
8. Verfahren nach Anspruch 6 oder 7, wobei das künstliche Altern während Schritt g.)
aus einem ersten Alterungsschritt besteht bei einer Temperatur um 120°C während 2
bis 20 Stunden und aus einem zweiten Alterungsschritt bei einer Temperatur um 155°C
während 4 bis 12 Stunden bis zu einem Temper ausgewählt aus T79- und T76-Temper.
9. Verfahren nach einem der Ansprüche 1 bis 8, wobei die Menge an Zn in einem Bereich
von 7,4 bis 9,6 Gew.-% liegt.
10. Verfahren nach Anspruch 9, wobei die Menge an Zn in einem Bereich von 8,0 bis 9,6
Gew.-% liegt, und bevorzugt in einem Bereich von 8,4 bis 8,9 Gew.-%.
11. Verfahren nach einem der Ansprüche 1 bis 10, wobei die Menge an Cu in einem Bereich
von 1,7 bis 2,2 Gew.-% liegt, und bevorzugt in einem Bereich von 1,8 bis 2,1 Gew.-%.
12. Verfahren nach Anspruch 11, wobei die Menge an Mg in einem Bereich von 1,7 bis 2,2
Gew.-% liegt, und bevorzugt in einem Bereich von 1,7 bis 2,1 Gew.-%.
13. Verfahren nach einem der Ansprüche 1 bis 12, wobei die Menge an Sc in einem Bereich
von [Zr]+1,5[Sc]<0,15 Gew.-% liegt.
14. Verfahren nach einem der Ansprüche 1 bis 13, wobei die Menge an Sc in einem Bereich
von 0,03 bis 0,06% liegt, und wobei die Menge an Ce in einem Bereich von 0,03 bis
0,06% liegt.
15. Verfahren nach einem der Ansprüche 1 bis 14, wobei die Menge an unvermeidbaren Verunreinigungen
jeweils <0,05 Gew.-% und insgesamt <0,5 Gew.-% beträgt.
16. Verfahren nach einem der Ansprüche 1 bis 15, wobei über 80%, und bevorzugt über 90%,
der Dicke bzw. des Maßes des fertigen gewalzten Produkts eine im Wesentlichen nicht
rekristallisierte Mikrostruktur aufweisen.
17. Verfahren nach einem der Ansprüche 1 bis 16, wobei das Al-Zn-Produkt eine dünne Platte
mit einer Dicke im Bereich von 20 bis 60 mm, und bevorzugt 30 bis 50 mm, ist.
18. Verfahren nach einem der Ansprüche 1 bis 17, wobei das Al-Zn-Produkt ein Produkt ist
ausgewählt aus der Gruppe bestehend aus einem dünnen Flugzeugteil, einem Teil der
oberen Tragfläche, einem dünnen Hautteil der oberen Tragfläche oder einem Längs(versteifungs)träger
eines Flugzeugs.
1. Procédé pour produire un produit en alliage Al-Zn à haute résistance, à ténacité élevée,
offrant une bonne résistance à la corrosion, comprenant les étapes consistant à :
a.) couler un lingot comportant la composition suivante, en pourcentage par poids
:
Zn de 6,0 à 11,0 %
Cu de 1,4 à 2,2 %
Mg de 1,4 à 2,4%
Zr de 0,05 à 0,15%
Ti < 0,05%
Hf et/ou V < 0,25%
facultativement Sc et/ou Ce - de 0,05 à 0,25 %
facultativement Mn - de 0,05 à 0,12 %, et
des impuretés inévitables et le reste étant de
l'aluminium,
b.) homogénéiser et/ou à préchauffer le lingot après coulage,
c.) travailler à chaud le lingot pour en faire un produit pré-ouvré,
d.) réchauffer le produit pré-ouvré et effectuer un laminage à chaud du produit réchauffé,
effectuer un laminage à froid du produit ayant été laminé à chaud d'un degré de 10
à 20% jusqu'à l'épaisseur finale,
e.) effectuer un traitement thermique par mise en solution et tremper le produit ayant
été traité thermiquement par mise en solution,
f.) étirer ou comprimer facultativement le produit trempé en alliage, et
g.) soumettre facultativement à un vieillissement le produit trempé et facultativement
étiré ou comprimé afin d'obtenir le revenu désiré,
et dans le cadre duquel le produit lors de son étape de revenu final a une microstructure
à non-recristallisation sensiblement totale au moins à la position T/10 du produit
fini.
2. Procédé selon la revendication 1, le laminage à chaud du produit réchauffé étant effectué
jusqu'à environ 150-250 (en pourcentage de l'épaisseur finale), et puis le laminage
à froid du produit ayant été laminé à chaud est effectué jusqu'à l'épaisseur finale.
3. Procédé selon la revendication 1 ou 2, le laminage à chaud du produit réchauffé étant
effectué jusqu'à environ 105-140 (en pourcentage de l'épaisseur finale), et puis le
laminage à froid du produit ayant été laminé à chaud est effectué jusqu'à l'épaisseur
finale.
4. Procédé selon l'une quelconque des revendications 1 à 3, comprenant le laminage à
chaud du produit réchauffé à des températures faibles dans la gamme de 300°C à 420°C
afin d'empêcher le produit en alliage de se recristalliser.
5. Procédé selon l'une quelconque des revendications 1 à 4, le vieillissement artificiel
réalisé au cours de l'étape g.) consistant en un revenu sélectionné à partir du groupe
constitué de T79 et de T76, et de préférence au moyen d'un traitement de vieillissement
en deux phases.
6. Procédé selon l'une quelconque des revendications 1 à 5, le vieillissement artificiel
réalisé au cours de l'étape g.) consistant en une première phase de vieillissement
à une température dans la gamme de 105°C à 135°C pendant 2 à 20 heures, et en une
deuxième phase de vieillissement à une température supérieure à 135°C mais inférieure
à 210°C pendant 4 à 12 heures jusqu'à un revenu sélectionné parmi les trempes T79
et T76.
7. Procédé selon la revendication 6, le vieillissement artificiel réalisé au cours de
l'étape g.) consistant en une première phase de vieillissement à une température aux
alentours de 120°C pendant 2 à 20 heures, et en une deuxième phase de vieillissement
à une température supérieure à 135°C mais inférieure à 210°C pendant 4 à 12 heures
jusqu'à un revenu sélectionné parmi les trempes T79 et T76.
8. Procédé selon la revendication 6 ou 7, le vieillissement artificiel réalisé au cours
de l'étape g.) consistant en une première phase de vieillissement à une température
aux alentours de 120°C pendant 2 à 20 heures, et en une deuxième phase de vieillissement
à une température aux alentours de 155°C pendant 4 à 12 heures jusqu'à un revenu sélectionné
parmi les trempes T79 et T76.
9. Procédé selon l'une quelconque des revendications 1 à 8, la teneur en Zn se situant
dans une gamme de 7,4 à 9,6 % par poids.
10. Procédé selon la revendication 9, la teneur en Zn se situant dans une gamme de 8,0
à 9,6 % par poids, et de préférence dans une gamme de 8,4 à 8,9 % par poids.
11. Procédé selon l'une quelconque des revendications 1 à 10, la teneur en Cu se situant
dans une gamme de 1,7 à 2,2 % par poids, et de préférence dans une gamme de 1,8 à
2,1 % par poids.
12. Procédé selon la revendication 11, la teneur en Mg se situant dans une gamme de 1,7
à 2,2 % par poids, et de préférence dans une gamme de 1,7 à 2,1 % par poids.
13. Procédé selon l'une quelconque des revendications 1 à 12, la teneur en Sc se situant
dans une gamme de [Zr]+1,5 [Sc]<0,15 % par poids.
14. Procédé selon l'une quelconque des revendications 1 à 13, la teneur en Sc se situant
dans une gamme de 0,03 à 0,06 %, et la teneur en Ce se situant dans une gamme de 0,03
à 0,06 %.
15. Procédé selon l'une quelconque des revendications 1 à 14, la teneur en impuretés inévitables
étant < 0,05 % par poids chacune, et le total étant < 0,5 % par poids.
16. Procédé selon l'une quelconque des revendications 1 à 15, plus de 80 %, et de préférence
plus de 90 %, de l'épaisseur du produit laminé fini ayant une microstructure sensiblement
non-recristallisée.
17. Procédé selon l'une quelconque des revendications 1 à 16, le produit en Al-Zn étant
une fine plaque dont l'épaisseur se situe dans la gamme de 20 à 60 mm, et de préférence
de 30 à 50 mm.
18. Procédé selon l'une quelconque des revendications 1 à 17, le produit en Al-Zn étant
un produit sélectionné à partir du groupe constitué des postes suivants : un élément
mince pour avions, un élément d'aile haute, un élément à revêtement mince d'une aile
haute ou un longeron d'un avion.
REFERENCES CITED IN THE DESCRIPTION
This list of references cited by the applicant is for the reader's convenience only.
It does not form part of the European patent document. Even though great care has
been taken in compiling the references, errors or omissions cannot be excluded and
the EPO disclaims all liability in this regard.
Patent documents cited in the description