This invention relates to the heat treatment of aluminium alloys,
that are able to be strengthened by the well known phenomenon of age (or precipitation)
hardening.
Heat treatment for strengthening by age hardening is applicable to
alloys in which the solid solubility of at least one alloying element decreases
with decreasing temperature. Relevant aluminium alloys include some series of wrought
alloys, principally those of the 2XXX, 6XXX and 7XXX (or 2000, 6000 and 7000) series
of the International Alloy Designation System (IADS). However, there are some relevant
age-hardenable aluminium alloys which are outside these series. Also, some castable
aluminium alloys are age hardenable. The present invention extends to all such aluminium
alloys, including both wrought and castable alloys, and also can be used with alloy
products produced by processes such as powder metallurgy and with rapidly solidified
products, as well as with particulate reinforced alloy products and materials.
Processes for heat treatment of age-hardenable aluminium alloys normally
involve the following three stages:
(1) solution treatment at a relatively high temperature, below the melting point
of the alloy, to dissolve its alloying (solute) elements;
(2) rapid cooling, or quenching, such as into cold water, to retain the solute
elements in a supersaturated solid solution; and
(3) ageing the alloy by holding it for a period of time at one, sometimes at
a second, intermediate temperature, to achieve hardening or strengthening.
The strengthening resulting from ageing occurs because the solute, retained in
supersaturated solid solution by quenching, forms precipitates during the ageing
which are finely dispersed throughout the grains and which increase the ability
of the alloy to resist deformation by the process of slip. Maximum hardening or
strengthening occurs when the ageing treatment leads to formation of a critical
dispersion of at least one of these fine precipitates.
Ageing conditions differ for different alloy systems. Two common treatments
which involve only one stage are to hold for an extended time at room temperature
(T4 temper) or, more commonly, at an elevated temperature for a shorter time (for
example 8 hours) which corresponds to a maximum in the hardening process (T6 temper).
For certain alloys, it is usual to hold for a prescribed period of time (for example
24 hours) at room temperature before applying the T6 temper at an elevated temperature.
In other alloys, notably those based on the Al-Cu and Al-Cu-Mg systems (of the 2000
series), deformation (for example by stretching or rolling 5%) after quenching and
before ageing at an elevated temperature, causes an increased response to strengthening.
This is known as a T8 temper and it results in a finer and more uniform dispersion
of precipitates throughout the grains.
For alloys based on the Al-Zn-Mg-Cu system (of the 7000 series) several
special ageing treatments have been developed which involve holding for periods
of time at two different elevated temperatures. The purpose of each of these treatments
is to reduce the susceptibility of alloys of this series to the phenomenon of stress
corrosion cracking. One example is the T73 temper which involves ageing first at
a temperature close to 100°C and then at a higher temperature, e.g. 160°C. This
treatment causes some reduction in strength when compared to a T6 temper. Another
example is the treatment known as retrogression and re-ageing (RRA) which involves
three stages, for example 24 hours at 120°C, a much shorter time at a higher temperature
(200-280°C) and a further 24 hours at 120°C. Some such treatments tend to remain
confidential to companies that supply the alloys.
It is generally accepted that, once an aluminium alloy (or other suitable
material) is hardened by ageing at an elevated temperature, the mechanical properties
remain stable when the alloy is exposed for an indefinite time at a significantly
lower temperature. However, recent results have shown that this is not always the
case. A magnesium alloy, WE54, which is normally aged at 250°C to achieve its T6
temper, has shown a gradual increase in hardness together with an unacceptable decrease
in ductility if subsequently exposed for long periods at a temperature close to
150°C. This effect is attributed to slow, secondary precipitation of a finely dispersed
phase throughout the grains of the alloy. More recently certain lithium-containing
aluminium alloys, such as 2090 (Al - 2.7 Cu - 2.2 Li), have shown similar behaviour
if exposed for long times at temperatures in the range 60 to 135°C, after being
first aged to the T6 temper at 170°C.
JP-A 59 226 197 relates to age-hardening of Al-based alloys by aging
at 160°C for 3 hours, cooling to room temperature and final aging at 190°C for 3
hours.
The present invention is directed to providing a process for the heat
treatment of an age-hardenable aluminium alloy which has alloying elements in solid
solution, wherein the process includes the stages of:
a) artificially ageing the alloy at a temperature TA which would
be an appropriate temperature for a conventional T6 temper for the alloy, wherein
the artificial ageing is conducted for a period sufficient to achieve strengthening
of the alloy which corresponds to from 50% to 95% of the maximum strengthening obtainable
by a full T6 temper for the alloy at the temperature TA;
(b) quenching the alloy in an underaged condition attained at the end of the
period for stage (a), from the temperature TA to a temperature in the
range from ambient temperature to about -10°C, to arrest primary precipitation and
to provide the alloy in an underaged and quenched condition;
(c) holding the underaged and quenched alloy at temperature TB which
is below the temperature TA and is in the range of from -10°C to 120°C
to achieve secondary nucleation or continuing precipitation of solute elements;
and
(d) heating the alloy from the temperature TB to a temperature TC
in the range of (TA -50°C) to (TA +50°C) and holding the alloy
at the temperature Tc for further artificial ageing of the alloy;
wherein the alloy is further strengthened by the combination of steps (c) and (d)
to a level of strength which is in excess of the maximum strength obtainable for
the alloy by a full conventional T6 temper at temperature TA.
This series of treatment stages in accordance with the present invention
is termed T616, indicating the first ageing treatment before the stage (c) interrupt
("I") and the treatment after the interrupt.
Stages (c) and (d) may be successive stages. In that case, there may
be little or no applied heating in stage (c). However, it should be noted that stages
(c) and (d) may be effectively combined through the use of appropriately controlled
heating cycles. That is, stage (c) may utilise a heating rate, to the final ageing
temperature Tc which is sufficiently slow to provide the secondary nucleation
or precipitation at relatively lower average temperature than the final ageing temperature
Tc.
We have found that, with the heat treatment of the present invention,
substantially all aluminium alloys capable of age hardening can undergo additional
age hardening and strengthening to higher levels than are possible with a normal
T6 temper. Maximum hardness can be increased such as by 10 to 15%, while yield strength
(i.e. 0.2% proof stress) and tensile strength can be increased such as by 5 to 10%
or, with at least some alloys, even higher, relative to levels obtainable with conventional
T6 heat treatments. Moreover, at least In many cases and contrary to usual behaviour
after conventional treatments, the increases obtainable with the present invention
are able to be achieved without any significant decrease in ductility as measured
by elongation occurring on testing alloys to failure.
As indicated, the process of the present invention enables alloys
to undergo additional age hardening and strengthening to higher levels relative
to the age hardening and strength obtainable for the same alloy subjected to a normal
T6 temper. The enhancement can be in conjunction with mechanical deformation of
the alloy before stage (a); after stage (b) but before stage (c); and/or during
stage (c). The deformation may be by appreciation of thermomechanical deformation;
while deformation may be applied in conjunction to rapid cooling. The alloy may
be aged in stage (a) directly after fabrication or casting with no solution treatment
stage.
The process of the present invention is applicable not only to the
standard T6 temper but also applicable to other tempers. These include such instances
as the T5 temper, where the alloy is aged directly after fabrication with no solution
treatment step and a partial solution of alloying elements is formed. Other tempers,
such as the T8 temper, include a cold working stage. In the T8 temper the material
is cold worked before artificial ageing, which results in an improvement of the
mechanical properties in many aluminium alloys through a finer distribution of precipitates
nucleated on dislocations imparted through the cold working step. The equivalent
new temper is thus designated T8I6, following the same convention in nomenclature
as the T6I6 temper. Another treatment involving a cold working step, again following
the process of the present invention, is designated T9I6. In this case the cold
working step is introduced after the first ageing period, TA and before
the interrupt treatment at temperature TB. After the interrupt treatment
is completed, the material is again heated to the temperature TC, again
following the convention of the T6I6 treatment.
Similar parallels exist with temper designations termed T7X, as exemplified
previously, where a decreasing integer of X refers to a greater degree of overageing.
These treatments consist of a two step process where two ageing temperatures are
used, the first being relatively low (e.g. 100°C) and the second at a higher temperature
of, for example, 160°C-170°C. In applying the new treatment to such tempers, the
final ageing temperature TC is thus in the range of the usual second
higher temperatures of 160°C-170°C, with all other parts of the treatment being
equivalent to the T6I6 treatment. Such a temper is thus termed T8I7X when employing
the new nomenclature.
It should also be noted that the new treatment can be similarly applied
to a wide variety of existing tempers employing significantly differing thermomechanical
processing steps, and is in no way restricted to those listed above.
The process of the invention has proved to be effective in each of
the classes of aluminium alloys that are known to respond to age hardening. These
include the 2000 and 7000 series mentioned above, the 6000 series (Al-Mg-Si), age
hardenable casting alloys, as well as particulate reinforced alloys. The alloys
also include newer lithium-containing alloys such as 2090 mentioned above and 8090
(Al - 2.4 Li - 1.3 Cu - 0.9 Mg), as well as silver-containing alloys, such as, 2094,
7009 and experimental Al-Cu-Mg-Ag alloys.
The process of the invention can be applied to alloys which, as received,
have been subjected to an appropriate solution treatment stage followed by a quenching
stage to retain solute elements in supersaturated solid solution. Alternatively,
these can form preliminary stages of the process of the invention which precede
stage (a). In the latter case, the preliminary quenching stage can be to any suitable
temperature ranging from TA down to ambient temperature or lower. Thus,
in a preliminary quenching stage to attain the temperature TA, the need
for reheating to enable stage (a) can be avoided.
The purpose of the solution treatment, whether of the alloy as received
or as a preliminary stage of the process of the invention, is of course to take
alloying elements into solid solution and thereby enable age hardening. However,
the alloying elements can be taken into solution by other treatments and such other
treatments can be used instead of a solution treatment.
As will be appreciated, the temperatures TA, TB
and TC for a given alloy are capable of variation, as the stages to which
they relate are time dependent. Thus, TA for example can vary with inverse
variation of the time for stage (a). Correspondingly, for any given alloy, the temperatures
TA, TB and TC can vary over a suitable range during
the course of the respective stage, Indeed, variation in TB during stage
(c) is implicit in the reference above to stages (c) and (d) being effectively combined.
The temperature TA used in stage (a) for a given alloy
can be the same as, or close to, that used in the ageing stage of a conventional
T6 heat treatment for that alloy. However, the relatively short time used in stage
(a) is significantly less than that used in conventional ageing. The time for stage
(a) may be such as to achieve a level of ageing needed to achieve from about 50%
to about 95% of maximum strengthening obtainable by full conventional T6 ageing.
Preferably, the time for stage (a) is such as to achieve from about 85% to about
95% of that maximum strength.
For many aluminium alloys, the temperature TA most preferably
is that used when ageing for any typical T6 temper. The relatively short time for
stage (a) may be, for example, from several minutes to, for example, 8 hours or
more, such as from 1 to 2 hours, depending on the alloy and the temperature TA.
Under such conditions, an alloy subjected to stage (a) of the present invention
would be said to be underaged.
The cooling of stage (b) is by quenching. The quenching medium may
be cold water or other suitable media. The quenching can be to ambient temperature
or lower, such as to about -10°C. However, as indicated, the cooling of stage (b)
is to arrest the ageing which results directly from stage (a); that is, to arrest
primary precipitation of solute elements giving rise to that ageing.
The temperatures TB and TC and the respective
period of time for each of stages (c) and (d) are inter-related with each other.
They also are inter-related with the temperature TA and the period of
time for stage (a); that is, with the level of underageing achieved in stage (a).
These parameters also vary from alloy to alloy . For many of the alloys, the temperature
TB can be in the range of from about -10°C to about 90°C, such as from
about 20°C to about 90°C. However for at least some alloys, a temperature TB
in excess of 90°C, such as to about 120°C, can be appropriate.
The period of time for stage (c) at temperature TB is to
achieve secondary nucleation or continuing precipitation of solute elements of the
alloy. For a selected level of TB, the time is to be sufficient to achieve
additional sufficient strengthening. The additional strengthening, while still leaving
the alloy significantly underaged, usually results in a worthwhile level of improvement
in hardness and strength. The improvement can, in some instances, be such as to
bring the alloy to a level of hardness and/or strength comparable to that obtainable
for the same alloy by that alloy being fully aged by a conventional T6 heat treatment.
Thus if, for example, the underaged alloy resulting from stage (a) has a hardness
and/or strength value which is 80% of the value obtainable for the same alloy fully
aged by a conventional T6 heat treatment, heating the alloy at TB for
a sufficient period of time may increase that 80% value to 90%, or possibly even
more.
The period of time for stage (c) may, for example, range from less
than 8 hours at the lower end, up to about 500 hours or more at the upper end. Simple
trials can enable determination of an appropriate period of time for a given alloy.
However, a useful degree of guidance can be obtained for at least some alloys by
determining the level of increase in hardness and/or strength after relatively short
intervals, such as 24 and 48 hours, and establishing a curve of best fit for variation
in such property with time. The shape of the curve can, with at least some alloys,
give useful guidance of a period of time for stage (c) which is likely to be sufficient
to achieve a suitable level of secondary strengthening.
The temperature TC used during stage (d) can be substantially
the same as TA. For a few alloys, TC can exceed TA,
such as by up to about 20°C or even up to 50°C (for example, for T617X treatment).
However for many alloys it is desirable that TC be at TA or
lower than TA, such as 20°C to 50°C, preferably 30 to 50°C, below TA.
Some alloys necessitate TC being lower than TA, in order to
avoid a regression in hardness and/or strength values developed during stage (c).
The period of time at temperature TC during stage (d) needs
to be sufficient for achieving substantially maximum strength. In the course of
stage (d), strength values and also hardness are progressively improved until, assuming
avoidance of significant regression, maximum values are obtainable. The progressive
improvement occurs substantially by growth of precipitates produced during stage
(c). The final strength and hardness values obtainable can be 5 to 10% or higher
and 10 to 15% or higher, respectively, than the values obtainable by a conventional
T6 heat treatment process. A part of this overall improvement usually results from
precipitation achieved during stage (c), although a major part of the improvement
results from additional precipitation achieved in stage (d).
In order that the invention may more readily be understood, description
now is directed to the accompanying drawings, in which:
Figure 1 is a schematic time-temperature graph illustrating an application of
the process of the present invention;
Figure 2 is a plot of time against hardness, illustrating application of the
process of the invention to Al-4Cu alloy, during T6I6 processing compared with a
conventional T6 temper;
Figure 3 shows respective photomicrographs for T6 and T6I6 processing of Figure
2 for Al-4 Cu alloy;
Figure 4 shows a plot of time against hardness, showing the effect of cooling
rate from TA in the process of the invention for Al-4 Cu alloy;
Figure 5 corresponds to Figure 2, but is in respect of alloy 2014;
Figure 6 corresponds to Figure 2, but is in respect of Al-Cu-Mg-Ag alloy for
both a T6 temper and, according to the present invention, a T6I6 temper;
Figure 7 illustrates stage (c) of the invention for the Al-Cu-Mg-Ag alloy of
Figure 6;
Figure 8 shows the effect of cooling rate from TA for the Al-Cu-Mg-Ag
alloy T6I6 temper according to the invention;
Figure 9 illustrates for the Al-Cu-Mg-Ag alloy regression able to occur in the
T6I6 temper;
Figure 10 corresponds to Figure 2, but is in respect of 2090 alloy;
Figure 11 shows a T6I6 hardness curve for 8090 alloy;
Figure 12 shows a hardness curve for the 8090 alloy with a T9I6 temper including
a cold working stage;
Figure 13 shows T8 and T8I6 hardness curves for the 8090 alloy cold worked after
solution treatment;
Figure 14 to 17 illustrate T6 and T6I6 hardness curves for respective 6061,
6013, 6061 + Ag and 6013 + Ag alloys;
Figure 18 shows a T6I6 hardness curve for alloy material comprising 6061 + 20%
SiC;
Figures 19 to 22 show plots for the respective alloys of Figures 14 to 17 as
a function of interrupt hold temperature in T6I6 tempers according to the invention;
Figure 23 shows the effect of a cold working step between stages (b) and (c)
in the T6I6 temper for the respective alloys of Figures 19 to 22;
Figure 24 shows hardness curves for T6I6 and T6I76 tempers according to the
invention for 7050 alloy;
Figures 25 and 26 show hardness curves for T6I6 tempers for respective 7075
and 7075 + Ag alloys;
Figure 27 shows the effect of temperature on the interrupt of stage (c) for
the process and respective alloys of Figures 25 and 26;
Figure 28 shows a comparison of T6 and T6I6 ageing curves for an Al-8Zn-3Mg
alloy;
Figure 29 shows a T6I6 hardness curve for Al-6Zn-2Mg-0.5Ag alloy on a linear
time scale;
Figures 30 and 31 show ageing curves for T6 and T6I6 tempers for 356 and 357
casting alloys respectively;
Figures 32 and 33 show plots illustrating fracture toughness/damage tolerance
behaviour for 6061 and 8090 alloys after each of T6 and T6I6 tempers; and
Figure 34 compares cycles to failure in fatigue tests on 6061 alloy after T6
and T6I6 tempers.
The present invention enables the establishment of conditions whereby
aluminium alloys which are capable of age hardening may undergo this additional
hardening at a lower temperature TB if they are first underaged at a
higher temperature TA for a short time and then cooled by being quenched
to room temperature. This general effect is demonstrated in Figure 1, which is a
schematic representation of how the interrupted ageing process of the invention
is applied to age hardenable alloys in a basic form of the present invention. As
shown in Figure 1, the ageing process utilises successive stages (a) to (d). However,
as shown, stage (a) is preceded by a preliminary solution treatment in which the
alloy is held at a relatively high initial temperature and for a time sufficient
to facilitate solution of alloy elements. The preliminary treatment may have been
conducted in the alloy as received, in which case the alloy typically will have
been quenched to ambient temperature, as shown, or below ambient temperature. However,
in an alternative, the preliminary treatment may be an adjunct to the process of
the invention, with quenching being to the temperature TA for stage (a)
of the process of the invention, thereby obviating the need to reheat the alloy
to TA.
In stage (a), the alloy is aged at temperature TA. The
temperature TA and the duration of stage (a) are sufficient to achieve
a required level of underaged strengthening, as described above. From TA,
the alloy is quenched in stage (b) to arrest the primary precipitation ageing in
stage (a); with the stage (b) quenching being to or below ambient temperature. Following
the quenching stage (b), the alloy is heated to temperature TB in stage
(c), with the temperature at TB and the duration of stage (c) sufficient
to achieve secondary nucleation, or continuing precipitation of solute elements.
After stage (c), the alloy is further heated in stage (d) to temperature TC,
with the temperature TC and the duration of step (d) sufficient to achieve
ageing of the alloy to achieve the desired properties. The temperatures and durations
may be as described early herein.
In relation to the schematic representation shown in Figure 1 of the
interrupted ageing process and how it is applied to all age hardenable aluminium
alloys, the time at temperature TA is commonly from between a few minutes
to several hours, depending on the alloy. The time at temperature TB
is commonly from between a few hours to several weeks, depending on the alloy. The
time at temperature TC is usually several hours, depending on both the
alloy and the re-ageing temperature TC, where is here represented by
the shaded region in the diagram.
Figure 2 shows application of the process of the present invention
to Al-4Cu alloy. In Figure 2, the solid line shows the hardness-time (ageing) curve
obtained when the Al-4Cu alloy is first solution treated at 540°C, quenched into
cold water and aged at 150°C. A peak T6 value of hardness of 132 VHN is achieved
after 100 hours. The dashed curves show respective hardening responses if a low
temperature interrupt stage is introduced, i.e. the process of the invention is
introduced, for the treatment (designated as a T6I6 treatment). In this case, the
alloy has been:
(a) aged for only 2.5 hours at 150°C;
(b) quenched into quenchant;
(c) held at 65°C for 500 hours;
(d) re-aged at 150°C.
The peak hardness is now achieved in the shorter time of 40 hours and has been
increased to 144 VHN.
As indicated, the solid line in Figure 2 (filled diamonds) is the
ageing response for Al - 4Cu alloy conventionally aged at 150°C in accordance with
the T6 heat treatment. The dashed lines in the main diagram shows the ageing response
for a TC temperature after an interrupt quench and TB interrupt
hold at 65°C. The TC reageing was at each of 130°C (triangles) and 150°C
(squares). The inset diagram shows the ageing response plot for the interrupt hold
at 65°C, with this being represented by the vertical dashed line in the main diagram.
Figure 3 shows examples of micrographs developed in the T6 and T6I6
tempering of Al-4Cu alloy as described with reference to Figure 2. The variation
in microstructures of the T6 and T6I6 processing shown in Figure 3 is considered
representative of the difference in structure developed in all age hardenable aluminium
alloys processed in a similar fashion. As seen in Figure 3, the T6I6 process results
in the development of microstructures having a higher precipitate density and a
finer precipitate size than the peak aged material resulting from the T6 processing.
Figure 4 shows for the Al-4Cu alloy, treated as described with reference
to Figure 2, the effect of cooling rates from the first ageing temperature TA,
on the ageing response developed in the low temperature (TB) ageing period.
Here it is seen that some benefit may be gained by the use of cold water or other
cooling media appropriate to the particular alloy. More specifically, Figure 4 shows
the effect of cooling rate from the ageing temperature of 150°C (TA)
on the low temperature interrupt response for Al-4Cu. Filled diamonds are for a
quench into water at ~65°C, open squares are for a quench into cold water at ~15°C
and filled triangles for a quench into a quenchant mixture of ethylene glycol, ethanol,
NaCl and water at ~-10°C. The effect shown by Figure 4 varies from alloy to alloy.
Examples of the increases in hardness, in response to age hardening
by applying the T6I6 treatment in accordance with the invention are shown in Table
1 for a range of alloys, as well as selected examples of variants of the standard
treatments. Typical tensile properties developed in response to T6I6 age hardening
according to the invention are shown in Table 2. In each of Tables 1 and 2, the
corresponding T6 values for each alloy are presented. In most cases, it will be
seen from Table 2 that the ductility as measured by the percent elongation after
failure is either little changed or increased, although this is alloy dependent.
It also is to be noted that there is no detrimental effect to either fracture toughness
or fatigue strength with the T6I6 treatment.
The strain to failure in the comparison of Table 2 for casting alloy
357 appears to be inconsistent with other data presented. However it should be noted
that the test batch from which these samples were taken typically display levels
between 1 and 8% strain, with a mean of ~4.5%. Therefore it should be considered
that the values presented for the T6 and T6I6 tempers in alloy 357 are effectively
equivalent.
Table 3 shows typical hardness values associated with T6 peak ageing,
and the maximum hardness developed during stage (d) for the T6I6 condition for the
various alloys. Table 3 also shows the time of the first ageing temperature during
stage (a) and the typical hardness at the end of stage (a). Additionally, Table
3 shows for each alloy the approximate increase in hardness during the entire TB
hold of stage (c), as well as the increase in hardness during the TB
hold, after 24 and 48 hours and at different TB temperatures.
Figure 5 corresponds to Figure 2, but relates to 2014 alloy, again
with an interrupt hold at 65°C. The alloy 2014 was aged according to the T6I6 temper,
after benign solution treated at 505°C for 1 hour. The inset plot shows an interrupt
hold at 65°C, represented by vertical dashed line in main diagram.
Figure 6 illustrates respective hardness curves for Al-Cu-Mg-Ag alloy
for a conventional T6 temper (triangles) and a T6I6 temper according to the invention
(squares). The alloy, specifically Al-5.6Cu-0.45Mg-0.45Ag-0.3Mn-0.18Zr was solution
treated at 525°C for 8 hours. The T6 curve (triangles) applies to the alloy aged
at 185°C, while the T6I6 curve (open squares) applies to the alloy aged initially
at 185°C, held for interrupt at 25°C, and re-aged at 185°C.
Figure 7 shows for that alloy hardening during respective interrupt
holds (stage (c)) each at 25°C, but with respective levels of underageing as represented
by the solid curve. Figure 8, for that Al-Cu-Mg-Ag alloy, shows the effect of cooling
rate from ageing temperature on interrupt response, with the interrupt hold again
at 25°C. Figure 8 shows the effect of cooling rate from solution treatment temperature
on low temperature interrupt response for Al-5.6Cu-0.45Mg-0.45Ag-0.3Mn-0.18Zr. Diamonds
represent the response when the quench from the first ageing treatment temperature
(TA) was conducted into cooled quenchant, and triangles represent the
interrupt response when the sample was naturally cooled in hot oil from the first
ageing temperature.
Figure 9, for Al-Cu-Mg-Ag alloy, exhibits the effect of the regression
which may occur when reheating to the final ageing temperature Tc. For
this case, the time of the first ageing temperature during stage (a) and the typical
hardness at the end of stage (a) are identical. More specifically, Figure 9 shows
the effect of slower quenching rate from the solution treatment temperature of 525°C
on alloy 5.6Cu-0.45Mg-0.45Ag-0.3Mn-0.18Zr. The material was quenched into room temperature
tap water, aged 2 hours at 185°C, interrupt at 65°C 7 days. When reheated at 185°C
(diamonds) the hardness regresses early, unlike the response shown in Figure 6.
In this case the higher properties are gained through the use of a re-ageing temperature
of 150°C (circles), which is then not affected by regression. Table 3 also shows
a Tc temperature of 150°C instead of 185°C is appropriate to achieve
the maximum strengthening.
Figure 10 corresponds to Figure 2, but relates to alloy 2090. Figure
10 shows comparison of T6 and T6I6 ageing curves for alloy 2090. The alloy was solution
treated at 540°C for 2 hours. The T6 ageing was at 185°C. For the T6I6 treatment,
the alloy was aged at 185°C for 8 hours, held at 65°C for interrupt (inset plot),
and reaged at 150°C.
Figure 11 shows the T6I6 curve for alloy 8090. The alloy was solution
treated for 2 hours at 540°C, quenched and aged at 185°C for 7.5 hours, held at
65°C for interrupt (inset plot), and re-aged at 150°C.
Figure 12 shows an example of the T9I6 curve for 8090, where cold
work has been applied immediately following stage (b), and directly before stage
(c), before continuing ageing according to the invention. Specifically, the alloy
was aged for 8 hours at 185°C, quenched, cold worked 15%, held at 65°C for interrupt
(inset plot) and re-aged at 150°C. Note here that the interrupt response was not
as great as in the T6I6 condition shown in Figure 11.
Figure 13 shows an example comparison of T8 and T8I6 curves for alloy
8090, where the cold work has been applied immediately following solution treatment
and quenching, but before any artificial ageing. For the T8 treatment, the alloy
was solution treated at 560°C, quenched, and aged at 185°C. For the T8I6 treatment,
the solution treated alloy was aged 10 minutes at 185°C, held at 65°C for interrupt
treatment (inset plot), and then reaged at 150°C.
Figures 14 to 17 show example comparisons between the T6 hardness
curves and the T6I6 hardness curves for alloys 6061, 6013, 6061+Ag, 6013+Ag respectively.
In the case of Figure 14, the alloy 6061 was solution treated for 1 hour at 540°C.
T6 ageing (filled diamonds) was at 177°C: while the T6I6 ageing (open diamonds)
was at 177°C for 1 hour, quenched, held at 65°C for interrupt treatment, and re-ageing
at 150°C. With Figure 15, the alloy 6013 was solution treated for 1 hour at 540°C.
T6 ageing (filled diamonds) was at 177°C. The T6I6 ageing (open diamonds) was at
177°C for 1 hour, quenched, held at 65°C for interrupt treatment, and re-ageing
at 150°C. Figure 15 also represents results obtainable with alloys 6056 and 6082
under similar T6I6 conditions due to compositional similarity. Figure 16 shows results
for alloy 6061+Ag, solution treated for 1 hour at 540°C. The T6 ageing (filled diamonds)
was at 177°C. The T6I6 ageing (open diamonds) was at 177°C for 1 hour, quenched,
held at 65°C for interrupt treatment, and re-ageing at 150°C. With Figure 17, the
results are for alloy 6013+Ag, solution treated for 1 hour at 540°C. The T6 ageing
(filled diamonds) was at 177°C. The T6I6 ageing (open diamonds was at 177°C for
1 hour, quenched, held at 65°C for interrupt treatment, and reageing at 150°C.
Figure 18 shows the T6I6 curve for 6061+20%SiC. This alloy was solution
treated for 1 hour at 540°C. T6I6 ageing was at 177°C for 1 hour, quenched, held
at 65°C for interrupt treatment, and re-ageing at 150°C.
Figures 19 to 22 show respective plots for the interrupt hold step
of stage (c) for each of the alloys 6061, 6013, 6061 +Ag, 6013+Ag, as a function
of interrupt hold temperature, TB. In each case, the respective alloy
was aged 1 hour before the interrupt treatment at temperatures of 45°C (asterisks),
65°C (squares) and 80°C (triangles).
Figure 23 shows the effect of 25% cold work immediately after stage
(b) before the interrupt on the interrupt step. The alloys to which Figure 23 relates
are 6061 (diamonds), 6061+Ag (squares), 6013 (triangles) and 6013+Ag (circles),
with the interrupt hold temperature TB being 65°C for the solid diamonds,
squares, triangles and circles and 45°C for those symbols shown in open form.
Figure 24 shows examples of the T6I6 and T6I76 treatments, as applied
to alloy 7050. In each case, the alloy was solution treated at 485°C, quenched,
aged at 130°C, quenched with interrupt treatment at 65°C (inset plot), then re-aged
at 130°C (diamonds) or at 160°C (triangles). Note that the peak hardness for the
T6 condition is 213 VHN.
Figures 25 and 26 show examples of the T6I6 heat treatments for the
alloys 7075 and 7075+Ag (similar to alloy AA-7009), respectively. Each alloy was
solution treated at 485°C for 1 hour, quenched, aged 0.5 hours at 130°C, with an
interrupt at 35°C, and reaged at 100°C.
Figure 27 shows the effect of temperature on the interrupt stage of
the invention, respectively for each of 7075 and 7075+Ag. The upper plot relates
to alloy 7075 and the lower plot relates to alloy 7075+Ag. in each case, a low temperature
interrupt step was at 25°C (diamonds), 45°C (squares) or 65°C (triangles). Note
that with each alloy there is a difference in behaviour between 25°C and the slightly
higher interrupt temperatures of 45°C and 65°C.
Figure 28 shows an example comparison of T6 and T6I6 ageing curves,
for an Al-8Zn-3Mg alloy with an interrupt hold at 35°C. The T6 temper was at 150°C
and is shown by filled diamonds while the T6I6 temper is shown by open diamonds.
T6I6 alloy was solution treated at 480°C for 1 hour, quenched, aged at 150°C 20
minutes, quenched, interrupt treatment at 35°C and reaged at 150°C. The inset plot
shows the ageing response during the stage (c) interrupt hold.
Figure 29 exhibits the T6I6 ageing curve for Al-6Zn-2Mg-0.5Ag alloy
(interrupt hold at 35°C), where the interrupt step is included in context in the
plot of ageing on a linear time scale. In this case, the alloy was solution treated
for 1 hour at 480°C, quenched, then aged for 45 minutes at 150°C, quenched, interrupt
treatment at 35°C, and reaged at 150°C. The open squares represent the interrupt
step.
Figure 30 and 31 exhibit example comparisons of the T6 and T6I6 ageing
curves for each of the casting alloys 356 and 357. The alloy 356 to which Figure
30 relates was solution treated at 520°C for 24 hours and quenched. For the T6 treatment,
the alloy was aged 3 hours at 177°C, quenched, interrupt treatment at 65°C, and
reaged at 150°C. The alloy 356 was from a secondary aluminium billet, sand cast
with no modifiers or chills. The alloy 357 alloy was solution treated at 545°C for
16 hours, quenched into water at 65°C, and cooled quickly to room temperature. For
the T6 treatment, the alloy 357 alloy was aged at 177°C. For the T6I6 temper, the
alloy 357 was aged for 20 minutes at 177°C, quenched, interrupt treatment at 65°C.
and reaged at 150°C. The alloy 357 was high quality permanent mould cast with chills
and Sr modifier.
Table 4 provides an example of fracture toughness comparison values,
comparing the T6 and T6I6 tempers of the various alloys.
Figures 32 and 33 exhibit example comparisons of the fracture toughness
/ damage tolerance behaviour for alloys 6061 and 8090 tested in the s-l orientation
for each of the T6 and T6I6 conditions.
Figure 34 exhibits an example comparison of the fatigue life of alloy
6061 aged to either the T6 or T6I6 tempers, which indicates that the fatigue life
is not detrimentally affected by the increases in strength.
Finally, it is to be understood that various alterations, modifications
and/or additions may be introduced into the constructions and arrangements of parts
previously described without departing from the scope of the claims.
Anspruch[de]
Verfahren zur Wärmebehandlung einer härtbaren Aluminiumlegierung, die Legierungselemente
in fester Lösung aufweist, wobei das Verfahren die Schritte umfasst:
a) künstliches Altern der Legierung bei einer Temperatur TA, welche
eine geeignete Temperatur für ein konventionelles T6-Härten für die Legierung wäre,
wobei das künstliche Altern in einem für das Erreichen einer Festigkeitssteigerung
der Legierung, die zwischen 50 und 95 % der maximal erreichbaren Festigkeit bei
einem vollständigen T6-Härten für die Legierung bei einer Temperatur TA
entspricht, ausreichendem Zeitraum durchgeführt wird;
b) Abschrecken der Legierung in einem am Ende des Zeitraums für Schritt (a)
erreichten, nicht ausgehärteten Zustand von der Temperatur TA auf eine
Temperatur im Bereich zwischen Raumtemperatur und - 10 °C, um die Primärfällung
zu stoppen und die Legierung in einem nicht ausgehärteten und abgeschreckten zustand
zu erhalten;
c) Halten der nicht ausgehärteten und abgeschreckten Legierung bei einer Temperatur
TB, welche unter der Temperatur TA liegt und im Bereich von
-10 °C bis 120 °C liegt, um eine Sekundärkeimung oder eine Fortsetzung der Fällung
der gelösten Elemente zu erreichen; und
d) Erwärmen der Legierung von der Temperatur TB auf eine Temperatur
TC im Bereich von (TA -50 °C) bis (TA +50 °C) und
Halten der Legierung bei der Temperatur TC zum weiteren künstlichen Altern der Legierung;
wobei die Legierung durch die Kombination der Schritte (c) und (d) weiter verfestigt
wird auf ein Festigkeitsniveau, das über der für die Legierung maximal durch ein
vollständiges konventionelles T6-Härten bei einer Temperatur TA erreichbaren
Festigkeit liegt.
Verfahren nach Anspruch 1, wobei die Schritte (c) und (d) aufeinander folgen.
Verfahren nach Anspruch 2, wobei in Schritt (c) kein Erwärmen durchgeführt wird.
Verfahren nach Anspruch 1, wobei die Schritte (c) und (d) durch den Einsatz
von kontrollierten Heizzyklen miteinander kombiniert sind, wobei sich Schritt (c)
eine Heizrate zu der Temperatur TC zunutze macht, die die Sekundärkeimung
oder die Fällung für Schritt (c) bei einer verhältnismäßig tieferen Temperatur
als der Endtemperatur TC liefert.
Verfahren nach einem der Ansprüche 1 bis 4, wobei die Legierung nach der Behandlung
zur Lösung, aber vor Schritt (a) einer mechanischen Verformung unterzogen wird.
Verfahren nach Anspruch 5, wobei die Legierung nach Schritt (b), aber vor Schritt
(c) einer mechanischen Verformung unterzogen wird.
Verfahren nach Anspruch 5 oder 6, wobei die Legierung während des Schrittes
(c) einer mechanischen Verformung unterzogen wird.
Verfahren nach einem der Ansprüche 5 bis 7, wobei eine thermo-mechanische verformung
erfolgt.
Verfahren nach einem der Ansprüche 5 bis 8, wobei die mechanische Verformung
in Verbindung mit schnellem Abkühlen erfolgt.
Verfahren nach einem der Ansprüche 5 bis 9, wobei die Legierung bei TA
direkt nach der Herstellung oder dem Guse ohne einen diskreten Behandlungsschritt
zur Lösung gehärtet wird.
Verfahren nach einem der Ansprüche 1 bis 10, wobei die Endhärte um mindestens
10 bis 15 % gegenüber den Härteniveaus, die mit einem konventionellen T6-Wärmebehandlung
erreichbar sind, erhöht ist.
Verfahren nach einem der Ansprüche 1 bis 11, wobei die Endfließfestigkeit
(0.2 % Zugfestigkeit) um mindestens 5 bis 10 %, bezogen auf die Festigkeitsniveaus,
die mit einer konventionellen T6-Wärmebehandlung erreicht werden können, erhöht
ist.
Verfahren nach einem der Ansprüche 1 bis 12, wobei die Bruchfestigkeit um mindestens
5 bis 10 %, bezogen auf die Festigkeiteniveaus, die mit einer konventionellen T6-Wärmebehandlung
erreicht werden können, erhöht ist.
Verfahren nach einem der Ansprüche 1 bis 13, wobei die Zeit bei der Temperatur
TA so ausgewählt ist, dass zwischen etwa 85 % bis etwa 95 % der maximalen
Festigkeit, die bei einem vollständigen T6-Härten erreicht werden kann, erhalten
werden.
Verfahren nach einem der Ansprüche 1 bis 14, wobei die Zeit bei der Temperatur
TA zwischen 2 oder 3 Minuten und mindestens 8 Stunden beträgt.
Verfahren nach Anspruch 15, wobei die Zeit bei der Temperatur TA
zwischen mehr als 2 bis 3 Minuten und etwa 8 Stunden beträgt.
Verfahren nach Anspruch 15, wobei die Zeit bei einer. Temperatur TA
zwischen 1 und 2 Stunden beträgt.
Verfahren nach einem der Ansprüche 1 bis 17, wobei das Abkühlen in Schritt (b)
durch Abschrecken in eine Flüssigkeit durchgeführt wird.
Verfahren nach Anspruch 18, wobei eine Flüssigkeit als Abschreckmittel eingesetzt
wird.
Verfahren nach Anspruch 19, wobei kaltes Wasser als Abschreckmittel eingesetzt
wird.
Verfahren nach einem der Ansprüche 1 bis 20, wobei die Temperatur TB
im Bereich zwischen etwa -10 °C und etwa 120 °C liegt.
Verfahren nach Anspruch 21, wobei die Temperatur TB im Bereich zwischen
etwa -10 °C und etwa 90 °C liegt.
Verfahren nach einem der Ansprüche 1 bis 22, wobei die Zeitdauer für Schritt
(c) sich von weniger als 8 Stunden bis zu mehr als 500 Stunden erstreckt.
Verfahren nach Anspruch 23, wobei die Zeitdauer für Schritt (c) sich von etwa
8 Stunden bis zu etwa 500 Stunden erstreckt.
Verfahren nach einem der Ansprüche 1 bis 24, wobei die Temperatur TC
in Schritt (d) die gleiche ist wie die Temperatur TA in Schritt (a).
Verfahren nach einem der Ansprüche 1 bis 24, wobei die in Schritt (d) eingesetzte
Temperatur TC die Temperatur TA in Schritt (a)um bis zu 50
°C überschreitet.
Verfahren nach Anspruch 26, wobei die Temperatur TC die Temperatur
TA um bis zu 20 °C überschreitet.
Verfahren nach einem der Ansprüche 1 bis 24, wobei die in Schritt (d) eingesetzte
Temperatur TC um 20 °C bis 50 °C niedriger ist als die Temperatur TA
in Schritt (a).
Verfahren nach. Anspruch 28, wobei die Temperatur TC um 30 °C bis
50 °C niedriger ist als die Temperatur TA.
Anspruch[en]
A process for the heat treatment of an age-hardenable aluminium alloy which
has alloying elements in solid solution, wherein the process includes the stages
of:
(a) artificially ageing the alloy at a temperature TA which would
be an appropriate temperature for a conventional T6 temper for the alloy, wherein
the artificial ageing is conducted for a period sufficient to achieve strengthening
of the alloy which corresponds to from 50% to 95% of the maximum strengthening obtainable
by a full T6 temper for the alloy at the temperature TA;
(b) quenching the alloy in an underaged condition attained at the end of the
period for stage (a), from the temperature TA to a temperature in the
range from ambient temperature to about -10°C, to arrest primary precipitation and
to provide the alloy in an underaged and quenched condition;
(c) holding the underaged and quenched alloy at temperature TB which
is below the temperature TA and is in the range of from -10°C to 120°C
to achieve secondary nucleation or continuing precipitation of solute elements;
and
(d) heating the alloy from the temperature TB to a temperature TC
in the range of (TA -50°C) to (TA +50°C) and holding the alloy
at the temperature TC for further artificial ageing of the alloy;
wherein the alloy is further strengthened by the combination of steps (c) and (d)
to a level of strength which is in excess of the maximum strength obtainable for
the alloy by a full conventional T6 temper at temperature TA.
The process of claim 1, wherein stages (c) and (d) are successive.
The process of claim 2, wherein there is no applied heating in stage (c).
The process of claim 1, wherein stages (c) and (d) are combined through use
of controlled heating cycles whereby stage (c) utilises a heating rate, to the temperature
TC which provides the secondary nucleation or precipitation for stage
(c) at a relatively lower temperature than the final temperature Tc.
The process of any one of claims 1 to 4. wherein the alloy is subjected to mechanical
deformation after solution treatment but before stage (a).
The process of claim 5, wherein the alloy is subjected to mechanical deformation
after stage (b) but before stage (c).
The process of claim 5 or claim 6, wherein the alloy is subjected to mechanical
deformation during stage (c).
The process of any one of claims 5 to 7, wherein thermomechanical deformation
is applied.
The process of any one of claims 5 to 8, wherein the mechanical deformation
is applied in conjunction to rapid cooling.
The process of any one of claims 5 to 9, wherein the alloy is aged at TA
directly after fabrication or casting with no discrete solution treatment stage.
The process of any one of claims 1 to 10, wherein the final hardness is increased
by at least 10 to 15%, relative to hardness levels obtainable with a conventional
T6 heat treatment.
The process of any one of claims 1 to 11, wherein the final yield strength (0.2%
proof stress) is increased by at least 5 to 10%, relative to strength levels obtainable
with a conventional T6 heat treatment.
The process of any one of claims 1 to 12, wherein the tensile strength is increased
by at least 5 to 10%, relative to strength levels obtainable with a conventional
T6 heat treatment.
The process of any one of claims 1 to 13, wherein the time at temperature TA
is such as to achieve from about 85% to about 95% maximum strength obtainable by
full conventional T6 ageing.
The process of any one of claims 1 to 14, wherein the time at temperature TA
is from several minutes to at least 8 hours.
The process of claim 15, wherein the time at temperature TA is from
several minutes to about 8 hours.
The process of claim 15, wherein the time at temperature TA is from
1 to 2 hours.
The process of any one of claims 1 to 17, wherein the cooling of step (b) is
by quenching into a fluid.
The process of claim 18, wherein a liquid is used as the quenching medium.
The process of claim 19, wherein cold water is used as the quenching medium.
The process of any one of claims 1 to 20, wherein the temperature TB
is in the range of from about -10°C to about 120°C
The process of claim 21, wherein the temperature TB is in the range
of from about -10°C to about 90°C.
The process of any one of claims 1 to 22, wherein the period of time for stage
(c) ranges from less than 8 hours up to in excess of 500 hours.
The process of claim 23, wherein the period of time for stage (c) ranges from
about 8 hours to about 500 hours.
The process of any one of claims 1 to 24, wherein the temperature TC
in stage (d) is the same as temperature TA in stage (a).
The process of any one of claims 1 to 24, wherein the temperature TC
used in stage (d) exceeds temperature TA in stage (a) by up to 50°C.
The process of claim 26, wherein the temperature TC exceeds temperature
TA by up to about 20°C.
The process of any one of claims 1 to 24, wherein the temperature TC
used In stage (d) is lower than the temperature TA in stage (a) by 20°C
to 50°C.
The process of claim 28, wherein the temperature TC is lower than
temperature TA by 30°C to 50°C.
Anspruch[fr]
procédé pour le traitement thermique d'un alliage d'aluminium durciesable par
vieillissement comportant des éléments d'alliage en solution solide, lequel procédé
comprend les étapes de :
(a) vieillissement artificiel de l'alliage à une température TA qui
serait une température appropriée poux un traitement T6 classique pour l'alliage,
le vieillissement artificiel étant conduit pendant une période suffisante pour atteindre
un renforcement de l'alliage qui correspond à 50 % à 95 % du renforcement maximal
accessible par un traitement T6 complet pour l'alliage à la température TA
;
(b) trempe de l'alliage dans un état sous-vieilli atteint à la fin de la période
de l'étape (a), de la température TA à une température comprise dans
l'intervalle de la température ambiante à environ -10 °C, pour arrêter la précipitation
primaire et obtenir l'alliage à l'état sous-vieilli et trempé ;
(c) maintien de l'alliage sous-vieilli et trempé à une température TB
qui est inférieure à la température TA et se situe dans l'intervalle
de -10°C à 120°C pour réaliser une nualéation secondaire ou une précipitation poursuivie
d'éléments de soluté ; et
(d) chauffage de l'alliage de la température TB à une température
TC dans l'intervalle de (TA -50°C) à (TA +50°C)
et maintien de l'alliage à la température TC pour un vieillissement artificiel
supplémentaire de l'alliage ;
dans lequel l'alliage est davantage renforcé par la combinaison des étapes (c)
et (d) jusqu'à un degré de résistance mécanique qui est supérieur à la résistance
mécanique maximale pouvant être atteinte pour l'alliage par un traitement T6 classique
complet à la température TA.
Procédé selon la revendication 1, dans lequel les étapes (c) et (d) sont successives.
Procédé selon la revendication 2, dans lequel il n'est pas appliqué de chauffage
dans l'étape (c).
Procédé selon la revendication 1, dans lequel les étapes (c) et (d) sont combinées
par utilisation de cycles de chauffage réglés en sorte que l'étape (c) utilise une
vitesse de chauffage, jusqu'à la température TC, qui assure la nucléation
secondaire ou la précipitation pour l'étape (c) à une température relativement inférieure
à la température TC finale.
Procédé selon l'une quelconque des revendications 1 à 4, dans lequel l'alliage
est soumis à une déformation mécanique après le traitement de dissolution mais avant
l'étape (a).
Procédé selon la revendication 5, dans lequel l'alliage est soumis à une déformation
mécanique après l'étape (b) mais avant l'étape (c).
Procédé selon la revendication 5 ou la revendication 6, dans lequel l'alliage
est soumis à une déformation mécanique pendant l'étape (c).
Procédé selon l'une quelconque des revendications 5 à 7, dans lequel une déformation
thermomêcanique est appliquée.
Procédé selon l'une quelconque des revendications 5 à 8, dans lequel la déformation
Mécanique est appliquée conjointement à un refroidissement rapide.
Procédé selon l'une quelconque des revendications 5 à 9, dans lequel l'alliage
est vieilli à TA directement après la fabrication ou la coulée, sans
étape séparée de traitement de dissolution.
Procédé selon, l'une quelconque des revendications 1 à 10, dans lequel la dureté
finale est accrue d'au moins 10 à 15 % par rapport aux degrés de dureté pouvant
être obtenus avec un traitement thermique T6 classique.
Procédé selon l'une quelconque des revendications 1 à 11, dans lequel la limite
élastique finale (limite conventionnelle d'élasticité 0.2 %) est accrue d'au moins
5 à 10 % par rapport aux degrés de limite élastique pouvant être obtenus avec un
traitement thermique T6 classique.
Procédé selon l'une quelconque des revendications 1 à 12, dans lequel la résistance
à la traction est accrue d'au moins 5 à 10 % par rapport aux degrés de résistance
pouvant être obtenus avec un traitement thermique T6 classique.
Procédé selon l'une quelconque des revendications 1 à 13, dans lequel le temps
à la température TA est tel que soit atteint un degré d'environ 85 %
à environ 95 % de la résistance mécanique maximale pouvant être obtenue par un vieillissement
T6 classique complet.
Procédé selon l'une quelconque des revendications 1 à 14, dans lequel le temps
à la température TA est de deux à trois minutes jusqu'à au moins 8 heures.
Procédé selon la revendication 15, dans lequel le temps à la température TA
est de plus de deux ou trois minutes à environ 8 heures.
Procédé selon la revendication 15, dans lequel le temps à la température TA
est de 1 à 2 heures.
Procédé selon l'une quelconque des revendications 1 à 17, dans lequel le refroidissement
de l'étape (b) est effectué par trempe dans un fluide.
Procédé selon la revendication 18, dans lequel un liquide est utilisé comme
milieu de trempe.
Procédé selon la revendication 19, dans lequel de l'eau froide est utilisée
comme milieu de trempe.
Procédé selon l'une quelconque des revendications 1 à 20, dans lequel la température
TB se situe dans l'intervalle d'environ -10°C à environ 120°C.
Procédé selon la revendication 21, dans lequel la température TB
se situe dans l'intervalle d'environ -10°C à environ 90°C.
Procédé selon l'une quelconque des revendications 1 à 22, dans lequel la période
de temps pour l'étape (c) est comprise entre moins de 8 heures et plus de 500 heures.
Procédé selon la revendication 23, dans lequel la période de temps pour l'étape
(a) est comprise entre environ B heures et environ 500 heures.
Procédé selon l'une quelconque des revendications l'a 24, dans lequel la température
TC dans l'étape (d) est la même que la température TA dans
l'étape (a).
Procédé selon l'une quelconque des revendications 1 à 24, dans lequel la température
TC utilisée dans l'étape (d) dépasse d'au plus 50°C la température TA
dans l'étape (a).
Procédé selon la revendication 26, dans lequel la température TC
dépasse d'au plus environ 20°C la température TA.
Procédé selon l'une quelconque des revendications 1 à 24, dans lequel la température
TC utilisée dans l'étape (d) est inférieure de 20°C à 50°C à la température
TA dans l'étape (a).
Procédé selon la revendication 28, dans lequel la température TC
est inférieure de 30°C à 50°C à la température TA.