[0001] The present invention relates to a valve for internal-combustion engines, in particular
a titanium valve, in which at least one region of the valve has a nitrided layer formed
by titanium nitrides and/or aluminium-titanium nitrides, providing excellent wear
resistance and high hardness.
Description of the prior art
[0002] Nowadays, internal-combustion engines are subjected to increasingly high loads under
extreme conditions, both high temperatures and/or high speeds, with a view to increasing
the fuel efficiency of the engine or delivering more power. These loads cause severe
wear to the components of the engines, in particular to alternating components, such
as valves.
[0003] High-speed engines result in high levels of inertia in the movement of the valves,
causing excessive wear of the components. For this reason, high-speed engines usually
use valves made of a titanium-based material in order to reduce the weight of these
components. The lighter weight and the greater strength at high temperatures of titanium
alloys result in same being used in these valves, due to the inertial characteristics
thereof.
[0004] However, titanium alone provides relatively limited wear resistance. In this regard,
to increase the durability of the valve, a common approach is to use a steel cover
known as a "lash cap" made of hardened carbon steel that can withstand wear and is
usually used at the tip of the stem of the valve, a portion that is highly subject
to wear.
[0005] Although very commonly used, the steel lash cap is a somewhat unsatisfactory solution
for the problem of the low wear resistance of titanium. In particular at the tip of
the valve, the assembly of the steel lash cap is a problem, since said lash cap may
become removed from the valve when the engine is running. Since the engines that use
titanium valves run at very high speeds, there is a very high level of inertia and
the wear that may be caused between the parts can cause the steel lash cap to become
detached and to cause significant damage to the engine.
[0006] In addition to improving the wear resistance of the tip of the valve, treating the
valve seat can also improve the durability of the component in the most critical applications
in terms of wear resistance combined with contact fatigue.
[0007] Patent document
US 5051140 discloses a method for treating a titanium or titanium-alloy surface comprising a
process for pre-treating a workpiece comprising titanium or a titanium alloy with
an acid to clean said workpiece, a heating process for heating the pre-treated workpiece
in an oxidative atmosphere for a predetermined period of time to form a composite
layer comprising oxide layers and oxygen-enriched layers on the surface of the workpiece,
and a process for rapidly cooling the treated workpiece to remove a scale layer formed
on the outermost layer of said composite layer on the surface of the workpiece. This
method is limited in that it can only be applied to layers up to 10 microns thick
and causes dimensional distortions as a result of the high heat treatment temperatures,
as well as being a very slow method.
[0008] Patent document
US 4852531 discloses a valve for internal-combustion engines having a valve stem of a titanium
alloy strengthened by the inclusion of a compound containing titanium such as titanium
carbide (TiC), titanium boride (TiB) or titanium diboride (TiB
2). The valve stem is joined to a valve tip formed from a powder of a titanium alloy,
preferably of the same composition as the alloy of the stem. The tip and the stem
are joined by cold compaction followed by vacuum sintering and a high temperature
compaction. However, this method uses expensive, explosive materials with a complex
consolidation method, and the product has limited resistance.
[0009] Furthermore, patent document
US 5441235 discloses a valve made from titanium with an in situ zone of titanium nitride extending
from the valve's outer surface by means of a plasma nitriding process. This solution
is limited by the thickness of the coating, typically below 50 microns, investment
in a costly technology and low nitride content.
[0010] There is therefore a need for a valve for internal-combustion engines, in particular
a titanium valve, in which at least one region of the valve has a nitrided layer formed
by titanium nitrides and/or aluminium-titanium nitrides, providing excellent wear
resistance and high hardness and durability.
Objectives of the invention
[0011] A first objective of the present invention is to provide a valve for internal-combustion
engines, in particular a titanium valve, in which at least one region of the valve
has a nitrided layer formed by titanium nitrides (TiN) and/or aluminium-titanium nitrides
(AlTiN
2).
[0012] Furthermore, the present invention is intended to provide a valve that has a nitrided
layer that is up to 500 microns thick, with surface hardness of between 1100 HV and
2000 HV, and hardness of at least 700 HV to a depth of at least 200 microns in the
thickness of the nitrided layer.
[0013] Furthermore, the present invention is intended to provide a valve that has a nitrided
layer that comprises at least 50% by volume of titanium nitrides (TiN) and/or aluminium-titanium
nitrides (AlTiN
2) to a depth of at least 50 microns in the thickness of the nitrided layer.
[0014] The present invention is also intended to provide a valve that is provided with a
nitrided layer obtained by means of a nitriding process by laser remelting in a nitrogen-rich
atmosphere.
[0015] Finally, the present invention is intended to provide a valve that has excellent
wear resistance, with high hardness and durability, delivering properties that are
superior to valves made from a titanium alloy.
Brief description of the invention
[0016] The objectives of the present invention are achieved by a valve for internal-combustion
engines provided with a body or substrate including a titanium alloy, in which at
least one region of the valve has a nitrided layer formed by titanium nitrides (TiN)
and/or aluminium-titanium nitrides (AlTiN
2), the nitrided layer comprising at least 50% by volume of titanium nitrides (TiN)
and/or aluminium-titanium nitrides (AlTiN
2) to a depth of at least 50 microns in the thickness of the nitrided layer, that is
up to 500 microns thick and has a surface hardness of between 1100 HV and 2000 HV,
the hardness of the nitrided layer being at least 700 HV to a depth of at least 200
microns in the thickness of the nitrided layer, same being applied to all of the surfaces
of the valve, in particular to a region corresponding to the tip of the valve; the
substrate being made of the titanium alloy that contains between 5.5% and 6.75% by
weight of aluminium, and between 3.5% and 4.5% by weight of vanadium, the remainder
being titanium and impurities, or of a titanium alloy that contains between 5.5% and
6.75% by weight of aluminium, between 1.30% and 2.00% by weight of iron, between 0.07%
and 0.13% by weight of silicon, and between 0.15% and 0.20% by weight of oxygen, the
remainder being titanium and impurities, or of a titanium alloy that contains between
5.5% and 6.75% by weight of aluminium, between 2.4% and 3.00% by weight of tin, between
3.50% and 4.50% by weight of zirconium, between 0.35% and 0.50% by weight of silicon,
and between 0.35% and 0.50% by weight of molybdenum, the remainder being titanium
and impurities, or of a titanium alloy that contains between 5.5% and 6.75% by weight
of aluminium, between 1.80% and 2.20% by weight of tin, between 3.60% and 4.40% by
weight of zirconium, between 0.06% and 0.13% by weight of silicon, and between 1.80%
and 2.20% by weight of molybdenum, the remainder being titanium and impurities; the
valve being in particular an inlet valve.
[0017] The objectives of the present invention are also achieved by a method for obtaining
a valve for an internal-combustion engine, the valve having a body or substrate made
of a titanium alloy, the method including the following steps:
step i) forging and machining of the shape of the valve (1),
step ii) nitriding of at least one region of the valve (1) to obtain a nitrided layer
(10),
step iii) finishing by machining,
[0018] in which the nitriding step ii) is carried out by laser remelting in a nitrogen-rich
atmosphere, an additional thermal oxidation and polishing step being optionally carried
out on at least one region of the valve between steps i) and ii), the nitriding step
ii) being carried out in an atmosphere containing at least 50% by volume of nitrogen
using a laser beam with a diameter of between 0.5 and 6 millimetres, an angle of incidence
of between 75° and 110°, a laser speed of between 5.0 and 60 millimetres per second,
and a laser power of between 200 and 3000 watts, with a minimum nitrogen flow of 8
litres per minute, the step iii) of finishing by machining including removing material
from the treated surface up to 70 microns deep.
[0019] Furthermore, the objectives of the present invention are achieved by an internal-combustion
engine that includes at least one valve, as described above.
Brief description of the figures
[0020] The present invention is described in greater detail below on the basis of an example
embodiment shown in the drawings. The figures show:
Figure 1 - Schematic side view of a valve with all of the component parts thereof,
Figure 2 - Schematic drawing of the nitrided layer applied to the valve according
to the present invention,
Figure 3 - Photograph of the tip of a valve treated with a nitrogen atmosphere and
graphical representation of the elements that make up the nitrided layer obtained
(sample A),
Figure 4 - Photograph of the tip of a valve treated with no nitrogen atmosphere and
graphical representation of the elements that make up the nitrided layer obtained
(sample B),
Figure 5 - Graphical representation of the hardness obtained for a valve treated with
and without a nitrogen atmosphere and photograph of the nitrided layer,
Figure 6 - Graphical representation of the content of the phases through the depth
of the thickness of the nitrided layer for valves treated with and without nitrogen,
Figure 7 - Graphical representation of the resulting depth of wear for valves with
the nitrided layer obtained in the prior art and the nitrided layer obtained in the
present invention,
Figure 8 - Depth of wear measurements for a valve with the nitrided layer obtained
in the prior art and the nitrided layer obtained in the present invention, and
Figure 9 - Graphical representation of the content of phases through the depth of
the thickness of the nitrided layer for the valve according to the present invention.
Detailed description of the drawings
[0021] The present invention relates to a valve 1 for internal-combustion engines, in particular
a titanium valve 1, in which at least one region of the valve 1 has a nitrided layer
10 formed by titanium nitrides (TiN) and/or aluminium-titanium nitrides (AlTiN
2), the nitrided layer 10 being obtained by means of a nitriding process by laser remelting
carried out in a nitrogen-rich atmosphere and having high hardness, providing the
titanium valve 1 with excellent wear resistance.
[0022] As stated above, high-speed engines result in high levels of inertia in the movement
of the valves, causing excessive wear of the components. For this reason, high-speed
engines usually use valves made of a titanium-based material in order to reduce the
weight of these components. However, titanium alone provides relatively limited wear
resistance.
[0023] The valves used in internal-combustion engines are high-precision components installed
in the cylinder head of the engine, that are used for different tasks and are subjected
to high thermal and mechanical stresses.
[0024] On account of the different loads and stresses to which the valve is subjected, the
structural design thereof is usually very similar. Thus, as shown in Figure 1, a valve
1 comprises a disk-shaped head 2 having a seat region 3 and a neck region 4 that acts
as a transition portion to a stem 5, the tip 6 of the valve 1 being positioned at
the end of the stem opposite the head. Furthermore, there are one or more recesses
that form the channels 7 in the valve 1 in the region of the stem 5 next to the tip
6 of the valve 1. Each region of the valve 1 is subjected to different working loads
and is therefore stressed in a distinct way.
[0025] There are conventional titanium nitriding methods in the prior art, for example gas
nitriding, that typically result in nitrided layers that are up to 30 microns thick.
Valves with thin layers have reduced durability.
[0026] Unlike the valves obtained traditionally using nitriding methods, the valve 1 according
to the present invention has a nitrided layer 10, shown in Figure 2, made of titanium
nitrides (TiN) and/or aluminium-titanium nitrides (AlTiN
2) with a high nitride content provided on the surface of the valve 1 and throughout
the thickness of the nitrided layer 10.
[0027] The valve 1 according to the present invention includes a body or substrate 8 preferably
made of an alloy containing between 5.5% and 6.75% by weight of aluminium, and between
3.5% and 4.5% by weight of vanadium, the remainder being titanium and impurities,
the alloy being known commercially as Ti6Al4V.
[0028] In a second preferred embodiment, the substrate 8 is made of an alloy that contains
between 5.5% and 6.75% by weight of aluminium, between 1.30% and 2.00% by weight of
iron, between 0.07% and 0.13% by weight of silicon, and between 0.15% and 0.20% by
weight of oxygen, the remainder being titanium and impurities, the alloy being known
commercially as Ti6Al2Fe0.1Si.
[0029] In a third preferred embodiment, the substrate 8 is made of an alloy containing between
5.5% and 6.75% by weight of aluminium, between 2.4% and 3.00% by weight of tin, between
3.50% and 4.50% by weight of zirconium, between 0.35% and 0.50% by weight of silicon,
and between 0.35% and 0.50% by weight of molybdenum, the remainder being titanium
and impurities, the alloy being known commercially as Ti6Al2.8Sn4Zr0.4Si.
[0030] In a fourth preferred embodiment, the substrate 8 is made of an alloy that contains
between 5.5% and 6.75% by weight of aluminium, between 1.80% and 2.20% by weight of
tin, between 3.60% and 4.40% by weight of zirconium, between 0.06% and 0.13% by weight
of silicon, and between 1.80% and 2.20% by weight of molybdenum, the remainder being
titanium and impurities, the alloy being known commercially as Ti6Al2Sn4Zr2Mo.
[0031] Being an aluminium-titanium alloy, both titanium nitrides (TiN) and aluminium-titanium
nitrides (AlTiN
2) are formed. It is also possible for nitrides to form from the other elements contained
in the alloy. However, these nitrides are much more difficult to obtain and no such
formation was observed in any relevant quantities for the method parameters used.
For these specific alloys, titanium nitrides (TiN) and/or aluminium-titanium nitrides
(AlTiN
2) are necessarily formed.
[0032] The high-wear-resistance nitrided layer 10 is defined by a predominance of titanium
nitrides (TiN) and/or aluminium-titanium nitrides (AlTiN
2) and is obtained by means of a nitriding process by laser remelting of the titanium
alloy in a nitrogen-rich atmosphere, preferably containing at least 50% by volume
of nitrogen.
[0033] The method for obtaining the nitrided layer 10, applied to the surface of at least
one region of the valve 1, is done by means of a laser, the treatment essentially
involving remelting the titanium alloy in a nitrogen-rich atmosphere to form nitrides.
The laser generates a treated remelted layer that is very rich in titanium nitrides
(TiN) and/or aluminium-titanium nitrides (AlTiN
2). Preferably, although not necessarily, the nitrided layer 10 is applied to the region
of the tip 6 of the valve 1, and may be applied to all of the surfaces of the valve
1.
[0034] The method for manufacturing the valve 1 according to the present invention includes
steps for forging and machining the shape of the valve 1, followed by an optional
step of thermal oxidation, polishing of the tip 6 of the valve 1, laser remelting
in a nitrogen-rich atmosphere and finally a machining finishing step to ensure a suitable
roughness of the surface of the tip 6.
[0035] The nitriding carried out by laser remelting in a nitrogen atmosphere enables nitrides
to form without the need for a thermal treatment, making the process quicker and able
to be localized, i.e. the nitriding need not be applied to all of the surfaces of
the valve 1, but only to the regions subject to the greatest wear. As well as being
quick, the method achieves high thicknesses of the nitride layer, with layers of up
to 500 microns thick and with high hardness and high nitride content being able to
be obtained, this enabling a finishing method to be carried out.
[0036] Alternatively, the nitrided layer 10 is obtained using a nitriding process by remelting
in a nitrogen-rich atmosphere, the remelting process being carried out with a tungsten
electrode (TIG - tungsten inert gas) or else using an electron beam (EBW - electron
beam welding), both processes being carried out in atmospheres containing at least
50% by volume of nitrogen.
[0037] A comparative study of the parameters of the laser remelting process was carried
out to assess the characteristics of the nitrided layer 10 as a function of the nitrogen
atmosphere.
[0038] Preferably, but not necessarily, the process used a laser beam with a diameter of
between 0.5 and 6 millimetres, preferably 0.5 millimetres, an angle of incidence of
the laser of between 75° and 110°, preferably 90°, a laser speed of between 5.0 and
60 mm/s (millimetres per second), preferably 8.0 mm/s, and a laser power of between
200 and 3000 watts, preferably 300 watts.
[0039] Two samples were prepared, in which a first sample, hereinafter referred to as sample
A, was subjected to a laser remelting process in a nitrogen-rich atmosphere with a
minimum nitrogen flow of 8 I/min (litres per minute), preferably between 10 I/min
and 15 I/min, and a second sample, hereinafter referred to as sample B, was subjected
to the same laser remelting process, but with no nitrogen-rich atmosphere, i.e. with
zero nitrogen flow.
[0040] Figure 3 is a photograph of the nitrided layer 10 obtained with sample A, and Figure
4 is a photograph of the nitrided layer 10 obtained with sample B.
[0041] For both samples A and B, with and without nitrogen respectively, a nitrided layer
10 between 150 and 500 microns deep, preferably between 200 and 300 microns deep,
was obtained, with a maximum surface deformation of 20 microns.
[0042] The B samples, treated without a nitrogen atmosphere, had surface cracks and therefore
lower wear resistance. A comparative analysis by wavelength dispersive X-ray (WDX)
shows a higher incorporation of nitrogen, up to 10% by weight of nitrogen, on the
surface of the tip 6 of the valve 1 of the present invention when a nitrogen atmosphere
is used (sample A). Conversely, a greater quantity of oxygen, up to 13% by weight
of oxygen, is incorporated when a nitrogen atmosphere is not used (sample B).
[0043] The high temperature and the high heat extraction given by the laser source associated
with the high incorporation of nitrogen or of oxygen led to an excellent increase
in surface hardness from 380 HV to 2000 HV (Vickers hardness). The hardness obtained
on the surface of the tip 6 of the valve 1 is between 1100 HV and 2000 HV, while the
hardness obtained at a depth of 200 microns into the thickness of the nitrided layer
10 is at least 700 HV, as shown in Figure 5.
[0044] A detailed X-ray diffraction (XRD) analysis through the depth of the nitrided layer
10 revealed the predominance of titanium nitrides (TiN) and/or aluminium-titanium
nitrides (AlTiN
2) formed on the tip 6 of the valve 1 of the present invention treated in a nitrogen-rich
atmosphere (sample A).
[0045] On the other hand, the B samples, treated without a nitrogen atmosphere, conversely
showed a predominance of titanium oxides (TiO), with almost no nitrides.
[0046] The analysis carried out confirmed the existence of nitrides on the surface of the
tip 6 of the valve 1 and a study was performed of how the nitrides behave through
the depth of the nitrided layer 10, to enable the nitrided layer 10 to have improved
wear resistance.
[0047] This study revealed that it is possible to obtain at least 50% by volume of titanium
nitrides (TiN) and/or aluminium-titanium nitrides (AlTiN
2) to a depth of up to at least 50 microns in the thickness of the nitrided layer 10.
In other words, the combination of the two nitrides (titanium and aluminium-titanium)
to a depth of at least 50 microns in the thickness of the nitrided layer 10, can guarantee
the existence of at least 50% by volume of nitrides.
[0048] The graph in Figure 6 shows the content of the phases found through the depth of
the thickness of the nitrided layer 10. Sample A, treated with a nitrogen atmosphere,
had at least 35% of titanium nitrides (TiN) and at least 47% of aluminium-titanium
nitrides (AITi2), containing at least 82% of nitrides (TiN + AlTiN
2) on the surface of the nitrided layer 10. Furthermore, sample A had at least 50%
by volume of titanium nitrides (TiN) and at least 19% by volume of aluminium-titanium
nitrides (AlTiN
2), containing at least 69% of nitrides (TiN + AlTiN
2) to a depth of at least 50 microns in the thickness of the nitrided layer 10.
[0049] Conversely, sample B, treated in an atmosphere without nitrogen, had just 16% of
titanium nitrides (TiN) and a predominance of 82% of titanium oxides (TiO) on the
surface of the nitrided layer 10, and 38% of titanium nitrides and/or titanium aluminium
nitrides (TiN and/or AlTiN
2) with a predominance of 48% of titanium oxides (TiO) to a depth of at least 50 microns
in the thickness of the nitrided layer 10.
[0050] The application of the laser in an environment that includes nitrogen ensures the
formation of nitrides through the depth of the thickness of the nitrided layer 10.
[0051] Figures 7 and 8 show the graphical results obtained from a durability test carried
out in order to measure the resulting depth of wear for valves in the prior art that
include nitrided steel, obtained by induction hardening, and the titanium valves according
to the present invention that include the nitrided layer 10 obtained by the remelting
process.
[0052] Figures 7 and 8 show that the resulting wear of the nitrided-steel valves (prior
art) and the titanium valves treated by remelting (present invention) was similar,
around 2.1 to 2.8 microns.
[0053] As can be seen in Figure 8, the valve 1 according to the present invention has a
single region of greater wear, up to 4.6 microns, which is nonetheless very advantageous
and enables the replacement of the steel lash cap on the tip of the valve. The other
valves show wear similar to the treated-steel valve, i.e. less than 2.8 microns in
the other regions of the surface thereof.
[0054] Consequently, it can be confirmed that the presence of large quantities of titanium
nitrides and/or aluminium-titanium nitrides on the surface of the tip 6 of the valve
1 provides high wear resistance, achieving wear resistance similar to valves made
of hardened steels, but with less weight on account of the use of a titanium alloy.
Furthermore, the valve 1 according to the present invention can achieve the same strength
as a titanium valve that uses the steel lash cap.
[0055] Finally, Figure 9 shows graphical results for an analysis carried out by X-ray diffraction,
demonstrating that the wear resistance is guaranteed up to approximately 270 microns
from the treated surface, since same has at least 50% of hard nitride phases, such
as TiN and AlTiN
2.
[0056] This replacement of the steel lash cap with the nitrided layer 10 has advantages
in terms of the method, since same comprises just one part and one step, as well as
advantages in terms of the product on account of the elimination of the steel lash
cap, which is liable to become detached and to cause damage to the engine.
[0057] Although a preferred embodiment has been described, it should be noted that the scope
of the present invention covers other possible variations and is only limited by the
content of the attached claims, including the possible equivalents therein.
1. Valve (1) for internal-combustion engines provided with a body or substrate (8) including
a titanium alloy, characterized in that at least one region of the valve (1) has a nitrided layer (10) formed by titanium
nitrides (TiN) and/or aluminium-titanium nitrides (AlTiN2).
2. Valve (1) according to Claim 1, characterized in that the nitrided layer (10) comprises at least 50% by volume of titanium nitrides (TiN)
and/or aluminium-titanium nitrides (AlTiN2) to a depth of at least 50 microns in the thickness of the nitrided layer (10).
3. Valve (1) according to Claim 1, characterized in that the thickness of the nitrided layer (10) is up to 500 microns.
4. Valve (1) according to Claim 1, characterized in that the surface hardness of the nitrided layer (10) is between 1100 HV and 2000 HV.
5. Valve (1) according to Claim 1, characterized in that the hardness of the nitrided layer (10) is at least 700 HV to a depth of at least
200 microns in the thickness of the nitrided layer (10).
6. Valve (1) according to Claim 1, characterized in that the nitrided layer (10) is applied to all of the surfaces of the valve (1).
7. Valve (1) according to Claim 1, characterized in that the nitrided layer (10) is applied to a region corresponding to the tip (6) of the
valve (1).
8. Valve (1) according to Claim 1, characterized in that the substrate (8) is made of the titanium alloy that contains between 5.5% and 6.75%
by weight of aluminium, and between 3.5% and 4.5% by weight of vanadium, the remainder
being titanium and impurities.
9. Valve (1) according to Claim 1, characterized in that the substrate (8) is made of the titanium alloy that contains between 5.5% and 6.75%
by weight of aluminium, between 1.30% and 2.00% by weight of iron, between 0.07% and
0.13% by weight of silicon, and between 0.15% and 0.20% by weight of oxygen, the remainder
being titanium and impurities.
10. Valve (1) according to Claim 1, characterized in that the substrate (8) is made of the titanium alloy that contains between 5.5% and 6.75%
by weight of aluminium, between 2.4% and 3.00% by weight of tin, between 3.50% and
4.50% by weight of zirconium, between 0.35% and 0.50% by weight of silicon, and between
0.35% and 0.50% by weight of molybdenum, the remainder being titanium and impurities.
11. Valve (1) according to Claim 1, characterized in that the substrate (8) is made of the titanium alloy that contains between 5.5% and 6.75%
by weight of aluminium, between 1.80% and 2.20% by weight of tin, between 3.60% and
4.40% by weight of zirconium, between 0.06% and 0.13% by weight of silicon, and between
1.80% and 2.20% by weight of molybdenum, the remainder being titanium and impurities.
12. Valve (1) according to Claim 1, characterized in that it is an intake valve (1).
13. Method for obtaining a valve (1) for internal-combustion engines, the valve (1) having
a body or substrate (8) made of a titanium alloy, the method including the following
steps:
step i) forging and machining of the shape of the valve (1),
step ii) nitriding of at least one region of the valve (1) to obtain a nitrided layer
(10),
step iii) finishing by machining,
the method being
characterized in that the nitriding step ii) is carried out by laser remelting in a nitrogen-rich atmosphere.
14. Method according to Claim 13, characterized in that an additional thermal oxidation and polishing step is optionally carried out on at
least one region of the valve (1) between steps i) and ii).
15. Method according to Claim 13, characterized in that the nitriding step ii) is carried out in an atmosphere containing at least 50% by
volume of nitrogen.
16. Method according to Claim 13, characterized in that the nitriding step ii) by laser remelting uses a laser beam with a diameter of between
0.5 and 6.0 millimetres, an angle of incidence of between 75° and 110°, a laser speed
of between 5.0 and 60 millimetres per second, and a laser power of between 200 and
3000 watts, with a minimum nitrogen flow of 8 litres per minute.
17. Method according to Claim 13, characterized in that the step iii) of finishing by machining includes removing material from the treated
surface up to 70 microns deep.
18. Internal-combustion engine, characterized in that it includes at least one valve (1) as defined in claim 1.