[0001] The present invention relates to a valve for use in internal combustion engines wherein
at least one region of the valve comprises a nitrided layer formed by up to 10 % by
weight of nitrogen in solid solution provided in the metallic matrix of the valve,
conferring excellent wear resistance, in addition to high corrosion resistance.
Description of the State of the Art
[0002] The valves for use in internal combustion engines are high precision components submitted
to high thermal and mechanical stresses. They are housed in the head(s) of the engine
for the purpose of undertaking different tasks, such as perfectly and sealing areas
of flow, controlling the exchange of gases, and sealing the cylinders from the exterior,
in addition to dissipating the heat absorbed from the gases resulting from combustion,
transferring it to a valve seat ring and to a valve guide.
[0003] The valves are divided into inlet, controlling the intake of gaseous mixture into
the cylinder of the engine, and exhaust, permitting the escape of the gases following
the explosion. There is a generic difference between inlet and exhaust valves such
that the inlet valves, cooled by the unburnt gases, need to resist high mechanical
stresses, particularly in the contact thereof with the valve seat.
[0004] The exhaust valves, in addition to great mechanical demands, also need to resist
high thermal stresses and chemical corrosion. Furthermore, they work under temperatures
ranging around 800 °C, opening and closing approximately 70 times per second, and
are subjected to an average of 300 million load alternations.
[0005] By virtue of the different stresses whereto a valve is subjected, the constructional
configuration thereof is, in general, very similar. Consequently, as may be observed
in figure 1, a valve is constituted by a head in disc form comprising a seating region
and a neck region acting as transitional region to the stem, whilst at the extremity
of the stem opposite to the head the tip of the valve is located. Moreover, in the
region of the stem, adjacent to the tip of the valve, one or more neckings may be
observed forming the grooves of the valve. Each region of the valve is submitted to
different working conditions, being stressed as a consequence in a different manner.
[0006] In summary, the valves must be resistant to three different types of stress, mechanical,
thermal and chemical. In relation to the mechanical strength, the valves must present
resistance to impacts in the seating region and in the region of the tip. In terms
of wear resistance, the principal parts affected are the seating region, the stem
and the tip of the valve. In turn, resistance to pressure must be a characteristic
of the face of the head. Finally fatigue strength is necessary by virtue of the constant
alternation between the tensile and compression stresses.
[0007] The requirement for thermal resistance arises from the temperature of combustion,
from the high temperatures of the exhaust gases and from the fatigue caused by the
alternation between high and low temperatures. Furthermore, chemical resistance is
necessary to prevent the facility of corrosion in the corrosive environment of the
gases, humidity and working temperatures to which the valve is subject.
[0008] Current engines are, increasingly, stressed under extreme conditions, whether at
high temperatures and/or speeds, the objective being to increase the fuel efficiency
thereof and deliver greater power. As a consequence of these new stresses, the components
of the engines, in particular the valves, present successive modifications, always
with the objective of increasing the working life of these elements.
[0009] In this manner, having the objective of overcoming the demanding working conditions
whereto the valves are subjected, it is very common that the valves are monometallic
of special alloys, bimetallic, or that they be provided with inserts.
[0010] The monometallic valves are constructed of a single material and are applied in parts
experiencing moderate demand. On the other hand, the bimetallic valves are applied
in situations of greater demand, a specific material being applied for each part of
the valve. Naturally, these valves have a higher cost by virtue of the manufacturing
process thereof, presenting limitations and, consequently, not being justifiable for
a great proportion of the applications.
[0011] Up to the present time, among the most common solutions of coating engine valves
in the state of the art is nitridation, conferring high hardness upon the surface
of the valve by virtue of the formation of hard phases of nitrides/carbides, with
the consequent increase of the wear strength thereof.
[0012] However, nitridation also presents a great disadvantage in the sense that it diminishes
the corrosion resistance of the valves. There exist two principal mechanisms inherent
to the nitridation responsible for rendering the valves susceptible to corrosion:
[0013] Depassivation: all the stainless steels, principal material of manufacture of the
valves, comprise a film of oxide (Cr
2O
3), "passive" and rich in chromium, formed naturally upon the surface of the steel.
In spite of the film having an insignificant thickness (from 1 to 5 nanometres), it
is extremely adherent and chemically stable. The process of nitridation ruptures the
passive film in order to render possible the diffusion of the nitrogen into the structure.
This rupture of the passive film signifies that the steel loses its anticorrosive
properties, in this manner diminishing the corrosion resistance of the material.
[0014] Chromium depletion: the process of nitridation causes the depletion of the chromium
of the solid solution comprised within the matrix of the steel, by virtue of the formation
and precipitation of chromium nitrides. The chromium nitrides "rob" the chromium from
the metallic matrix causing the diminution of the corrosion resistance of the nitrided
surface, and may render the use of the steel unviable in many applications.
[0015] In this respect, in spite of the nitridation process conferring high wear resistance
on the valve, this also drastically lowers the corrosion resistance of the stainless
steels, leaving the valves susceptible to corrosion in acidic environments.
[0016] Whilst diverse attempts exist which endeavour to minimise the wear to which the valves
are subject, the solutions of the state of the art do not offer an engine valve achieving,
concomitantly, a superior performance in the matter of wear resistance and corrosion
resistance.
[0017] It is consequently necessary to obtain a valve for internal combustion engines receiving
a heat treatment with diffusion of nitrogen in solid solution provided in the metallic
matrix of the valve, conferring excellent wear strength and high corrosion resistance.
Objects of the Invention
[0018] A first object of the present invention is the provision of a valve for use in internal
combustion engines receiving a heat treatment with diffusion of nitrogen in solid
solution provided in a metallic matrix.
[0019] The present invention furthermore has as object the provision of a valve provided
with a nitrided layer comprising between 3 and 50 micrometres, having a hardness exceeding
900 HV in at least one region of the valve.
[0020] Finally, the present invention has as object the provision of a valve presenting
excellent wear resistance in general, in addition to high corrosion resistance, combining
different properties in the valve.
Brief Description of the Invention
[0021] The objects of the present invention are achieved by a valve for internal combustion
engines provided with a ferrous body or substrate comprising chromium, such that at
least one region of the valve comprises a nitrided layer formed by up to 10 % by weight
of nitrogen in solid solution provided in the metallic matrix of the substrate of
the valve, the nitrided layer presenting a gradual transition of the percentage by
weight of nitrogen, wherein the outermost portion of the nitrided layer presents 10
% by weight of nitrogen decreasing gradually until reaching the substrate of the valve,
the nitrided layer comprising a thickness of between 3 and 50 micrometres and hardness
exceeding 900 HV.
[0022] The objects are furthermore achieved by a valve comprising a nitrided layer provided
upon all the surfaces thereof, being preferentially an inlet valve.
Brief Description of the Figures
[0023] The present invention will, hereinafter, be described in greater detail on the basis
of an example of embodiment represented in the figures. The figures show:
Figure 1: schematic lateral view of a valve with all the parts constituting it;
Figure 2: schematic drawing and photograph of the nitrided layer provided upon the
valve of the present invention;
Figure 3: photographs showing the difference in depth of corrosion between a valve
of the state of the art and of the present invention in a first corrosion test;
Figure 4: graphic representation of the difference in depth of corrosion between valves
of the state of the art and of the present invention for the first corrosion test;
Figure 5: photographs showing the difference in depth of corrosion between a valve
of the state of the art and of the present invention in a second corrosion test; and
Figure 6: graphic representation of the difference in depth of corrosion between valves
of the state of the art and of the present invention for the second corrosion test.
Detailed Description of the Figures
[0024] The present invention relates to a valve 1 for internal combustion engines wherein
at least one region of the valve 1 comprises a nitrided layer 10 formed by a solid
solution of nitrogen provided in the metallic matrix of the substrate 8 of the valve
1, the nitrided layer 10 being obtained by means of a heat treatment with diffusion
of nitrogen, comprising high hardness, conferring upon the valve 1 excellent wear
resistance in addition to high corrosion resistance, combining different properties
in the valve 1.
[0025] As aforementioned, the valves 1 for use in internal combustion engines are components
of high precision, housed in the head of the engine, responsible for different tasks
and subjected to high thermal and mechanical stresses.
[0026] By virtue of these different loads and stresses to which the valve 1 is submitted,
the constructional configuration thereof is, in general, very similar. Consequently,
as may be observed in figure 1, a valve 1 is constituted of a head 2 in the form of
a disc comprising a seating region 3 and a neck region 4 acting as region of transition
to the stem 5, whilst at the extremity of the stem 5 opposite to the head 2 there
is located the tip 6 of the valve 1. Moreover, in the region of the stem 5, adjacent
to the tip 6 of the valve 1, one or more neckings may be observed forming the grooves
7 of the valve 1.
[0027] Among the materials utilised in the manufacture of the valves 1 for internal combustion
engines are, preferentially, the austenitic and martensitic stainless steels characterised
by presenting excellent properties of corrosion resistance, having however low surface
hardness and, consequently, low wear resistance.
[0028] In this respect, the processes of hardening by nitridation are commonly applied,
increasing the surface hardness, however significantly prejudicing the corrosion resistance
of the material by virtue of the intense precipitation of nitrides and carbides which
impoverish the matrix of chromium.
[0029] The process of nitridation consists, basically, in the addition of nitrogen, in the
atomic form thereof, upon the surface of a metal, usually steel. The nitrogen tends
to occupy the interstices of the crystalline structure, migrating by diffusion into
the interior of the metal. Traditionally, the processes of nitridation applied to
stainless steels utilise temperatures in the band between 500 °C and 600 °C in salt
baths or are carried out under a reductive nitriding atmosphere obtained from the
dissociation of ammonia gas.
[0030] Differing from the valves traditionally obtained through nitridation processes, the
valve 1 of the present invention comprises a nitrided layer 10 formed by solid solution
having a very high concentration of nitrogen provided within the metallic matrix of
the valve 1, without the formation of the aforementioned undesirable nitrides. Figure
2 presents the structure of the nitrided layer 10 of the valve 1 of the present invention.
The metallographic test carried out revealed a nitrided layer of 8 micrometres devoid
of the presence of nitrides.
[0031] The heat treatment utilised comprises low-temperature diffusion of the nitrogen,
providing the hardening of the surface together with a method of depassivation which
does not destroy the film of chromium oxide. In figure 2 the film of oxide 11 formed
upon the nitrided layer 10 may be observed. In this manner there is formed upon the
surface a new phase, a supersaturated and metastable solid solution of high hardness
without the diminution of the corrosion resistance inherent to the stainless steels.
The heat treatment with diffusion of nitrogen causes a modification to the surfaces
of the valve 1, transforming the structure of the substrate 8.
[0032] The nitrided layer 10 presents a gradual transition, or a gradient, of percentage
by weight of nitrogen contained in solid solution, comprising up to 10 % by weight
of nitrogen in an outermost portion of the nitrided layer 10 and decreasing gradually
until reaching the substrate 8 of the valve 1. In the same manner, the nitrided layer
10 presents a gradient of hardness comprising a hardness of up to 2000 HV in the outermost
portion of the nitrided layer and gradually decreasing. Preferentially, the nitrided
layer 10 comprises a hardness exceeding 900 HV.
[0033] In this sense, the present invention presents a valve 1 for internal combustion engines,
particularly a valve 1 provided with a ferrous body wherein at least one region of
the valve 1 comprises a nitrided layer 10, having the objective, principally, of increasing
the wear resistance thereof together with increased corrosion resistance.
[0034] The valve 1 which is the object of the present invention has as innovation the fact
that received upon at least one of the parts thereof is a nitrided layer 10 comprising
nitrogen in a solid solution provided within the metallic matrix of the material.
The nitrided layer 10 is provided upon the totality of the ferrous body or substrate
8 of the valve 1, provided with high hardness, not revealed by any document of the
prior art, and confers upon the valve 1 excellent wear resistance in addition to high
corrosion resistance.
[0035] Moreover, according to the preferential embodiment, the nitrided layer 10 is provided
with a thickness of between 3 and 50 micrometres, preferentially provided with a thickness
of between 3 and 35 micrometres, being obtained by a heat treatment rendering possible
the addition of nitrogen in solid solution, in this manner there being obtained a
nitrided layer 10 of high hardness, without prejudicing the anticorrosive properties
inherent to stainless steels.
[0036] In a preferable embodiment, the heat treatment for diffusion of nitrogen is realised
at a temperature of less than 450 °C, having a period of duration of the process of
3 to 20 hours. The nitrided layer 10 is obtained by the reaction of the atmosphere
rich in nitrogen with the metallic matrix of the substrate 8, preventing the formation
of nitrides.
[0037] Figures 3 to 6 present results of corrosion tests realised upon the valve 1 of the
present invention. Two types of corrosion test were carried out, the first test being
conducted by the Moneypenny Strauss method wherein the test piece of the valve 1 is
immersed in a solution of pentahydrated copper and sulphuric acid (CuSO
4.5H
2O). The results of the first corrosion test are presented in figures 3 and 4 wherein
there are compared three possibilities of materials for the valves applied in internal
combustion engines:
- 1) State of the Art 1: stainless steel, austenitic or martensitic, without any surface
hardness treatment;
- 2) State of the Art 2: stainless steel, austenitic or martensitic, submitted to a
conventional process of hardening by nitridation;
- 3) Present Invention: stainless steel, austenitic or martensitic, subjected to the
process of hardening by nitridation utilised in the present invention.
[0038] Figure 3 presents two photographs showing the depth of intergranular corrosion following
the implementation of the first test. As may be observed, the valve having conventional
nitridation (state of the art) presents intergranular corrosion of up to 500 micrometres
whilst the valve of the present invention presents corrosion of less than 300 micrometres.
The areas of corrosion are represented by the whitish bands apparent in the photographs.
[0039] Figure 4 represents graphically the results of the first corrosion test carried out.
It may be observed that the valve not subjected to any process of hardening (state
of the art 1) presents very low levels of corrosion, having a corrosion depth of 100
micrometres. It is important that it be recalled that those valves without heat treatment
present high corrosion resistance, but low hardness and wear resistance. The valve
subjected to the conventional process of nitridation presented high corrosion, having
a depth of 500 micrometres. In contrast, the valve of the present invention, presenting
a hardness exceeding 900 HV and high wear resistance, also presented high corrosion
resistance, having a depth of less than 300 micrometres. Consequently, the valve of
the present invention presents a depth of corrosion at least 40 % less than that presented
by the valve subjected to the conventional nitridation.
[0040] Figure 5 presents two photographs showing the depth of corrosion following the implementation
of a second corrosion test using method VDA 230-214 for metallic materials applied
upon components subjected to the exhaust gases of the engine. It may be observed that
the valve having conventional nitridation (state of the art) presents a visible band
of corrosion having a depth exceeding 20 micrometres. In contrast, the valve of the
present invention presents a minimal band of corrosion having a depth of less than
3 micrometres. These values of depth of corrosion are represented graphically in figure
6.
[0041] It is important that it be noted that the results of the second corrosion test carried
out show that the valve 1 of the present invention presents a depth of corrosion 85
% less than the valve of the state of the art.
[0042] Consequently, both the corrosion tests carried out clearly demonstrate an improvement
in the corrosion resistance of the valves of the present invention in relation to
the valves subjected to the conventional nitridation.
[0043] In summary, the valve 1 which is the object of the present invention presents a series
of advantages and benefits in relation to the valves presently known, these being:
- I. Nitrided layer having high hardness, exceeding 900 HV, up to 2000 HV;
- II. Excellent wear resistance in combination with high corrosion resistance;
- III. Maintenance of the passive film of oxide 11 of the material by virtue of the
low temperature of diffusion of nitrogen in the solid solution into the metallic matrix
of the substrate 8 of valve 1.
[0044] An example of a preferred embodiment having been described, it shall be understood
that the scope of the present invention covers other possible variations being limited
solely by the content of the appended claims, therein included the possible equivalents.