Sliding element for internal combustion engines

Abstract

A sliding element may include a base material having an annular external surface upon which a bonding layer and a sliding layer are sequentially deposited. The sliding layer may be composed of hard amorphous carbon of a combined matrix with sp3/sp2 bonds. The sliding layer may include a plurality of nanoparticles of graphite incorporated within the combined matrix of sp3/sp2.

Claims

1. A sliding element for an internal combustion engine, the sliding element comprising a base material having an annular external surface upon which a bonding layer and a sliding layer are sequentially deposited, the sliding layer composed of hard amorphous carbon of a combined matrix of sp3/sp2 bonds, wherein: the sliding layer includes a plurality of nanoparticles of graphite incorporated within the combined matrix of sp3/sp2 bonds; the sliding layer includes a first depth region, a second depth region, and a third depth region disposed sequentially one after the other; the first depth region includes a prominence of sp3 bonds; the second depth region includes a prominence of sp2 bonds; and the third depth region includes a prominence of sp3 bonds.

2. The sliding element as claimed in claim 1, wherein a size of the plurality of nanoparticles of graphite is from 1 nanometer to 1000 nanometers.

3. The sliding element as claimed in claim 1, wherein a size of the plurality of nanoparticles of graphite is from 5 nanometers to 500 nanometers.

4. The sliding element as claimed in claim 1, wherein the bonding layer is composed of at least one of metallic chromium having a body centered cubic structure, nickel, cobalt, tungsten, and chromium carbide.

5. The sliding element as claimed in claim 1, further comprising an intermediate layer disposed between the bonding layer and the sliding layer, wherein the intermediate layer is composed of a ceramic material.

6. The sliding element as claimed in claim 5, wherein the intermediate layer has a thickness from 5 micrometers to 50 micrometers.

7. The sliding element as claimed in claim 5, wherein: the bonding layer is a PVD-deposited bonding layer; and the intermediate layer is a PVD-deposited intermediate layer.

8. The sliding element as claimed in claim 1, wherein the sliding layer is composed of less than 2% by weight of hydrogen.

9. The sliding element as claimed in claim 1, wherein the sliding layer has a thickness from 1 micrometer to 50 micrometers.

10. The sliding element as claimed in claim 1, wherein the sliding layer has a thickness from 3 micrometers to 35 micrometers.

11. The sliding element as claimed in claim 1, wherein the sliding layer has a hardness from 20 GPa to 50 GPa.

12. The sliding element as claimed in claim 1, wherein the base material is composed of stainless steel having from 10% to 17% of at least one of chromium, cast iron, and carbon steel.

13. The sliding element as claimed in claim 1, wherein the sliding element is a piston ring.

14. A method for coating a sliding element for an internal combustion engine, the method comprising: applying a bonding layer on an annular external surface of a base material; forming a sliding layer on the bonding layer via physical vapor deposition by cathodic arc; wherein the sliding layer is composed of hard amorphous carbon of a combined matrix of sp3/sp2 bonds; wherein forming the sliding layer includes incorporating a plurality of nanoparticles of graphite within the combined matrix of sp3/sp2 bonds; and wherein forming the sliding layer further includes forming a first depth region, a second depth region, and a third depth region disposed sequentially one after the other, the first depth region including a prominence of sp3 bonds, the second depth region including a prominence of sp2 bonds, and the third depth region including a prominence of sp3 bonds.

15. An internal combustion engine, comprising at least one sliding element including a base material having an annular external surface upon which a bonding layer and a sliding layer are sequentially deposited, the sliding layer composed of hard amorphous carbon of a combined matrix of sp3/sp2 bonds, wherein: the sliding layer includes a plurality of nanoparticles of graphite incorporated within the combined matrix of sp3/sp2 bonds; the sliding layer is substantially free of hydrogen; the sliding layer includes a first depth region, a second depth region, and a third depth region disposed sequentially one after the other; the first depth region includes a prominence of sp3 bonds; the second depth region includes a prominence of sp2 bonds; and the third depth region includes a prominence of sp3 bonds.

16. The sliding element as claimed in claim 1, wherein the plurality of nanoparticles of graphite have a structure of sp2 bonding that is different from that of the combined matrix of sp3/sp2 bonds.

17. The sliding element as claimed in claim 1, wherein: the bonding layer has a body centered cubic polycrystalline columnar structure of metallic chromium; and the bonding layer has a thickness of 0.01 micrometers to 0.5 micrometers.

18. The sliding element as claimed in claim 1, wherein: the first depth region extends to a depth of 320 nanometers and includes 55% to 65% sp3 bonds; the second depth region extends from the depth of 320 nanometers to 430 nanometers and includes 65% to 70% sp2 bonds; and the third depth region begins at the depth of 430 nanometers and includes 60% to 65% sp3 bonds.

19. The sliding element as claimed in claim 1, wherein a greater quantity of the plurality of nanoparticles of graphite are present in the second depth region than in the first depth region and the third depth region.

20. The method of claim 14, wherein forming the sliding layer on the bonding layer via physical vapor deposition by cathodic arc is performed under a condition of pressure from 0.01 mbar to 0.2 mbar, with a cathode current of 40 A to 100 A, a flow of an argon gas from 50 sccm to 200 sccm, a polarization voltage from 30 V to 45 V, and a temperature from 150° C. to 240° C.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The present invention shall, hereinafter, be described in greater detail on the basis of an example of embodiment represented in the drawings. The figures show:

(2) FIG. 1: a representation of the disposition of a piston ring within the interior of a cylinder of an internal combustion engine;

(3) FIG. 2: a cross-section of the piston ring revealing the structure of the coating of the present invention;

(4) FIG. 2a: a cross-section of the piston ring revealing the structure of the coating of the present invention;

(5) FIG. 3: a graphical representation of the tribological behavior of the coating of the present invention;

(6) FIG. 4: a graphical representation of the hardness of the coating of the present invention and of the percentage of sp.sup.3 bonds as a function of the temperature of the PVD process;

(7) FIG. 5: maps obtained by EELS revealing the distribution of sp.sup.3 and sp.sup.2 bonds in the structure of the coating of the present invention; and

(8) FIG. 6: a graphical representation of the profile of distribution of sp.sup.3 and sp.sup.2 bonds in the structure of the coating of the present invention.

DETAILED DESCRIPTION OF THE DRAWINGS

(9) The present invention relates to a sliding element, such a piston ring for internal combustion engines, having a coating of hard amorphous carbon comprising nanoparticles of a solid lubricant capable of bringing about a reduction in the friction and, consequently, reducing the wear upon the sliding face of the ring, together with diminishing the internal stresses generated in the application of the coating of hard amorphous carbon, in addition to ensuring high hardness.

(10) In an alternative preferential configuration, the sliding element of the present invention may be an engine component maintaining contact with a thin layer of lubricating fluid, experiencing wear, such as for example, inter alia, a cylinder liner, an oil scraper piston ring, a first groove piston ring.

(11) Initially, it should be noted that the sliding element of the present invention is preferentially a piston ring 10 for internal combustion engines operating under high load and/or power, as illustrated in FIG. 1. Usually these piston rings work with very close tolerances and a thin film of oil to ensure excellent performance and low emissions of CO.sub.2.

(12) The piston ring 10 of the present invention comprises a base material 12 having an external annular surface 11, being composed, preferentially, of stainless steel having 10% to 17% chromium, the balance being cast iron and carbon steel. The annular external surface 11 corresponds to the portion of the ring parallel to the liner of the cylinder 20, in other words it is the surface acting as interface between the ring and a cylinder liner 20, wherein it is upon the external surface 11 that the coating is deposited.

(13) In a preferential configuration, illustrated in FIG. 2, the external surface 11 receives, sequentially, a bonding layer 13 and, upon the bonding layer 13, a sliding layer 14 composed of hard amorphous carbon.

(14) The bonding layer 13 has as objective to bring about the relief of the stresses between the metal structure of the ring and the sliding layer 14 of amorphous carbon, in this manner ensuring an excellent adhesion between the functional sliding layer 14 and the base material 12. In a preferential, however not obligatory, manner the bonding layer 13 is formed by a body centered cubic (bcc) polycrystalline columnar structure of metallic chromium (Cr), the thickness whereof ranges between 0.01 micrometers and 2.0 micrometers, preferentially 0.01 micrometers and 0.5 micrometers. In an alternative preferential configuration, the bonding layer 13 is composed of one from among the materials such as nickel (Ni), cobalt (Co), tungsten (W), chromium carbide (CrC) or by a ceramic material.

(15) In its turn, the sliding layer 14 acts as an antifriction layer and is formed of hard amorphous carbon (DLC), the carbon being totally amorphous, free or substantially free of hydrogen, comprising less than 2% by weight of hydrogen.

(16) In an alternative preferential configuration, illustrated in FIG. 2a, the external surface 11 of the ring 10 receives, sequentially, a bonding layer 13, an intermediate layer 13a and a sliding layer 14. The intermediate layer 13a is composed of a ceramic material such as chromium nitride (CrN), or titanium nitride (TiN), or multilayers of chromium-aluminum nitride and chromium nitride (CrAlN/CrN). The intermediate layer 13a comprises a thickness ranging between 5 micrometers and 50 micrometers and is deposited by a process of physical vapor deposition (PVD).

(17) In a manner differing from the solutions found in the state of the art, the present invention presents a sliding layer 14 of hard amorphous carbon comprising a matrix combining bonds of type sp.sup.3 (diamond) and type sp.sup.2 (graphite), wherein islands, or nanoparticles, of graphite are incorporated, revealing a nanostructure provided with islands of solid lubricant embedded within an sp.sup.3/sp.sup.2 matrix.

(18) In this manner, the present invention has as object a piston ring 10 having a coating comprising a hardness ranging between 20 GPa and 50 GPa, preventing however high wear of the cylinder liner 20, the hardness whereof is considerably lower, by virtue of the reduction of the friction and of the wear of the sliding components through the rendering available of a flow of solid lubricant in the sliding layer 14.

(19) In order to achieve the objects of the present invention, the sliding layer 14 of the piston ring 10 comprises islands, or nanoparticles, of graphite incorporated within the sp.sup.3/sp.sup.2 matrix capable of relieving and reducing internal stresses of the matrix, resulting in a sliding layer 14 having high resistance to wear, by virtue of the reduction of the friction, and high hardness with reduced internal stresses, preventing the spalling of the coating, in addition to rendering available a flow of lubricant in a thin film of oil, considerably diminishing the probability of seizure of the piston ring/cylinder liner assembly.

(20) It is important to note that, when describing nanoparticles, particles of the order of nanometers are being considered, any particles having a size of less than 1000 nanometers being considered to be nanoparticles. Consequently, the present invention reveals islands, or nanoparticles, of graphite incorporated within an sp.sup.3/sp.sup.2 matrix of a DLC coating, the size of the nanoparticles of graphite ranging between 1 nanometer and 1000 nanometers, preferentially between 5 nanometers and 500 nanometers.

(21) By virtue of the possibility of relief of internal stresses of the sp.sup.3/sp.sup.2 matrix of high hardness, the sliding layer 14 of DLC of the present invention comprises a thickness ranging between 1 micrometer and 50 micrometers. In a preferential configuration the thickness of the sliding layer ranges between 3 micrometers and 35 micrometers.

(22) The new technologies of coating piston rings comprise the combination of the concepts of deposition by a process of physical vapor deposition based upon chromium nitride (CrN based PVD), the coating being composed of hydrogen free DLC hard amorphous carbon, wherein the thickness of the coating ranges between 1 and 50 micrometers, in accordance with application in light or heavy engines. These concepts combine advantages of the ceramic PVD and DLC coating, being capable of satisfying the requirement for low friction and high seizure resistance within a low cost solution utilizing a robust coating process. This combination furthermore permits the obtainment of a great thickness of coating having lower internal stresses, ensuring high durability of the ring with appropriate finish. The DLC coating is based upon hard amorphous carbon, being hydrogen free and having high resistance to wear, preventing the coating from experiencing incompatibilities with oil additives.

(23) The present invention is based upon recent discoveries regarding the morphology and the microstructure of the DLC coating together with the new processes of deposition, ensuring a better adherence utilizing cathodic arc processes, and a bonding layer 13, or adherence layer, having a specific nanostructure. Furthermore, the process of optimized control of temperature diminishes the activation energy necessary to convert diamond into graphite and increases the kinetics of the reaction. These temperature controls have an impact upon the control of internal stresses and achieve better carbon bonds, as may be observed in FIG. 3.

(24) FIG. 3 presents a graph describing the tribological behavior of the coating of hydrogen free hard amorphous carbon of the present invention, having three different regions.

(25) In region 1 there is a sliding layer 14 obtained by a PVD process realized at temperatures exceeding 240° C., great quantities of nanoparticles of graphite incorporated within the sp.sup.3/sp.sup.2 matrix being obtained. Consequently, the coating obtained in region 1 presents characteristics of a soft material with reduction of friction which, however, experiences high wear in the contact between the annular external surface 11 of the base material 12 of the piston ring 10 and the cylinder liner 20. In this respect the coating presents reduced resistance to wear at temperatures exceeding 240° C.

(26) In contrast, in region 3 of the graph there is a DLC sliding layer 14 obtained by a PVD process realized at temperatures below 150° C., small quantities of nanoparticles of graphite incorporated within the sp.sup.3/sp.sup.2 matrix being obtained. Consequently, the coating obtained in region 3 presents high hardness, having however high internal stresses which, eventually, cause the fragmentation or spalling of the coating.

(27) In region 2 there is the sliding layer 14 obtained by a PVD process realized at temperatures ranging between 150° C. and 240° C., capable of bringing about the development of nanoparticles of graphite incorporated within a matrix combining sp.sup.3/sp.sup.2 bonds. The coating obtained in region 2 is capable of bringing about a reduction in the friction, with consequent reduction in the wear of the piston ring 10 in contact with a cylinder liner 20, in addition to ensuring high hardness, having lower internal stresses for high durability of the ring.

(28) The transition between the functional regions of the sliding layer 14 is governed, principally, by the temperature at the surface of the substrate whereupon the coating is synthesized. Coatings of hydrogen free hard amorphous carbon are, typically, produced by evaporation of graphite through a process of physical vapor deposition by cathodic arc. The temperature of the substrate is governed, in general, by the electrical energy applied for evaporation of graphite. In other words, the greater the power applied, the greater the evaporation and the greater the temperature of the substrate.

(29) Another important phenomenon, also dependent upon the electrical energy applied in the process, is the generation of particles upon the DLC coating. Due to the energetic reaction, a certain quantity of unevaporated material is ejected from the target and incorporated within the sp.sup.3/sp.sup.2 matrix of the sliding layer 14 in a structure of graphite, generating islands of graphite (sp.sup.2). These islands of graphite may be understood as being nanoparticles of graphite having a structure of sp.sup.2 bonding, differing from the structure of the matrix. It is essential to emphasize that, the greater the evaporation from the surface of the target, the greater will be the quantity of molten material ejected from the surface of the target, in this manner increasing the generation of islands of sp.sup.2 graphite in the sliding layer 14.

(30) It should be noted that a DLC coating having a predominance of sp.sup.a bonds is desirable by virtue of the high hardness which the coating may attain, achieving values exceeding 40 GPa. On the other hand, coatings of high hardness represent lower wear upon the coated face, significantly increasing the combined wear between the piston ring 10 and the cylinder liner 20 by virtue of more aggressive working conditions for the cylinder liners 20. A further disadvantage of extremely hard coatings arises from the thickness of the coating which must be limited to a few micrometers, considerably diminishing the durability of the coated face. The greater the thickness of the hard coating, the greater the internal stresses of the material, generating the spalling of the coating during the operation of the engine. Spalling may be understood to be a process wherein fragments of coating debond from the base material 12 of the ring due to working impacts or pressures.

(31) Diversely, coa tings having sp.sup.2 bonds are very soft and excellent solid lubricants. As a consequence, the correct balance between hardness, brought about by the sp.sup.a bonds, and lubrication, brought about by the sp.sup.2 bonds and by the nanoparticles of graphite incorporated within the sp.sup.a/sp.sup.2 matrix, is capable of achieving an ideal tribological performance, principally for piston rings working under critical operational conditions with high wear, requiring excellent hardness and lubrication.

(32) In this critical state, the coating must provide good mechanical strength, a characteristic which cannot be achieved when a high content of graphite exists in the structure of the coating. This condition is capable of explaining the behavior of the coating in region 1 of the graphic of FIG. 3, wherein when the temperature of the substrate increases great quantities of islands, or nanoparticles, of graphite are generated.

(33) Preferentially, the coating of the present invention is deposited upon the external surface 11 of the ring by a process of physical vapor deposition by cathodic arc occurring under a condition of pressure ranging between 0.01 mbar and 0.2 mbar, preferentially of 0.0022 mbar, with a cathode current of between 40 A and 100 A, preferentially of 80 A, a flow of argon gas of between 50 sccm and 200 sccm, preferentially of 100 sccm, and at a polarization voltage ranging between 30 V and 45V, preferentially of 40 V, with a variable temperature of deposition during the process comprising temperatures ranging between 150° C. and 240° C.

(34) The temperature of the process is controlled by the time wherein the current from the cathode remains connected. The duty cycle parameter, or working cycle, represents the percentage of time wherein the current remains connected. The greater the average temperature desired the longer the duty cycle. In this manner, in table 1 hereinbelow the temperatures attained may be observed in the process in accordance with the duty cycle:

(35) TABLE-US-00001 TABLE 1 Temperature Duty Cycle Time connected Time disconnected (° C.) (%) (min) (min) 160 18 4 18 180 21 4 15 200 26 5 14 210 31 5 11 220 34 5 10 240 42 6 8

(36) FIG. 4 shows two graphs representing the trends of hardness obtained and percentage of sp.sup.3 bonds for the coating of the present invention as a function of the temperature of the PVD process utilized.

(37) Consequently, observing FIG. 4 it may be seen that for a process temperature of 150° C. there is obtained a coating having an effective microhardness of at least 50 GPa (HIT hardness) having a percentage of sp.sup.3 bonds ranging between 60% and 70%. For a temperature of 200° C. there is obtained a coating having a hardness ranging between 30 GPa and 35 GPa with a percentage of sp.sup.3 bonds ranging between 40% and 50%. Furthermore, for a temperature of 240° C. there is obtained a softer coating having a hardness of less than 30 GPa and a percentage of sp.sup.3 bonds ranging between 20% and 30% with predominant formation of sp.sup.2 bonds (graphite), highly lubricant, however of extremely low hardness.

(38) Although the sliding layer 14, described in the present invention, is formed solely from carbon, the new technology of coating proposed differs from any other found in the state of the art by virtue of the fact that it reveals a sliding layer 14 of hard amorphous carbon comprising islands, or nanoparticles, of graphite incorporated within an sp.sup.3/sp.sup.2 matrix, capable of providing high hardness with reduction of friction under severe working conditions.

(39) The images shown in FIG. 5 are able to prove the existence of islands of graphite embedded or incorporated within a matrix combining sp.sup.3/sp.sup.2 bonds within the sliding layer 14 of the present invention. In this respect, FIG. 5 shows maps obtained by electron energy loss spectroscopy (EELS) in STEM mode revealing the distribution of sp.sup.3 and sp.sup.2 bonds within the sliding layer 14. Four maps are shown in this figure, as follows:

(40) i. The first map, shown in the upper left corner, presents a photograph of the coating having a resolution of 0.5 micrometers, wherein there may be observed the islands of graphite incorporated within the sp.sup.3/sp.sup.2 matrix. One island of graphite, particularly larger than the other islands, was selected for the purpose of illustration of the profile of distribution of sp.sup.3 and sp.sup.2 bonds composing the sliding layer 14.

(41) ii. The second map, shown in the upper right corner, presents a photograph of the coating having a resolution of 50 nanometers, detailing the profile illustrated for studying the sp.sup.3/sp.sup.2 bonds.

(42) iii. The third map, shown in the left lower corner, presents a photograph of the coating at a resolution of 50 nanometers, wherein the sp.sup.2 bonds are highlighted. In this map it is possible to observe all the sp.sup.2 bonds (graphite) in blue.

(43) iv. The fourth map, shown in the right lower corner, presents a photograph of the coating at a resolution of 50 nanometers, wherein the sp.sup.3 bonds are highlighted. In this map it is possible to observe all the sp.sup.3 bonds (diamond) in green.

(44) The profile illustrated, shown in the first and second maps, crosses an island of graphite. The percentage of the types of bonds (sp.sup.3 and sp.sup.2) found along a line of EELS analysis in the direction of growth of the coating is shown graphically in FIG. 6. Consequently, on observing FIGS. 5 and 6 together, it will be seen that the profile line crosses a large green portion having a predominance of sp.sup.3 bonds, ranging between 55% and 65% of sp.sup.3 bonds (diamond) and ranging between 35% and 45% of sp.sup.2 bonds. On crossing the blue portion, the profile of material of the coating changes radically, presenting a predominance of sp.sup.2 bonds, ranging between 65% and 70% of sp.sup.2 bonds (graphite) and ranging between 30% and 35% of sp.sup.3 bonds. Subsequently, the profile again crosses a green portion wherein again there is a predominance of sp.sup.3 bonds (diamond).

(45) Consequently, by means of FIGS. 5 and 6 it is possible to clearly observe the presence of islands of graphite (sp.sup.2) incorporated within an sp.sup.3/sp.sup.2 matrix, rich in sp.sup.3. It should be noted that the islands of graphite incorporated within the sp.sup.3/sp.sup.2 matrix of the sliding layer 14 comprise sizes of the order of nanometers and, for this reason, are referred to as nanoparticles of graphite.

(46) The coating of the piston ring 10 of the present invention acts such that, in the wear of the sliding layer 14, the nanoparticles of graphite become exposed, rendering solid lubricant available for the sliding between the ring and the cylinder liner 20. In this manner, the sliding layer 14 does not wear immediately, by virtue of the fact that the sp.sup.3/sp.sup.2 matrix comprises high hardness with nanometric particles of lubricant graphite which, in addition to bringing about a reduction in the friction, reduce the internal stresses of the hard sp.sup.3/sp.sup.2 matrix.

(47) In summary, the piston ring 10 of the present invention is capable of rendering possible a coating of hard amorphous carbon substantially free of hydrogen comprising a matrix of high hardness with nanoparticles of solid lubricant capable of relieving and reducing internal stresses of the matrix of high hardness, preventing the spalling of the coating, in addition to making available a flow of lubricant capable of bringing about a reduction in the friction and, consequently, an increase in the resistance to wear of the ring, preventing the seizure of the sliding components and ensuring excellent durability.

(48) An example of 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 claims appended, included therein the possible equivalents.