Technical Background Very specific demands have to be met by high temperature applications e. g. piston rings that are intended for use in for instance marine diesel engines, particularly as concerns strength, anti-corrosive properties, wear resistant, and material resilience. When used in a diesel engine the piston ring is arranged to abut on the one hand against an associated piston groove, on the other against an engine cylinder-bore.

Consequently, the ring should be wear-resistant, particularly at the interface towards the cylinder bore, where high friction is generated when the engine is in operation. The piston ring should therefore also possess an inherent tension or resilience whereby the piston ring will constantly be forced outwards, into abutment against the cylinder bore. In addition, upon each explosive stroke of the engine, the piston ring is urged with considerable force radially outwards, into abutment against the cylinder bore, with consequential increase of stress. Due to a high working temperature in engines and especially due to the impact of produced heat, from contact between piston rings and cylinder liner during the process, many materials loose some of their yield strength and show softening.

In operation, especially some contact areas between the piston ring and cylinder liner material are exposed to high temperatures, to considerable temperature

differences, and to the effects of a highly corrosive environment.

In order to withstand the effects of these stress- inducing causes, the piston ring therefore also must exhibit considerable wear resistant, ductility, and thermal stability. By ductility is to be understood herein the maximum possible deformation of the material before cracking begin.

Today, piston rings are generally manufactured from a cast-iron blank, which meets the requirements imposed on the material as regards strength and resilience but not on wear resistance on the surface thereof that faces the cylinder bore. Cast iron does not possess the required thermal stability at high temperature. A cast- iron piston ring blank therefore usually is provided with a wear-resistant wear layer on the surfaces most exposed to wear.

The wear layer, which usually is formed by a chromium-compound material, is generally applied to the piston ring blank in an electrolysis process as described e. g. in EP 0 668 375. In accordance with the teachings of this specification the piston ring blank is given a hard chromium layer in an electrolysis process. However, difficulties do arise in achieving a sufficiently strong bond between the material of the blank and the material of the wear layer, which causes problems, because of the risk that the material of the wear layer be torn away from the material of the blank. When this happens, the comparatively soft material of the blank-material surface is exposed to wear in the area of contact against the cylinder bore, with resulting considerable shortening of the life of the piston ring.

Another problem is that the coating gradually wears away, even if the bond between the surfaces is comparatively strong. The wear on the piston ring progresses slowly as long as the wear layer is intact but very rapidly, once that layer has disappeared. As a

result, it may be difficult to determine in time when a piston ring change should be made.

Another issue is to increase the oxidation resistance of the piston ring at high temperatures. In W09532314 there is provided a nickel-aluminium intermetallic basis alloy considered suitable for pieces, such as gas turbine blades, exposed to a high and continuous thermal stress. This alloy is claimed to improve thermal, oxidation and thermo-chock resistance.

However, the hardness properties and wear-resistance of this compound are considered insufficient for use by other pieces and elements exposed to wear and thermal stress.

Summary of the Invention The object of the present invention is to provide a material, particularly intended for medium to high temperature applications such as piston rings, that meets the requirements necessary as regards wear resistance, resilience, anti-corrosiveness, hardness, thermal stability and ductility.

Another object is to provide a piston ring, which does not suffer from the above drawbacks found in the prior art. Other features and advantages of the present invention will become apparent from the following description of the invention.

The present invention provides according to a first aspect of the invention a piston ring comprising a piston ring substrate, wherein said piston ring substrate comprises at least 50 volume%, of intermetallic alloy, based on the total volume of the wear-resistant composition.

The inventive piston ring comprising an intermetallic alloy has shown unexpectedly good characteristics in relation to piston rings, which comprises a piston ring substrate of cast iron, being of more conventional type.

Preferably the piston ring substrate comprises at least 70 volume%, and more preferably 90-100 volume%, of intermetallic alloy, based on the total volume of the piston ring substrate.

It has been discovered that a piston ring, which is substantially formed by at least one intermetallic alloy shows very good characteristics for the extreme environment to which the piston rings are exposed. For great piston rings intended for marine diesel engines, the properties of a piston ring with the inventive composition causes such considerable improvement in quality that the need for further coating to withstand wear is reduced. This will make many of the conventional price raising post treatment steps regarding coating, in order to achieve equal quality, unnecessary.

In cases when it is preferred a coating can be arranged on a piston ring substrate in order to further improve the piston ring according to the invention.

Suitably, such a coating comprises an intermetallic alloy in accordance with the invention, even though also other coatings are possible.

Preferably the piston ring substrate comprises an intermetallic alloy based on at least one of the metals from a group consisting of Al, Fe, Ni, Si, Ti, Mg, Be, Nb, Co, Zr, Ta, Mo and W. According to a preferred embodiment of the invention the piston ring substrate comprises at least one of the intermetallic alloys NiAl and Ni3Al. A mixture of said intermetallic alloys is also a possible.

According to a further preferred embodiment of the invention the piston ring substrate comprises at least one of the intermetallic alloys FeAl and Fe3Al. A mixture of said intermetallic alloys is also a possible.

The present invention provides according to a second aspect of the invention a wear-resistant composition, intended for medium to high temperature applications, particularly for piston rings, wherein the material

comprises a composite ceramic compound (hard phase). Said composite composition also comprises at least one intermetallic alloy.

One of the advantages of the inventive wear- resistant composition is the ability to withstand yield strength softening up to a temperature of around 600 °C.

It is not unusual that a piston ring locally has to withstand temperatures in the range of 400 to 500 °C or more in working conditions. If the metallic material (the matrix) in such a composite for some reason, e. g. softening caused by high temperature, can not withstand movement of the hard phase in the composite, the hard phase is not likely to stay in place. The hard phase will leave their place and then work like a polishing agent and cause higher wear (three body wearing).

It is thus beneficial to use an intermetallic alloy for providing support to the ceramic compound in the composite material. An important object for the intermetallic alloy is to keep the hard phase in place during contact with liner material in order to avoid the earlier described polishing effect also in the above- mentioned temperature range.

Preferably, said composite composition comprises an intermetallic alloy based on at least one of the metals from a group consisting of, Al, Fe, Ni, Si, Ti, Mg, Be, Nb, Co, Zr, Ta, Mo and W.

In a preferred embodiment of the present invention said composite composition comprises a matrix formed by intermetallic nickel-aluminides from said group.

It is thus advantageous to use an intermetallic alloty, e. g. a nickel-aluminide matrix for providing support to the ceramic compound in the composite material. An important object for the intermetallic nickel-aluminide matrix is to keep the hard phase in place.

The wear-resistant composition according to the invention also comprises a hard phase consisting

preferably of at least a ceramic compound chosen from a group consisting of aluminium oxide, chromium carbide, chromium oxide and silicon carbide e. g. Al203, Cr3C2, Cr203, and SiC.

The hard phase improves the wear resistance and the ability to resist thermal fatigue deformation of the composite. At the same time the coefficient of thermal expansion of the inventive composition is reduced. The compatibility of hard phase and matrix is an important factor in this case. A1203 is preferred together with Al- based intermetallic alloys due to higher interface bonding with the matrix material but the other hard phases are also working well in this respect.

It is also an object of the present invention to provide a piston ring, particularly intended for large marine diesel engines, consisting of the inventive wear- resistant composition.

It is also provided in accordance with the present invention a piston ring, particularly intended for diesel engines, wherein said piston ring comprises a coating of the inventive wear resistant composition. By using the wear-resistant composition especially as coating on a substrate a more cost efficient product is obtained, particularly in those cases when the cost of material forms a great part of the total production cost.

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent for one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. Thus it is understood that various methods such as plasma-, HVOF spraying or other related prior art methods can be used to apply the inventive composition to a substrate such as e. g. a piston, a piston ring and a cylinder liner or at least parts of them.

Brief Description of the Drawing Currently preferred embodiments of the present invention will now be described in more detail, with reference to the accompanying drawing.

Fig. 1 is a schematic representation of superlattice dislocations in a two-dimensional simple cubic lattice.

Fig. 2 is a table showing the rate of wear relative to pressure-exposure in tests of a composition in accordance with one embodiment of the invention vis-a-vis a well-known cast iron for piston rings named Darcast.

Fig. 3 is a SEM-picture of a composition in accordance with the invention.

Fig. 4 is one embodiment of a piston ring in accordance with the present invention.

Detailed Description of Preferred Embodiments In accordance with a preferred embodiment of the invention it is provided a wear-resistant composite composition, intended for medium to high temperature applications and particularly for piston rings, wherein the wear-resistant composite composition comprises a ceramic mixture of intermetallic composition and a ceramic compound. The wear-resistant composite composition specifically comprises at least one intermetallic nickel-aluminide chosen from the group consisting of NiAl and Ni3Al. The intermetallic nickel- aluminide or nickel-aluminides forms a matrix to which a hard phase is added.

As used herein the term intermetallic compounds are a class of materials, which can be viewed as occupying an intermediate position regarding the properties of the material between metallic alloys and ceramics. They are also considered as a unique class of metallic materials that form long-range ordered crystal structures below a critical temperature, generally referred to as the critical ordering temperature (Tc).

The essential condition for a substitutional solid solution of a suitable composition to become ordered is that unlike atoms i. e. different elements must attract each other more than like atoms in order to lower the free energy upon ordering. In other words, the degree of order of intermetallic compounds is closely related to the nature of the bonding. These ordered intermetallics usually exist in relatively narrow compositional ranges around simple stoichiometric ratio.

The ordered crystal structure of nickel aluminides makes it feasible to achieve high tensile ductility. The ductility of polycrystalline Ni3Al is further increased by micro alloying with boron addition that segregates the grain boundaries and suppresses brittle intergranular fraction.

An above-mentioned effect depending on the crystal structure is represented schematically in Fig. 1 by a super lattice dislocation in a two-dimensional simple cubic lattice. Intermetallic compounds exhibit a very high yield stress that is often maintained to elevated temperatures. Deformation in ordered alloys is controlled by the glide of super lattice or paired dislocations, as super dislocations, further illustrated in Fig. 1 for a two-dimensional ordered lattice having an AB composition.

The first, or leading, dislocation creates a layer of anti-phase domain, which can be thought of simply as a layer of wrong bonding, and the second, or following, dislocation restores the order. The relatively low mobility of super dislocations gives higher yield strength; that is, yield strength increases rather than decreases with increasing temperature.

The wear-resistant composition comprises a matrix formed by an intermetallic nickel-aluminide chosen from a group consisting of NiAl and Ni3Al. The composition also comprises a ceramic compound chosen from a group consisting of chromium carbide, chromium oxide and aluminium oxide e. g. Cr203, Cr3C2, SiC and Al203.

Examples of embodiments of the present invention are given below.

Example 1 A composition was prepared by forming a mixture of the following ingredients in the parts by weight quoted in table 1 : Table 1 No. Name Element Ni AI Cr Zr Nb 1 |NiAI-Nb| wt% 65-66 | 27-28 | 2-3 0,5-1 4-4, 5 A powder was prepared by forming the mixture of components as set out in table 1 of example 1.

Furthermore, 5-10% by volume of the initial mixture was replaced by 5-10% by volume of A1203. The resulting composition was heated and applied to a substrate in accordance with prior art techniques to form a wear- resistant composition on the substrate. The resulting composite had good wear resistance, ductility, and thermal stability properties.

Fig. 2 is a figure showing the rate of wear relative to pressure-exposure in tests of a composition in accordance with one embodiment of the invention vis-a-vis a well-known cast iron for piston rings known as Darcast.

In order to further illustrate the properties of the invention, reference is made to Fig. 3, which is an SEM- picture of a preferred embodiment of a wear-resistant composition in accordance with the invention. The picture discloses a matrix comprising darker"islands"of a hardphase. In this case the hardphase is a chromium carbide. By means of diffusion between matrix and hardphase a mixed zone, which is also clearly visible on the picture, is formed. The mixed zone provides for that a hard bonding is formed between hardphase and matrix and preferably the mixed zone is formed symmetrically around the hardphase.

A further embodiment of the wear-resistant composition according to the invention is outlined in the following example 2.

Example 2 Table 2 No. Name Element Ni Al Fe Mn ti Zr B 2 Ni3Al-Fe wt% 77-78 9-10 11-12 0,5 0,5 0,01 O,1 A powder was prepared by forming an initial mixture of components as set out in table 2 of example 2.

Furthermore, 5-10% by volume of the initial mixture was replaced by 5-10% by volume of A1203. The resulting composition was exposed to heat treatment and applied to a substrate in accordance with e. g. prior art techniques to form a wear-resistant composition on a substrate. The resulting composite had good wear resistance, ductility, and thermal stability.

Example 3 A third example of a wear-resistant composition according to the invention is given in the below table 3.

Table 3 No. Name Element Ni Al Cr C Mn Ti Zr B 3 Ni3Al-Cr wt% 81-83 8-9 7-8 0,1 0,4-0,5 1 0,6 0,1 A wear resistant composition was prepared by forming the mixture of components as set out in Table 3 of example 3. In this example chromium carbide is used as hard phase compared to the previous given examples. By, in accordance with the previous examples adding the hard phase Al203 to the mixture in table 3 instead, an increased thermal stability is obtained compared to the mixture according to table 3. Though A1203 is given as the preferred alternative for a hard phase compound in the

above stated examples, excellent results were achieved with other hard phase compounds as well.

Example 4 A fourth example of a wear-resistant composition according to the invention is given in the below table 4.

Table 4 No. Name Element Fe Al Cr C Mo Ti Zr B 4 Fe3Al-Cr wt% Rem* 13-17 2-6 0,1 0,1-1,5 1 0,6 0,1 *Rem=remaining It is of course possible to use any hard phase from the group consisting of chromium carbide, chromium oxide, silicon carbide and aluminium oxide e. g. Cr203, Cr3C2, SiC and A1203 in combination with any composition given in the tables 1-4. It is further realized that according to a first aspect of the invention a piston ring can be provided by casting an optional composition according to for example the tables 1-4 without adding a hardphase.

Casting of a piston ring substrate according to a first aspect of the invention will now be described. The raw material for the casting is melt in presence of an inert gas. An example of the melting process for working a material composition, comprising Ni3Al, of about 100 kg is given in the below table 5: Table 5 Step Time Effect Action 1 0 60 kW 300 Hz Heat treatment starts 2 +20 min 80 kW 400 Hz Reaction starts 3 +65 min 145 kW All Ni is melted 4 +85 min 100 kW 1530 degrees C 5 +85 min 100 kW Cover with Ca-comp. 6 +90 min 100 kW Add compounds 7 +95 min 100 kW 1533 degrees C

Thereafter the composition is transferred to a mould. The mould is preferably of sand type, suitably hardened by CO2. After the moulding step the piston ring substrate can be treated as a known substrate in order to provide a piston ring according to the invention.

Fig. 4 is one embodiment of a piston ring in accordance with the invention. The piston ring preferably comprises a coating of said wear-resistant composition.

In a second preferred embodiment of the invention the piston ring consists of the inventive wear resistant composition.

As will be appreciated, the present invention is not limited to the embodiments and examples described herein.

For example, further substances may be added to the wear- resistant composition in order to modify its properties in some respect. Also other mixtures and combinations than those listed in the tables 1-3 are possible within the scope of the invention. For special conditions up to 50 %, preferably between 1-30 %, and most preferably between 5-10 % by volume of the total composition can be hard phase such as, chromium oxide, silicon carbide, Cr3C2 and Al203.

It is also realized that the piston ring substrate, or a coating of a piston ring substrate according to the invention can comprise an intermetallic alloy based on at least one of the metals from a group consisting of, Al, Fe, Ni, Si, Ti, Mg, Be, Nb, Co, Zr, Ta, Mo and W.