METAL-BASE ALLOY PRODUCT AND METHODS FOR PRODUCING THE SAME
A metal base alloy and methods for producing the alloy. The metal base alloy product includes the formula Mebase Ta Sib Crc Mnj Ve Cf, wherein—Mebase is a metal base selected from the group having Fe, Co and Ni, in an amount ranging from about 45-75 w %. The metal base alloy product contains a substantially homogenous dispersion of separate precipitated carbide particles in an amount ranging from 10-65 percentages by volume and the precipitate carbide particles have an average diameter of 0.01-5 micrometers.
The present invention relates to a metal base alloy and to methods for producing the alloy. More particular, the present invention relates to a high alloy metal base alloy product having advanced mechanical and physical properties as a result of its microstructure.
BACKGROUND OF THE INVENTIONThere is a great demand for metal based alloys, in particular iron based alloys, with advanced mechanical and physical properties.
The properties of iron base alloys are decided by the aligning elements and the main phases are normally ferrite, austenite and carbides which are characterizing the different structures such as martensite, perlite and bainite. The distribution and fraction of carbides influences together with the grain size the mechanical properties.
From 1960 towards today an impressive amount of research has been performed about rapid solidification of metal alloys to produce amorphous metals. During the years a large number of metal base alloys and in particular iron base alloys have been investigated. As a spin of from these investigations, new crystalline phases and new structures have been reported in a number of publications and patents for rapidly quenched iron based liquids. In this case the cooling rates has been 105K/sec and higher. A featureless phase with high hardness was reported to be found in iron base alloys at cooling rates of 105K/sec for example in U.S. Pat. No. 4,582,536B. A similar featureless phase formed at these high cooling rates was also reported in an article by Satheees Ranganathan et al, “Rapid solidification behavior of Fe-Cr-Mn-Mo-Si-C alloys”, from Metallurgical and Materials Transactions B, Volume 38B, December 2007.
The rapidly solidified alloys described in the prior art are only possible to produce as rather small products or articles of less than 500 μm of thickness by using special casting technologies. This results in high production costs and also gives large problems to control the structure and properties. Some of the prior art metal base alloys show interesting microstructures but which are brittle and therefore difficult to make use of commercially. Further, the alloys known in the prior art may have good mechanical properties but which are difficult to control and to predict.
SUMMARY OF THE INVENTIONIt is an object of the present invention to provide a metal base alloy product having a microstructure resulting in advanced mechanical and physical properties.
It is a further object of the present invention to provide a metal base alloy having outstanding mechanical and physical properties that can be produced in cost effective production processes and in an amount that provides a wide range of opportunities for articles to be produced from the alloy.
At least one of the above objects is obtained by a metal base alloy product consisting of the formula Mebase Ta Sib Crc Mnd Ve Cf, wherein
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- Mebase is a metal base selected from the group consisting of Fe, Co and Ni, in an amount ranging from about 45-75 w %,
- Ta is an alloying material selected from the group consisting of Mo, Nb and Ta in an amount a ranging from about 5-10 w %,
- Sib is a further alloying member in an amount b ranging from about 4-10 w %,
- Crc is a further alloying member in an amount c ranging from about 8-30 w %,
- Mnd is a further alloying member in an amount d ranging from about 0-10 w %
- Ve is a further alloying member in an amount ranging from about 0-10 w %, and
- Cf is a further alloying member in an amount a ranging from about 2-4 w %,
and wherein the metal base alloy product contains a substantially homogenous dispersion of separate precipitated carbide particles in an amount ranging from 10-65 percentages by volume and wherein the precipitated carbide particles have an average diameter of 0.01-5 micrometer.
The metal base alloy in accordance with the present invention shows a microstructure with fine precipitated carbide particles in a relatively high volume fraction compared to available advanced materials of today. The volume fraction of carbides is directly proportional to the carbon content according to the principle of the level rule. The carbide particles are further relatively small compared to available advanced materials of today.
The obtained structure having a large amount of small carbide particles is proven to give excellent strength and hardness to the material. For example, a hardness of 900-1300 Vickers and a yield stress of 1200 MPa may be obtained. In this context it may be interesting to mention that the so-called hard metals normally have a carbide size of about 5-10 micrometer and has a hardness of 1100-1400 Vickers.
Fe-base alloys with this high carbon content normally give a cast structure of coarse carbides. An advantage of the present alloy is that it can be casted and solidified using conventional methods to form a featureless structure, defined as the η-phase. If the η-phase is preserved to room temperature the alloy or product will be very brittle. Therefore the cooling conditions after solidification has to be controlled to achieve the fine carbide structure as described above.
A further advantage with the metal base alloy of the invention is that the microstructure may be further controlled through at least one heat treatment. Depending on the conditions during the solidification of the melt and the following cooling conditions after solidification, one or more suitable heat treatments may be performed.
The combination of high volume fraction of precipitated carbide particles and the carbide particles having a small average diameter or size ranging from 0.01-5 micrometers gives the material several advantages both related to mechanical properties and to the manufacture possibilities. As a result, at least one of the above mentioned objects is achieved.
According to an embodiment of the invention the precipitated carbide particles are substantially spherical carbides having an average diameter or size of 0.1-5 micrometer. The precipitation of fine, i.e. small, carbides of this size may be provided in the following ways. The alloy is casted or solidified using known methods. The cooling conditions after solidification are controlled in such a way that the η-phase is decomposed into carbides and austenite or ferrite.
By performing a heat treatment of the solidified and cooled alloy the morphology is further controlled. The heat treatment can be performed at rather high temperatures, i.e. at 800-1000 degrees Celsius, whereby carbides having an average diameter or size of 0.5-5 micrometer may be obtained. An even more preferred temperature interval may be used, i.e. 850-950 degrees Celsius. The material may be treated from 0.1-50 hours or more preferably 2-10 hours. High temperature and long treatment time gives a softer and more ductile material than at low temperature and shorter time. This is compared with the properties of the featureless phase that is very hard and brittle. The austenite phase by its nature contains carbon and the carbides will form in moderate volume fractions, as much of the carbon is locked in the austenite phase. The longer the heat treatment may last, the more the carbides will grow. Further, the shape of the carbides becomes uniform and substantially spherical or rounded during the heat treatment.
By performing a heat treatment of the alloy at medium high temperatures, i.e. at 650-800 degrees Celsius, carbides having an average diameter or size of 0.1-5 micrometer may be obtained. An even more preferred temperature interval may be used which is 700-750 degrees Celsius. The material may be treated from 1-30 hours or more preferably in the interval of 2-10 hours. This somewhat lower heat treatment temperature gives a harder and more brittle article with a higher yield stress. In this case the microstructure consists of a ferrite and carbides. If this heat treatment is chosen, a single heat treatment is performed. Thus, it is not followed by a second heat treatment.
According to another embodiment of the invention a second heat treatment is performed after a heat treatment at high temperatures. In the second heat treatment carried out at low temperatures (200-600° C.) very fine carbides, i.e. of 0.01-0.5 in size are formed. These very fine carbides are nano-crystalline carbides showing an atomic lattice matching in the matrix. This means that they are preferably precipitated in the matrix in-between the larger carbides, which are formed during the high temperature (800-1000° C.) heat treatment. During the heat treatment at low temperatures for approximately 1-30 hours, some of the austenite may transform to ferrite. Ferrite has a low solubility of carbon and therefore carbides are formed in a large volume fraction.
According to a further embodiment of the invention the precipitated carbide particles are a mixture of substantially spherical carbides having an average diameter of 0.5-5 micrometer and of nano-crystalline carbides having an average diameter of 0.01-0.5 micrometer. This mixture of fine carbides is obtained by controlling the cooling conditions after solidification followed by a heat treatment at elevated temperatures (800-1000 degrees Celsius) and eventually followed by a second heat treatment at lower temperatures (200-600 degrees Celsius). The mixture of many and very fine nano-crystalline carbides with carbides having a slightly larger diameter and a different shape and matching in the matrix give the material of the invention unique properties.
According to an embodiment of the invention the precipitated carbide particles are surrounded by a matrix of ferrite and/or austenite depending on the chosen heat treatment(s). Accordingly, the matrix may consist of austenite after the high temperature heat treatment and of ferrite after the temperature heat treatment at 650-800 degrees Celsius.
According to an embodiment of the invention the alloy has a tensile strength of at least about 800 MPa. The excellent mechanical properties of the material are a result of its microstructure.
According to an embodiment of the Invention the Mebase is Fe present in an amount from about 45-75 w %.
According to an embodiment of the invention the Ta is Mo present in an amount from about 5-10 w %.
According to an aspect of the present invention it is provided a method to produce a metal base alloy product consisting of the formula Mebase Ta Sib Crc Mnd Ve Cf, wherein
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- Mebase is a metal base selected from the group consisting of Fe, Co and Ni, in an amount ranging from about 45-75 w %,
- Ta is an alloying material selected from the group consisting of Mo, Nb and Ta in an amount a ranging from about 5-10 w %,
- Sib is a further alloying member in an amount b ranging from about 4-10 w %,
- Crc is a further alloying member in an amount c ranging from about 8-30 w %,
- Mnd is a further alloying member in an amount d ranging from about 0-10 w %
- Ve is a further alloying member in an amount ranging from about 0-10 w %, and
- Cf is a further alloying member in an amount e ranging from about 2-4 w %, wherein the method comprises the steps of:
- melting said metal base together with chosen alloying components using different melting processes such as high frequency or arc melting
- casting said alloy providing segregation free solidification conditions forming a featureless structure of said alloy
- controlling cooling conditions after solidification of said alloy, and
- heat treating said alloy in at least a first heat treatment step whereby said metal base alloy product obtains a substantially homogenous dispersion of separate precipitated carbide particles in an amount ranging from 10-65 percentages by volume and said precipitate carbide particles have an average diameter of 0.01-5 micrometer.
To be able to produce articles with an amorphous or featureless structure by more conventional methods, lower cooling rates are desirable. Casting of the alloy provides the possibility to make larger articles with reliable properties at a low cost and in a process that is easy to control. The featureless structure in iron base alloys formed at casting starts to decompose under controlled cooling conditions. Cooling rates as low as 10−2 (0.01) K/sec may be obtained. At low cooling rates, most of the featureless phase decomposes into ferrite and precipitated carbides during the cooling after solidification. Depending on the obtained structure after casting and cooling, a suitable heat treatment is chosen. In some cases the final material or product is obtained after casting and cooling. However, in most cases the material undergoes an initial heat treatment at high temperatures and then eventually a second heat treatment at low temperatures. Heat treatment of the alloy after casting and controlled cooling is here used to change and control the properties of the articles. The different procedures are described in more detail below.
According to an embodiment of the invention the method comprises the further step of heat treating the alloy in an inert atmosphere or under vacuum at 800-1000 degrees Celsius for 1-10 hours wherein said precipitate carbide particles are formed as substantially spherical carbides having an average diameter of 0.5-5 micrometer. Depending on the result after casting, the exact time and temperature is chosen. Generally, longer time at high temperatures of the interval gives larger carbides than shorter times in the first part of the temperature interval.
According to an embodiment of the invention the method comprises the step of heat treating the alloy in an inert atmosphere or under vacuum at medium high temperatures of 650-800 degrees Celsius for 2-10 hours wherein said precipitate carbide particles are formed in a matrix of ferrite having an average diameter of 0.1-5 micrometer.
Depending on the outcome of the casting, it may be preferable to perform a single heat treatment at medium high temperatures only.
After a heat treatment at high temperatures a second heat treatment may be performed to improve the microstructure and thus the properties of the material further. For this purpose a heat treatment at low temperatures (200-600° C.) may be performed. In the heat treatment at low temperatures very fine carbides are precipitated. If a first heat treatment at high temperatures is followed by a heat treatment at low temperature, a mixture of carbide particles having an average diameter of 0.5-5 micrometer and nano-crystalline carbide particles having an average diameter of 0.01-0.5 micrometer is obtained. The result is a ductile material but which is at the same time hard with a high yield stress.
Heat treatment of the cast structure consisting of a decomposed featureless structure in iron base alloys may be used to change and control the properties of the articles. During heat treatment the microstructure is changed and a substantially uniform dispersion of carbide particles is formed in an amount ranging from 10-65 percentages by volume, or even more preferably 35-50 percentages by volume and the carbide particles have an average diameter of 0.01-5 μm.
According to a further aspect of the present invention, it is provided a method to produce a metal base alloy product according to claim 1, wherein the method comprises the steps of:
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- melting the metal base together with chosen alloying components using different melting processes such as high frequency or arc melting
- powder processing of the alloy to produce powder with a particle size of 0.1-200 μm size'
- heating the obtained powder to control the transformation of a featureless structure into carbides and austenite/ferrite,
- keeping the powder at a constant temperature during heating to ensure that the carbides become small and rounded,
- pressing the obtained powder using high isostatic pressing (HIP) at a pressure of 60-150 MPa at a temperature of 800-1050° C.,
- cooling the product to approximately room temperature (20° C.), and
- heat treating the alloy in an inert atmosphere or under vacuum, to further control the precipitate carbide particles to an average diameter of 0.01-5 micrometer.
The low temperature during heating of the powder, also mentioned as the transformation heat treatment of the powder, before the high temperature high isostatic pressure treatment, leads to the decomposition of the η-phase to the initial carbide structure as is also seen in the solidified casted material after controlled cooling conditions. Suggested temperatures for the transformation heat treatment are 200 to 800 degrees Celsius.
The high temperature heat treatment for a cast material is for a HIP processed material substituted by the heat treatment during the sintering process at 800-1050° C. The HIP processed material may then optionally be heat treated at a low temperature of 200-600° C. for approximately 1-30 hours.
Using this method to produce powder by atomization and by high isostatic pressing which makes it possible to produce articles of very large size with a good homogenous structure and with properties close to hard metal.
When performing the HIP process on the metal base powder, the temperature is elevated and corresponds to a heat treatment at high temperatures as described above. During the pressing step a carbide rich structure in austenite is formed. The carbides are substantially spherical or rounded and of a size of 0.5-5 μm in a volume fraction of 20-50%. Therefore, a single heat treatment at low temperatures may be sufficient for an article produced through the powder method in order to obtain the desired properties of the material.
Further features of, and advantages with, the present invention will become apparent when studying the appended claims and the following description. Those skilled in the art realize that different features of the present invention may be combined to create embodiments other than those described in the following, without departing from the scope of the present invention, as defined by the appended claims.
The present invention will hereinafter be further explained by means of non-limiting examples with reference to the appended figures where;
The invention will be described using examples of embodiments. It should however be realized that the example embodiments are included in order to explain principles of the invention and not to limit the scope of the invention, defined by the appended claims.
In
The volume fraction as well as the size and distribution of the precipitated carbide particles determine the properties of the article. An alloy with a small carbide size, but a high volume fraction gives a much harder material with better yield stress. Smaller volume fraction and larger carbide sizes gives lower hardness with a lower yield stress. Thus, the smaller the carbide size, the better the toughness of the material.
In cases where the η-phase still exists at room temperature the decomposition can be controlled and completed by heat treatment. Therefore, after casting the alloy may be subjected to heat treatment to further improve the microstructure of the material and thereby the mechanical properties. The time and temperature for the heat treatment is selected depending on the desired properties for the article.
In
After the casting the metal base alloy may be heat treated. A single heat treatment or a double heat treatment may be chosen depending on the required end result.
As illustrated in
- An example of double heat treatment is performed as follows;
A cast sample with fully transferred featureless structure, i.e. the featureless phase decomposed into ferrite and carbides is heat treated at 1000° C. for 8 hours. A coarse carbide structure in a matrix of austenite is formed. The sample is quenched to room temperature, parts of the austenite is preserved. The austenite keeps a high carbon content. The carbon content in austenite is high at high temperature and decreases with decreasing temperature. The decrease of the carbon content in austenite occurs by precipitation of carbides. To get those carbides as small as possible the sample is rapidly cooled to room temperature and then heat treated at 550° C. where small carbides are precipitated in the austenite matrix. The austenite might transform to ferrite.
Generally, the casted metal base alloy is primarily suitable for small articles or products, whereas the powdered HIP method is primarily used when larger articles or products are produced. Small artides are for instance dental instruments like brackets and dental tools such as luxators, chisels and curettes. There are also several areas within the medical field where advanced material requirements are necessary. For example, in orthopaedic surgery several special tools are being used, such as drills, cutters, chisels, saws etc. In the workshop industry, small special tools for tough materials are produced, such as drills, bits, chisels. For larger articles, large cutters and workshop-tools can be produced.
Example embodiments may be combined as understood by a person skilled in the art. Therefore, it is to be understood that the foregoing is illustrative of various example embodiments and is not to be limited to the specific embodiments disclosed and that modifications to the disclosed embodiments, combinations of features of disclosed embodiments as well as other embodiments are intended to be included within the scope of the appended claims.
Claims
1. A metal base alloy product consisting of the formula Mebase Ta Sib Crc Mnd Ve Cf, wherein said metal base alloy product contains a substantially homogenous dispersion of separate precipitated carbide particles in an amount ranging from 10-65 percentages by volume and said precipitate carbide particles have an average diameter of 0.01-5 micrometer.
- Mebase is a metal base selected from the group consisting of Fe, Co and Ni, in an amount ranging from about 45-75 w %,
- Ta is an alloying material selected from the group consisting of Mo, Nb and Ta in an amount a ranging from about 5-10 w %,
- Sib is a further alloying member in an amount b ranging from about 4-10 w %,
- Crc is a further alloying member in an amount c ranging from about 8-30 w %,
- Mnd is a further alloying member in an amount d ranging from about 0-10 w %
- Ve is a further alloying member in an amount e ranging from about 0-10 w %, and
- Cf is a further alloying member in an amount f ranging from about 2-4 w %, wherein
2. Metal base alloy product according to claim 1 wherein said precipitated carbide particles are substantially spherical carbides having an average diameter of 0.1-5 micrometer.
3. Metal base alloy according to claim 1, wherein said precipitated carbide particles are a mixture of substantially spherical carbides having an average diameter of 0.5-5 micrometer and of nano-crystalline carbides having an average size of 0.01-0.5 micrometer.
4. Metal base alloy according to claim 1, wherein said precipitated carbide particles are surrounded by a matrix of ferrite and/or austenite.
5. Metal base alloy according to claim 1, wherein said alloy has a tensile strength of at least about 800 MPa.
6. A metal base alloy according to claim 1, wherein the Mebase is Fe present in an amount from about 45-75 w %.
7. A metal base alloy according to claim 1, wherein the Ta is Mo present in an amount from about 5-10 w %.
8. A method to produce a metal base alloy product consisting of the formula Mebase Ta Sib Crc Mnd Ve Cf, wherein
- Mebase is a metal base selected from the group consisting of Fe, Co and NI, in an amount ranging from about 45-75 w %,
- Ta is an alloying material selected from the group consisting of Mo, Nb and Ta in an amount a ranging from about 5-10 w %,
- Sib is a further alloying member in an amount b ranging from about 4-10 w %,
- Crc is a further alloying member in an amount c ranging from about 8-30 w %,
- Mnd is a further alloying member in an amount d ranging from about 0-10 w %
- Ve is a further alloying member in an amount e ranging from about 0-10 w %, and
- Cf is a further alloying member in an amount f ranging from about 2-4 w %, wherein the method comprises the steps of:
- melting said metal base together with chosen alloying components using different melting processes such as high frequency or arc melting,
- casting said alloy providing segregation free solidification conditions forming a featureless structure of said alloy,
- controlling the cooling conditions of said alloy after casting transferring the featureless structure to carbides and austenite or ferrite, and
- heat treating said alloy in at least a first heat treatment step to further control the dispersion of a substantially homogenous separate precipitated carbide particles in an amount ranging from 10-65 percentages by volume and said precipitate carbide particles have an average diameter of 0.01-5 micrometer.
9. Method according to claim 8, wherein the step of casting said alloy is performed in a mould, which mould is kept at a constant temperature from about 20 (room temperature) to 800 degrees Celsius to control the decomposition of the featureless structure.
10. Method according to claim 8, wherein said first heat treatment step is performed in an inert atmosphere or under vacuum at 800-1000 degrees Celsius for 0.1-50 hours wherein said precipitate carbide particles are controlled or further precipitated to form substantially rounded carbides having an average diameter of 0.5-5 micrometer in a matrix of austenite.
11. Method according to claim 8, wherein said first heat treatment step is performed in an inert atmosphere or under vacuum at 650-800 degrees Celsius for 1-30 hours wherein said precipitate carbide particles are controlled or further precipitated to be substantially rounded carbides having an average diameter of 0.1-5 micrometer in a matrix of ferrite.
12. Method according to claim 8, wherein the step of heat treating said alloy comprises a second heat treatment at 200-600 degrees Celsius for 1-30 hours wherein said precipitate carbide particles are formed as nano- crystalline carbides having an average diameter of 0.01-0.5 micrometer.
13. Method according to claims 9, wherein the method comprises a further step of:
- quenching said alloy rapidly at the end of a heat treatment.
14. A method to produce a metal base alloy product according to claim 1, wherein the method comprises the steps of:
- melting said metal base together with chosen alloying components using different melting processes such as high frequency or arc melting
- powder processing of said alloy to produce powder with a particle size of 0.1-40 pm size, and
- heating said powder to control the transformation of featureless structure to carbides and austenite/ferrite,
- keeping said powder at a constant temperature during said heating to ensure that the carbides become small and rounded
- pressing said obtained powder using high isostatic pressing (HIP) at a pressure of 60-150 MPa at a temperature of 800-1050° C.,
- cooling said product rapidly to approximately room temperature (20° C.), and -heat treating said alloy in an inert atmosphere or under vacuum wherein said precipitate carbide particles are formed as nano-crystalline carbides having an average diameter of 0.01-5 micrometer.
Type: Application
Filed: Jun 23, 2011
Publication Date: Aug 1, 2013
Applicant: SUPERIOR METALS SWEDEN AB (Hagersten)
Inventors: Sathees Ranganathan (Sundbyberg), Sohrab Solaimanzadeh-Azar (Sandviken), Hasse Fredriksson (Hagersten), Advenit Makaya (Villefontaine)
Application Number: 13/806,455
International Classification: C22C 1/04 (20060101); C21D 6/00 (20060101); C22C 19/05 (20060101); C22C 19/07 (20060101); C22C 38/22 (20060101); C22C 38/38 (20060101); C22C 38/36 (20060101); C22C 38/34 (20060101); C22C 38/24 (20060101); C22F 1/10 (20060101); C22C 37/06 (20060101);