WO2016014653A1

WO2016014653A1 - Chromium free hardfacing materials

Info

Publication number: WO2016014653A1
Application number: PCT/US2015/041514
Authority: WO
Inventors: Justin Lee Cheney; Tianho JIANG
Original assignee: Scoperta, Inc.
Priority date: 2014-07-24
Filing date: 2015-07-22
Publication date: 2016-01-28
Also published as: US20160024628A1

Abstract

Disclosed are embodiments of Fe-based alloys for use as a hardfacing material having high hardness while avoiding the use of chromium. The alloys can be twin arc or thermally sprayed as coatings on different types of equipment. In some embodiments, the alloys can be readable even after heating of the alloys.

Description

CHROMIUM FREE HARDFACING MATERIALS

INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS

[0001] This Application claims from the benefit of U.S. Provisional Application

No. 62/028,706, filed July 24, 2014, titled "CHROMIUM FREE HARDFACING ALLOYS," the entirety of which is incorporated herein by reference.

BACKGROUND

Field

[0002] The disclosure generally relates to hardfacing materials which can be deposited as hardfacing coatings without the production of Cr, such as hexavalent Cr dust.

Description of the Related Art

[0003] Thermal spray processing is a technique which can be utilized to deposit a hard wear resistant and/or corrosion resistant layer onto the surface of a component. Thermal spray inherently creates a significant amount of dust due to the fact that about 10-40% or more of the feedstock material does not stick to the component of interest and rebounds of the surface in the form a fine metallic dust. One particular class of thermal spray materials which is used to form wear resistant layers is amorphous and/or nanocrystalline materials. Fe-based amorphous and nanocrystalline materials used in thermal spray contain chromium as an alloying element. Chromium is effective in stabilizing the fine-grained structure, can increase wear resistance through the formation of chromium carbides and/or borides, and is useful in providing a degree of corrosion resistance. However, chromium is considered undesirable for use in thermal spray applications due to the potential to form hexavalent chromium dust. Hexavalent chromium dust is known to cause cancer.

[0004] There are several Fe-based chromium free thermal spray materials which have been developed and are used by industry today. Currently available Fe-based Cr-free materials have hardness levels below 500 Vickers, as shown in Table 1, which can make them inapplicable for many different industrial uses. Table 1 : Conventional Fe-based Cr-free materials and reported hardness values

[0005] There have also been efforts to specifically design Cr-free hardfacing materials for welding processes, such as that shown in 2012/0097658. However, the alloys disclosed in the reference require the formation of borides and carbides. Further, the reference requires the use of boron.

SUMMARY

[0006] Disclosed herein are embodiments of alloy compositions used to produce thermal spray coatings, methods of identifying these compositions, the coatings themselves, and methods of making and using the coatings. Thermal spray coatings according to certain embodiments may be produced having a hardness above 500 Vickers without the use of chromium as an alloying element. Some embodiments are directed to a work piece having a coating on at least a surface, the work piece comprising a metal surface onto which a coating is applied, the coating comprising an Fe-based alloy without any chromium, wherein the alloy comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.

[0007] In some embodiments, the coating can be applied via the twin wire arc spray process.

[0008] In some embodiments, the coating can comprise, in weight percent, B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W: about 0-6, Zr: about 0-10, wherein B + C + Si is about 4-15, and wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.

[0009] In some embodiments, the coating can comprise Fe and, in weight percent, C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to 10. [0010] In some embodiments, the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an Elcometer™ thickness gauge or similar device. In some embodiments, the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an Elcometer™ thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less.

[0011] In some embodiments, the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less.

[0012] Also disclosed herein are embodiments of an article of manufacture comprising a coating which is Fe-based, without chromium, and possesses a melting temperature of 1500K or below and a large atom concentration of at least 5 atom %, large atoms being of the group Mn, Mo, Nb, Ta, Ti, V, W, and Zr.

[0013] In some embodiments, the coating can comprise a Vickers hardness of at least 400 and an adhesion strength of at least 5,000 psi. In some embodiments, the coating can be applied via the twin wire arc spray process.

[0014] In some embodiments, the coating can comprise, in weight percent, B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W: about 0-6, Zr: about 0-10, wherein B + C + Si is about 4-15, and wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.

[0015] In some embodiments, the coating can comprise Fe and, in weight percent, C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to 10.

[0016] In some embodiments, the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an Elcometer™ thickness gauge or similar device. In some embodiments, the coating can be non-magnetic and therefore the coating thickness can be accurately measured with an Elcometer™ thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less. [0017] In some embodiments, the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less.

[0018] Disclosed herein are embodiments of a work piece having at least one surface, the work piece comprising a coating applied to the at least one surface, the coating comprising an Fe-based alloy having substantially no chromium, having substantially no carbides, and having substantially no borides, wherein the alloy comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.

[0019] In some embodiments, the coating can comprise Fe and, in weight percent, B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W: about 0-6, Zr: about 0-10, wherein B + C + Si is about 4-15, and wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38. In some embodiments, the coating can comprise Fe and in weight percent, C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to 10. In some embodiments, the coating can comprise one or more of the following compositions in weight percent: Fe, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2; or Fe, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.

[0020] In some embodiments, the coating can be non-magnetic and the coating thickness can be accurately measured with an Elcometer™ thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less.

[0021] In some embodiments, the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less.

[0022] In some embodiments, the coating can be applied via a thermal spray process. In some embodiments, the coating can be applied via a twin wire arc spray process. In some embodiments, the work piece can be a yankee dryer. In some embodiments, the work piece can be a roller used in a paper making machine.

[0023] Also disclosed herein are embodiments of an article of manufacture comprising an Fe-based coating having substantially no chromium;, wherein the coating possesses a melting temperature of 1500K or below, wherein the coating possesses a large atom concentration of at least 5 atom %, large atoms being of the group consisting of Mn, Mo, Nb, Ta, Ti, V, W, and Zr, and wherein the coating is a primarily single phase finegrained structure of either martensite, ferrite, or austenite.

[0024] In some embodiments, the coating can comprise, in weight percent B: about 0-4, C: about 0-0.25, Si: about 0-15, Mn: about 0 to 25, Mo: about 0-29, Nb: about 0-2, Ta: about 0-4, Ti: about 0-4, V: about 0-10, W: about 0-6, Zr: about 0-10, wherein B + C + Si is about 4-15, and wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.

[0025] In some embodiments, the coating can comprise Fe and in weight percent C: about 0 to 0.25, Mn: about 5 to 19, Mo: about 7 to 23, Ni: about 0 to 4, and Si: about 5 to 10.

[0026] In some embodiments, the coating can comprise one or more of the following compositions in weight percent: Fe, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2; or Fe, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.

[0027] In some embodiments, the coating can be non-magnetic and the coating thickness can be accurately measured with an Elcometer™ thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less. In some embodiments, the coating can comprise a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.

[0028] In some embodiments, the coating can be applied via the twin wire arc spray process. In some embodiments, the coating can be applied via a thermal spray process.

[0029] In some embodiments, the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less.

[0030] In some embodiments, the coating can be applied onto a roller used in a paper making machine. In some embodiments, the coating can be applied onto a Yankee Dryer. In some embodiments, the coating can be applied onto a boiler tube.

[0031] Also disclosed herein are embodiments of a work piece having at least one surface, the work piece comprising a coating applied to the at least one surface, the coating comprising an Fe-based alloy having less than 1 wt. % chromium, less than 5 vol. % carbides, and less than 5 vol. % borides, wherein the alloy comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi. In some embodiments, the alloy can have less than 1 vol. % carbides and less than 1 vol. % borides.

DETAILED DESCRIPTION

[0032] Disclosed herein are embodiments of chromium free, iron based alloys, and methods of manufacturing the alloys. In some embodiments, the alloys can have high hardness and can be used as, for example, coatings. In some embodiments, computational metallurgy can be used to explore alloy compositional ranges where an alloy is likely to form an amorphous or nanocrystalline coating without the use of chromium as an alloying element. Prior to this disclosure, Fe-based thermal spray coatings with a hardness above 500 Vickers have used chromium as an alloying element. This disclosure demonstrates embodiments of alloy compositions which can produce thermal spray coatings with hardness values above 500 Vickers, in addition to describing the design techniques successfully used to identify them.

[0033] Specifically, disclosed herein are embodiments of alloys which can achieve high hardness levels through mechanisms other than the use of chromium or the formation of carbides and/or borides. Rather, in some embodiments, a very fine-grain structure can be achieved due to melting temperature and large atom criteria disclosed herein.

Metal Alloy Composition

[0034] In some embodiments, the alloy can be described by a composition in weight percent comprising the following elemental ranges at least partially based on the ranges disclosed in Table 2 and Table 3 :

• Fe: BAL

• B: 0-4 (or about 0 to about 4), C: 0-0.25 (or about 0 to about 0.25), and Si: 0-15 (or about 0 to about 15), where B+C+Si is 4-15 (or about 4 to about 15)

• Mn: 0-25 (or about 0 to about 25), Mo: 0-29 (or about 0 to about 29), Nb: 0-2 (or about 0 to about 2), Ta: 0-4 (or about 0 to about 4), Ti: 0-4 (or about 0 to about 4), V: 0-10 (or about 0 to about 10), W: 0-6 (or about 0 to about 6), Zr: 0-10 (about 0 to about 10), where (Mo+Mn+Nb+Ta+Ti+V+W+Zr) is 5-38 (or about 5 to about 38) 0 Cr (or about 0 Cr)

[0035] Generally, embodiments of an alloy can be designed using any of the large elements as long as the other elemental ratios are controlled properly. The following atomic sizes, in picometers, were used for the large elements, large atoms defined as atoms which are larger than iron atoms: Mn: 161, Mo: 190, Nb, 198, Ta: 200, Ti: 176, V: 171, W: 193, Zr: 206. Fe has an atomic size of 156pm. A large atom can be an atom that is larger than Fe. These large atoms can be advantageous as they can increase the viscosity of an alloy in liquid form and thus slow down the crystallization rate of the alloy. As the crystallization rate decreases, the probability of forming an amorphous, nanocrystalline, or fine-grained structure can increase.

[0036] In some embodiments, the coating can be amorphous. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 100 nm or less. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 50 nm or less. In some embodiments, the coating can be nanocrystalline, as defined by having a grain size of 20 nm or less.

[0037] In some embodiments, the alloy can be described by a composition in weight percent comprising the following elemental ranges at least partially based on a range composed form the alloys selected for manufacture into experimental ingots:

• Fe: BAL, C: 0-0.25 (or about 0 to about 0.25), Mn: 5-19 (or about 5 to about 19), Mo:

7-23 (or about 7 to about 23), Ni: 0-4 (or about 0 to about 4), Si: 5-10 (or about 5 to about 10)

[0038] In some embodiments, the alloy can be described by the specific compositions, which have been produced and experimentally demonstrated amorphous formation potential, in weight percent, comprising the following elements.

1. Fe: BAL, Mn: 5 (or about 5), Mo: 23 (or about 23), Si: 10 (or about 10)

2. Fe: BAL, Mn: 5 (or about 5), Mo: 19 (or about 19), Si: 10 (or about 10)

3. Fe: BAL, Mn: 5 (or about 5), Mo: 11 (or about 11), Si: 10 (or about 10)

4. Fe: BAL, Mn: 5 (or about 5), Mo: 13 (or about 13), Si: 10 (or about 10)

5. Fe: BAL, Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 10 (or about 10) 6. Fe: BAL, Al: 2 (or about 2), Mn: 5 (or about 5), Mo: 5 (or about 5), Si: 13 (or about 13)

7. Fe: BAL, Al: 2 (or about 2), Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 15 (or about 15)

8. Fe: BAL, C: 0.25 (or about 0.25), Mn: 19 (or about 19), Mo: 7 (or about 7), Si: (5 or about 5)

9. Fe: BAL, C: 0.25 (or about 0.25), Mn: 5 (or about 5), Mo: 7 (or about 7), Ni: (4 or about 4), Si: 5 (or about 5)

10. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Si: 7 (or about 7)

11. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Ni: 2 (or about 2), Si: 5 (or about 5)

12. Fe: BAL, Mn: 19 (or about 19), Mo: 15 (or about 15), Si: 6 (or about 6)

13. Fe: BAL, Mn: 19 (or about 19), Mo: 7 (or about 7), Ni: 2 (or about 2), Si: 5 (or about 5)

[0039] In some embodiments, aluminum can be further added to the above alloy ranges and chemistries to improve coating adhesion in the range of up to 5 (or about 5) wt.%. Some exemplary examples of aluminum additions, based upon the #4 and #5 base chemistries, are:

14. Fe: BAL, Mn: 5 (or about 5), Mo: 13 (or about 13), Si: 10 (or about 10), Al: 2 (or about 2)

15. Fe: BAL, Mn: 5 (or about 5), Mo: 7 (or about 7), Si: 10 (or about 10), Al: 2 (or about 2)

[0040] In some embodiments, the alloy may contain boron, such as between 0-4 wt. % (including 1, 2, and 3 wt. %) as indicated above. In some embodiments, the alloy may not contain any boron. In some embodiments, boron may act as an impurity and does not exceed 1 wt. %.

[0041] The Fe content identified in the composition above may be the balance of the composition as indicated above, or alternatively, the balance of the composition may comprise Fe and other elements. In some embodiments, the balance may consist essentially of Fe and may include incidental impurities. In some embodiments, the above alloys may not contain any chromium. In some embodiments, chromium may act as an impurity and does not exceed 1 wt. %. Thermodynamic and Kinetic Criteria

[0042] In some embodiments, the alloy can be described by thermodynamic and kinetic criteria. In some embodiments, the thermodynamic criteria can relate to the stability of the liquid phase, e.g., the melting temperature of the alloy. The melting temperature can be calculated via thermodynamic models and is defined as the highest temperature at which liquid is less than 100% of the mole fraction in the material. The kinetic criterion can be related to the viscosity of the liquid and the concentration in atom percent of large atoms. Large atoms are defined as atoms which are larger than iron atoms. Either or both criteria can be used to predict the tendency towards amorphous formation in thermal spray materials. In some embodiments, the alloys can have a microstructure of ferritic iron. In some embodiments, a primarily single phase fine-grained structure of either martensite, ferrite, or austenite can be formed. In some embodiments, <5% (or < about 5%) borides and carbides are formed. In some embodiments, <\% (or < about 1%) borides and carbides are formed. In some embodiments, <A% (or < about .1%) borides and carbides are formed. In some embodiments, no borides or carbides are formed.

[0043] In some embodiments, the melting temperature can be below 1500 K (or below about 1500K). In some embodiments, the melting temperature can be below 1450K (or below about 1450K). In some embodiments, the melting temperature can be below 1400K (or below about 1400K). In general, amorphous formation is encouraged with lower melting temperatures because, typically, as grain size decreases, hardness increases (known as the Hall-Petch relationship). Amorphous alloys effectively have zero grain size, and thus can be the hardest form of the alloy. As amorphous formation potential increases, the alloy, even if it doesn't always become amorphous in every process, will tend towards a smaller grain size. Thus, amorphous forming alloys of the disclosure, even if they form fine-grained or nanocrystalline structures and not actually an amorphous structure, will tend to be harder. For example, in some embodiments, while there is the potential for an amorphous structure, the alloy may end up being crystalline, specifically nanocrystalline, upon application, such as through thermal spray, while still achieving the high hardness levels disclosed herein.

[0044] In some embodiments, the large atom atomic fraction can be above 5 atom % (or above about 5 atom %). In some embodiments, the large atom atomic fraction can be above 7.5 atom % (or above about 7.5 atom %). In some embodiments, the large atom atomic fraction can be above 10 atom % (or above about 10 atom %). In some embodiments, the higher large atom atomic fraction can encourage amorphous formation and increase amorphous formation potential.

[0045] Table 2 lists the alloy compositions, all Fe-based, in weight percent which can meet the thermodynamic criteria detailed in this disclosure. In some embodiments, the Fe-based alloys can have a composition that is predominantly iron, e.g., at least 50 wt. % iron.

[0046] Combining the alloys in Table 2 and Table 3 yields 1,141 compositions which meet the criteria. These alloys were compiled through computational searching tools which evaluated 16,362 alloys according to the disclosed criteria. Thus, the alloys disclosed cover only 6.9% of the total explored space explicitly investigated to design an alloy with the disclosed performance parameters.

Table 2: List of alloy compositions with thermodynamic and kinetic parameters which meet disclosed criteria. Large atom % is the total atom % of elements larger than iron and melt T is the melting temperature of the alloy.

No B Mn Mo Nb Si Ta Ti V w Zr Large Atom % Melt T

Ml 0 0 10 1 10 0 0 0 0 0 6.1% 1500

M2 0 0 15 1 9 0 0 0 0 0 9.1% 1500

M3 0 0 15 1 10 0 0 0 0 0 9.0% 1500

M4 0 0 20 0 7 0 0 0 0 0 11.8% 1500

M5 0 0 20 0 8 0 0 0 0 0 11.7% 1500

M6 0 0 20 0 9 0 0 0 0 0 11.6% 1450

M7 0 0 20 0 10 0 0 0 0 0 11.5% 1450

M8 0 0 20 1 7 0 0 0 0 0 12.5% 1500

M9 0 0 20 1 8 0 0 0 0 0 12.3% 1500

M10 0 0 20 1 9 0 0 0 0 0 12.2% 1500

Mil 0 0 20 1 10 0 0 0 0 0 12.1% 1500

M12 0 1 10 0 10 0 0 0 0 0 6.5% 1500

M13 0 1 10 1 10 0 0 0 0 0 7.1% 1500

M14 0 1 15 1 8 0 0 0 0 0 10.2% 1500

M15 0 1 15 1 9 0 0 0 0 0 10.1% 1500

M16 0 1 15 1 10 0 0 0 0 0 10.0% 1450

M17 0 1 20 0 7 0 0 0 0 0 12.8% 1500 M18 0 1 20 0 8 0 0 0 0 0 12.7% 1500

M19 0 1 20 0 9 0 0 0 0 0 12.6% 1450

M20 0 1 20 0 10 0 0 0 0 0 12.5% 1450

M21 0 1 20 1 7 0 0 0 0 0 13.5% 1500

M22 0 1 20 1 8 0 0 0 0 0 13.4% 1450

M23 0 1 20 1 9 0 0 0 0 0 13.2% 1500

M24 0 1 20 1 10 0 0 0 0 0 13.1% 1500

M25 0 2 10 0 10 0 0 0 0 0 7.4% 1500

M26 0 2 10 1 9 0 0 0 0 0 8.1% 1500

M27 0 2 10 1 10 0 0 0 0 0 8.0% 1500

M28 0 2 15 1 8 0 0 0 0 0 11.2% 1500

M29 0 2 15 1 9 0 0 0 0 0 11.1% 1500

M30 0 2 15 1 10 0 0 0 0 0 11.0% 1450

M31 0 2 20 0 7 0 0 0 0 0 13.9% 1500

M32 0 2 20 0 8 0 0 0 0 0 13.7% 1450

M33 0 2 20 0 9 0 0 0 0 0 13.6% 1450

M34 0 2 20 0 10 0 0 0 0 0 13.5% 1400

M35 0 2 20 1 6 0 0 0 0 0 14.7% 1500

M36 0 2 20 1 7 0 0 0 0 0 14.5% 1500

M37 0 2 20 1 8 0 0 0 0 0 14.4% 1450

M38 0 2 20 1 9 0 0 0 0 0 14.2% 1500

M39 0 2 20 1 10 0 0 0 0 0 14.1% 1500

M40 0 3 10 0 9 0 0 0 0 0 8.5% 1500

M41 0 3 10 0 10 0 0 0 0 0 8.4% 1500

M42 0 3 10 1 9 0 0 0 0 0 9.1% 1500

M43 0 3 10 1 10 0 0 0 0 0 9.0% 1500

M44 0 3 15 1 7 0 0 0 0 0 12.3% 1500

M45 0 3 15 1 8 0 0 0 0 0 12.2% 1500

M46 0 3 15 1 9 0 0 0 0 0 12.1% 1450

M47 0 3 15 1 10 0 0 0 0 0 12.0% 1500

M48 0 3 20 0 6 0 0 0 0 0 15.0% 1500

M49 0 3 20 0 8 0 0 0 0 0 14.7% 1450

M50 0 3 20 1 6 0 0 0 0 0 15.7% 1500

M51 0 3 20 1 8 0 0 0 0 0 15.4% 1450

M52 0 3 20 1 10 0 0 0 0 0 15.1% 1500

M53 0 4 5 1 10 0 0 0 0 0 7.1% 1500

M54 0 4 10 0 9 0 0 0 0 0 9.4% 1500

M55 0 4 10 0 10 0 0 0 0 0 9.3% 1500

M56 0 4 10 1 8 0 0 0 0 0 10.1% 1500

M57 0 4 10 1 9 0 0 0 0 0 10.0% 1500

M58 0 4 10 1 10 0 0 0 0 0 10.0% 1500

M59 0 4 15 1 7 0 0 0 0 0 13.4% 1500

M60 0 4 15 1 8 0 0 0 0 0 13.2% 1500 M61 0 4 15 1 9 0 0 0 0 0 13.1% 1450

M62 0 4 15 1 10 0 0 0 0 0 13.0% 1500

M63 0 4 15 2 6 0 0 0 0 0 14.1% 1500

M64 0 4 20 0 6 0 0 0 0 0 16.1% 1500

M65 0 4 20 0 7 0 0 0 0 0 15.9% 1450

M66 0 4 20 0 8 0 0 0 0 0 15.8% 1450

M67 0 4 20 0 9 0 0 0 0 0 15.6% 1400

M68 0 4 20 0 10 0 0 0 0 0 15.5% 1400

M69 0 4 20 1 5 0 0 0 0 0 16.9% 1500

M70 0 4 20 1 6 0 0 0 0 0 16.8% 1500

M71 0 4 20 1 7 0 0 0 0 0 16.6% 1450

M72 0 4 20 1 8 0 0 0 0 0 16.4% 1450

M73 0 4 20 1 9 0 0 0 0 0 16.3% 1500

M74 0 4 20 1 10 0 0 0 0 0 16.1% 1500

M75 0 4 20 2 5 0 0 0 0 0 17.6% 1500

M76 0 5 5 1 10 0 0 0 0 0 8.0% 1500

M77 0 5 10 0 8 0 0 0 0 0 10.5% 1500

M78 0 5 10 0 9 0 0 0 0 0 10.4% 1500

M79 0 5 10 0 10 0 0 0 0 0 10.3% 1500

M80 0 5 10 1 8 0 0 0 0 0 11.1% 1500

M81 0 5 10 1 9 0 0 0 0 0 11.0% 1500

M82 0 5 10 1 10 0 0 0 0 0 10.9% 1450

M83 0 5 15 1 6 0 0 0 0 0 14.5% 1500

M84 0 5 15 1 7 0 0 0 0 0 14.4% 1500

M85 0 5 15 1 8 0 0 0 0 0 14.2% 1450

M86 0 5 15 1 9 0 0 0 0 0 14.1% 1450

M87 0 5 15 1 10 0 0 0 0 0 14.0% 1500

M88 0 5 15 2 6 0 0 0 0 0 15.2% 1500

M89 0 5 20 0 5 0 0 0 0 0 17.3% 1500

M90 0 5 20 0 6 0 0 0 0 0 17.1% 1500

M91 0 5 20 0 7 0 0 0 0 0 17.0% 1450

M92 0 5 20 0 8 0 0 0 0 0 16.8% 1450

M93 0 5 20 0 9 0 0 0 0 0 16.6% 1400

M94 0 5 20 0 10 0 0 0 0 0 16.5% 1400

M95 0 5 20 1 5 0 0 0 0 0 18.0% 1500

M96 0 5 20 1 6 0 0 0 0 0 17.8% 1500

M97 0 5 20 1 7 0 0 0 0 0 17.6% 1450

M98 0 5 20 1 8 0 0 0 0 0 17.5% 1500

M99 0 5 20 1 9 0 0 0 0 0 17.3% 1500

M100 0 5 20 1 10 0 0 0 0 0 17.1% 1500

M101 0 5 20 2 5 0 0 0 0 0 18.7% 1500

M102 4 0 0 0 0 0 0 2 0 6 5.1% 1350

M103 4 0 0 0 0 0 0 2 2 6 5.7% 1400 M104 4 0 0 0 0 0 0 2 4 4 5.2% 1500

M105 4 0 0 0 0 0 0 2 4 6 6.3% 1450

M106 4 0 0 0 0 0 0 4 0 4 5.9% 1350

M107 4 0 0 0 0 0 0 4 0 6 7.0% 1350

M108 4 0 0 0 0 0 0 4 2 2 5.4% 1400

M109 4 0 0 0 0 0 0 4 2 4 6.5% 1400

MHO 4 0 0 0 0 0 0 4 2 6 7.6% 1350

Mill 4 0 0 0 0 0 0 4 4 2 6.0% 1450

M112 4 0 0 0 0 0 0 4 4 4 7.1% 1450

M113 4 0 0 0 0 0 0 4 4 6 8.3% 1450

M114 4 0 0 0 0 0 0 6 0 0 5.6% 1350

M115 4 0 0 0 0 0 0 6 0 2 6.7% 1350

M116 4 0 0 0 0 0 0 6 0 4 7.8% 1350

M117 4 0 0 0 0 0 0 6 0 6 8.9% 1400

M118 4 0 0 0 0 0 0 6 2 0 6.2% 1400

M119 4 0 0 0 0 0 0 6 2 2 7.3% 1400

M120 4 0 0 0 0 0 0 6 2 4 8.4% 1350

M121 4 0 0 0 0 0 0 6 2 6 9.6% 1400

M122 4 0 0 0 0 0 0 6 4 0 6.8% 1450

M123 4 0 0 0 0 0 0 6 4 2 7.9% 1450

M124 4 0 0 0 0 0 0 6 4 4 9.1% 1450

M125 4 0 0 0 0 0 0 6 4 6 10.2% 1450

M126 4 0 0 0 0 0 0 6 6 0 7.4% 1500

M127 4 0 0 0 0 0 0 6 6 2 8.6% 1500

M128 4 0 0 0 0 0 0 6 6 4 9.7% 1500

M129 4 0 0 0 0 0 0 6 6 6 10.9% 1500

M130 4 0 0 0 0 0 0 6 6 8 12.1% 1500

M131 4 0 0 0 0 0 0 6 6 10 13.3% 1500

M132 4 0 0 0 0 0 0 8 6 6 12.9% 1500

M133 4 0 0 0 0 0 0 8 6 8 14.1% 1500

M134 4 0 0 0 0 0 0 8 6 10 15.3% 1500

M135 4 0 0 0 0 0 0 10 6 6 14.8% 1500

M136 4 0 0 0 0 0 0 10 6 8 16.0% 1500

M137 4 0 0 0 0 0 0 10 6 10 17.3% 1500

M138 0 3 20 0 10 0 0 0 0 0 14.5% 1400

M139 0 3 20 0 10 0 0 0 0 2 15.8% 1350

M140 0 3 20 0 10 0 0 0 0 4 17.1% 1350

M141 0 3 20 0 10 0 0 0 2 0 15.3% 1400

M142 0 3 20 0 10 0 0 0 2 2 16.6% 1400

M143 0 3 20 0 10 0 0 0 2 4 18.0% 1400

M144 0 3 20 0 10 0 0 0 4 0 16.1% 1450

M145 0 3 20 0 10 0 0 0 4 2 17.5% 1450

M146 0 3 20 0 10 0 0 0 4 4 18.9% 1450 M147 0 3 20 0 10 0 0 2 0 0 16.6% 1400

M148 0 3 20 0 10 0 0 2 0 2 17.9% 1350

M149 0 3 20 0 10 0 0 2 0 4 19.3% 1350

M150 0 3 20 0 10 0 0 2 2 0 17.4% 1400

M151 0 3 20 0 10 0 0 2 2 2 18.8% 1400

M152 0 3 20 0 10 0 0 2 2 4 20.2% 1400

M153 0 3 20 0 10 0 0 2 4 0 18.3% 1450

M154 0 3 20 0 10 0 0 2 4 2 19.7% 1450

M155 0 3 20 0 10 0 0 2 4 4 21.1% 1450

M156 0 3 20 0 10 0 0 4 0 0 18.7% 1400

M157 0 3 20 0 10 0 0 4 0 2 20.1% 1350

M158 0 3 20 0 10 0 0 4 0 4 21.4% 1350

M159 0 3 20 0 10 0 0 4 2 0 19.6% 1400

M160 0 3 20 0 10 0 0 4 2 2 20.9% 1400

M161 0 3 20 0 10 0 0 4 2 4 22.4% 1400

M162 0 3 20 0 10 0 0 4 4 0 20.5% 1450

M163 0 3 20 0 10 0 0 4 4 2 21.9% 1450

M164 0 3 20 0 10 0 0 4 4 4 23.3% 1450

M165 0 3 20 0 10 0 2 0 0 0 16.7% 1400

M166 0 3 20 0 10 0 2 0 0 2 18.0% 1350

M167 0 3 20 0 10 0 2 0 0 4 19.4% 1350

M168 0 3 20 0 10 0 2 0 2 0 17.5% 1450

M169 0 3 20 0 10 0 2 0 2 2 18.9% 1450

M170 0 3 20 0 10 0 2 0 2 4 20.3% 1450

M171 0 3 20 0 10 0 2 0 4 0 18.4% 1500

M172 0 3 20 0 10 0 2 0 4 2 19.8% 1500

M173 0 3 20 0 10 0 2 0 4 4 21.2% 1500

M174 0 3 20 0 10 0 2 2 0 0 18.8% 1400

M175 0 3 20 0 10 0 2 2 0 2 20.2% 1350

M176 0 3 20 0 10 0 2 2 0 4 21.5% 1350

M177 0 3 20 0 10 0 2 2 2 0 19.7% 1450

M178 0 3 20 0 10 0 2 2 2 2 21.1% 1450

M179 0 3 20 0 10 0 2 2 2 4 22.5% 1450

M180 0 3 20 0 10 0 2 2 4 0 20.6% 1500

M181 0 3 20 0 10 0 2 2 4 2 22.0% 1500

M182 0 3 20 0 10 0 2 2 4 4 23.4% 1500

M183 0 3 20 0 10 0 2 4 0 0 20.9% 1400

M184 0 3 20 0 10 0 2 4 0 2 22.3% 1350

M185 0 3 20 0 10 0 2 4 0 4 23.7% 1350

M186 0 3 20 0 10 0 2 4 2 0 21.8% 1450

M187 0 3 20 0 10 0 2 4 2 2 23.2% 1450

M188 0 3 20 0 10 0 2 4 2 4 24.6% 1400

M189 0 3 20 0 10 0 2 4 4 0 22.7% 1450 M190 0 3 20 0 10 0 2 4 4 2 24.2% 1450

M191 0 3 20 0 10 0 2 4 4 4 25.6% 1450

M192 0 3 20 0 10 0 4 0 0 0 18.9% 1400

M193 0 3 20 0 10 0 4 0 0 2 20.3% 1400

M194 0 3 20 0 10 0 4 0 0 4 21.7% 1400

M195 0 3 20 0 10 0 4 0 2 0 19.8% 1450

M196 0 3 20 0 10 0 4 0 2 2 21.2% 1450

M197 0 3 20 0 10 0 4 0 2 4 22.6% 1450

M198 0 3 20 0 10 0 4 0 4 0 20.7% 1500

M199 0 3 20 0 10 0 4 0 4 2 22.1% 1500

M200 0 3 20 0 10 0 4 0 4 4 23.5% 1500

M201 0 3 20 0 10 0 4 2 0 0 21.0% 1400

M202 0 3 20 0 10 0 4 2 0 2 22.4% 1400

M203 0 3 20 0 10 0 4 2 0 4 23.8% 1400

M204 0 3 20 0 10 0 4 2 2 0 21.9% 1450

M205 0 3 20 0 10 0 4 2 2 2 23.3% 1450

M206 0 3 20 0 10 0 4 2 2 4 24.7% 1450

M207 0 3 20 0 10 0 4 2 4 0 22.8% 1500

M208 0 3 20 0 10 0 4 2 4 2 24.3% 1500

M209 0 3 20 0 10 0 4 2 4 4 25.7% 1500

M210 0 3 20 0 10 0 4 4 0 0 23.1% 1400

M211 0 3 20 0 10 0 4 4 0 2 24.5% 1400

M212 0 3 20 0 10 0 4 4 0 4 25.9% 1400

M213 0 3 20 0 10 0 4 4 2 0 24.1% 1450

M214 0 3 20 0 10 0 4 4 2 2 25.5% 1450

M215 0 3 20 0 10 0 4 4 2 4 26.9% 1450

M216 0 3 20 0 10 0 4 4 4 0 25.0% 1500

M217 0 3 20 0 10 0 4 4 4 2 26.4% 1500

M218 0 3 20 0 10 0 4 4 4 4 27.9% 1500

M219 0 3 20 0 10 2 0 0 0 0 15.3% 1400

M220 0 3 20 0 10 2 0 0 0 2 16.6% 1350

M221 0 3 20 0 10 2 0 0 0 4 18.0% 1350

M222 0 3 20 0 10 2 0 0 2 0 16.1% 1400

M223 0 3 20 0 10 2 0 0 2 2 17.5% 1400

M224 0 3 20 0 10 2 0 0 2 4 18.9% 1400

M225 0 3 20 0 10 2 0 0 4 0 17.0% 1450

M226 0 3 20 0 10 2 0 0 4 2 18.4% 1500

M227 0 3 20 0 10 2 0 0 4 4 19.8% 1500

M228 0 3 20 0 10 2 0 2 0 0 17.4% 1400

M229 0 3 20 0 10 2 0 2 0 2 18.8% 1350

M230 0 3 20 0 10 2 0 2 0 4 20.2% 1350

M231 0 3 20 0 10 2 0 2 2 0 18.3% 1400

M232 0 3 20 0 10 2 0 2 2 2 19.7% 1400 M233 0 3 20 0 10 2 0 2 2 4 21.1% 1400

M234 0 3 20 0 10 2 0 2 4 0 19.2% 1450

M235 0 3 20 0 10 2 0 2 4 2 20.6% 1450

M236 0 3 20 0 10 2 0 2 4 4 22.0% 1450

M237 0 3 20 0 10 2 0 4 0 0 19.6% 1400

M238 0 3 20 0 10 2 0 4 0 2 21.0% 1350

M239 0 3 20 0 10 2 0 4 0 4 22.4% 1350

M240 0 3 20 0 10 2 0 4 2 0 20.5% 1400

M241 0 3 20 0 10 2 0 4 2 2 21.9% 1400

M242 0 3 20 0 10 2 0 4 2 4 23.3% 1400

M243 0 3 20 0 10 2 0 4 4 0 21.4% 1450

M244 0 3 20 0 10 2 0 4 4 2 22.8% 1450

M245 0 3 20 0 10 2 0 4 4 4 24.3% 1450

M246 0 3 20 0 10 2 2 0 0 0 17.5% 1350

M247 0 3 20 0 10 2 2 0 0 2 18.9% 1350

M248 0 3 20 0 10 2 2 0 0 4 20.3% 1350

M249 0 3 20 0 10 2 2 0 2 0 18.4% 1450

M250 0 3 20 0 10 2 2 0 2 2 19.8% 1450

M251 0 3 20 0 10 2 2 0 2 4 21.2% 1450

M252 0 3 20 0 10 2 2 0 4 0 19.3% 1500

M253 0 3 20 0 10 2 2 0 4 2 20.7% 1500

M254 0 3 20 0 10 2 2 0 4 4 22.1% 1500

M255 0 3 20 0 10 2 2 2 0 0 19.7% 1350

M256 0 3 20 0 10 2 2 2 0 2 21.1% 1350

M257 0 3 20 0 10 2 2 2 0 4 22.5% 1350

M258 0 3 20 0 10 2 2 2 2 0 20.6% 1450

M259 0 3 20 0 10 2 2 2 2 2 22.0% 1450

M260 0 3 20 0 10 2 2 2 2 4 23.4% 1450

M261 0 3 20 0 10 2 2 2 4 0 21.5% 1500

M262 0 3 20 0 10 2 2 2 4 2 22.9% 1500

M263 0 3 20 0 10 2 2 2 4 4 24.4% 1500

M264 0 3 20 0 10 2 2 4 0 0 21.8% 1350

M265 0 3 20 0 10 2 2 4 0 2 23.2% 1350

M266 0 3 20 0 10 2 2 4 0 4 24.6% 1350

M267 0 3 20 0 10 2 2 4 2 0 22.7% 1450

M268 0 3 20 0 10 2 2 4 2 2 24.2% 1450

M269 0 3 20 0 10 2 2 4 2 4 25.6% 1450

M270 0 3 20 0 10 2 2 4 4 0 23.7% 1500

M271 0 3 20 0 10 2 2 4 4 2 25.1% 1500

M272 0 3 20 0 10 2 2 4 4 4 26.6% 1450

M273 0 3 20 0 10 2 4 0 0 0 19.8% 1400

M274 0 3 20 0 10 2 4 0 0 2 21.2% 1400

M275 0 3 20 0 10 2 4 0 0 4 22.6% 1400 M276 0 3 20 0 10 2 4 0 2 0 20.7% 1450

M277 0 3 20 0 10 2 4 0 2 2 22.1% 1450

M278 0 3 20 0 10 2 4 0 2 4 23.5% 1450

M279 0 3 20 0 10 2 4 0 4 0 21.6% 1500

M280 0 3 20 0 10 2 4 0 4 2 23.0% 1500

M281 0 3 20 0 10 2 4 0 4 4 24.5% 1500

M282 0 3 20 0 10 2 4 2 0 0 21.9% 1400

M283 0 3 20 0 10 2 4 2 0 2 23.3% 1400

M284 0 3 20 0 10 2 4 2 0 4 24.7% 1400

M285 0 3 20 0 10 2 4 2 2 0 22.9% 1450

M286 0 3 20 0 10 2 4 2 2 2 24.3% 1450

M287 0 3 20 0 10 2 4 2 2 4 25.7% 1450

M288 0 3 20 0 10 2 4 2 4 0 23.8% 1500

M289 0 3 20 0 10 2 4 2 4 2 25.2% 1500

M290 0 3 20 0 10 2 4 2 4 4 26.7% 1500

M291 0 3 20 0 10 2 4 4 0 0 24.1% 1400

M292 0 3 20 0 10 2 4 4 0 2 25.5% 1400

M293 0 3 20 0 10 2 4 4 0 4 26.9% 1400

M294 0 3 20 0 10 2 4 4 2 0 25.0% 1450

M295 0 3 20 0 10 2 4 4 2 2 26.4% 1450

M296 0 3 20 0 10 2 4 4 2 4 27.9% 1450

M297 0 3 20 0 10 2 4 4 4 0 26.0% 1500

M298 0 3 20 0 10 2 4 4 4 2 27.4% 1500

M299 0 3 20 0 10 2 4 4 4 4 28.9% 1500

M300 0 3 20 0 10 4 0 0 0 0 16.1% 1350

M301 0 3 20 0 10 4 0 0 0 2 17.5% 1350

M302 0 3 20 0 10 4 0 0 0 4 18.9% 1350

M303 0 3 20 0 10 4 0 0 2 0 17.0% 1400

M304 0 3 20 0 10 4 0 0 2 2 18.4% 1400

M305 0 3 20 0 10 4 0 0 2 4 19.8% 1450

M306 0 3 20 0 10 4 0 0 4 0 17.8% 1500

M307 0 3 20 0 10 4 0 0 4 2 19.3% 1500

M308 0 3 20 0 10 4 0 0 4 4 20.7% 1500

M309 0 3 20 0 10 4 0 2 0 0 18.3% 1350

M310 0 3 20 0 10 4 0 2 0 2 19.7% 1350

M311 0 3 20 0 10 4 0 2 0 4 21.1% 1350

M312 0 3 20 0 10 4 0 2 2 0 19.2% 1400

M313 0 3 20 0 10 4 0 2 2 2 20.6% 1400

M314 0 3 20 0 10 4 0 2 2 4 22.0% 1400

M315 0 3 20 0 10 4 0 2 4 0 20.1% 1450

M316 0 3 20 0 10 4 0 2 4 2 21.5% 1450

M317 0 3 20 0 10 4 0 2 4 4 23.0% 1450

M318 0 3 20 0 10 4 0 4 0 0 20.5% 1350 M319 0 3 20 0 10 4 0 4 0 2 21.9% 1350

M320 0 3 20 0 10 4 0 4 0 4 23.3% 1350

M321 0 3 20 0 10 4 0 4 2 0 21.4% 1400

M322 0 3 20 0 10 4 0 4 2 2 22.8% 1400

M323 0 3 20 0 10 4 0 4 2 4 24.3% 1400

M324 0 3 20 0 10 4 0 4 4 0 22.3% 1450

M325 0 3 20 0 10 4 0 4 4 2 23.8% 1450

M326 0 3 20 0 10 4 0 4 4 4 25.3% 1450

M327 0 3 20 0 10 4 2 0 0 0 18.4% 1350

M328 0 3 20 0 10 4 2 0 0 2 19.8% 1400

M329 0 3 20 0 10 4 2 0 0 4 21.2% 1400

M330 0 3 20 0 10 4 2 0 2 0 19.3% 1450

M331 0 3 20 0 10 4 2 0 2 2 20.7% 1450

M332 0 3 20 0 10 4 2 0 2 4 22.2% 1450

M333 0 3 20 0 10 4 2 0 4 0 20.2% 1500

M334 0 3 20 0 10 4 2 0 4 2 21.7% 1500

M335 0 3 20 0 10 4 2 0 4 4 23.1% 1500

M336 0 3 20 0 10 4 2 2 0 0 20.6% 1350

M337 0 3 20 0 10 4 2 2 0 2 22.0% 1350

M338 0 3 20 0 10 4 2 2 0 4 23.4% 1350

M339 0 3 20 0 10 4 2 2 2 0 21.5% 1450

M340 0 3 20 0 10 4 2 2 2 2 22.9% 1450

M341 0 3 20 0 10 4 2 2 2 4 24.4% 1450

M342 0 3 20 0 10 4 2 2 4 0 22.4% 1500

M343 0 3 20 0 10 4 2 2 4 2 23.9% 1500

M344 0 3 20 0 10 4 2 2 4 4 25.4% 1500

M345 0 3 20 0 10 4 2 4 0 0 22.7% 1350

M346 0 3 20 0 10 4 2 4 0 2 24.2% 1350

M347 0 3 20 0 10 4 2 4 0 4 25.6% 1350

M348 0 3 20 0 10 4 2 4 2 0 23.7% 1450

M349 0 3 20 0 10 4 2 4 2 2 25.1% 1450

M350 0 3 20 0 10 4 2 4 2 4 26.6% 1450

M351 0 3 20 0 10 4 2 4 4 0 24.7% 1500

M352 0 3 20 0 10 4 2 4 4 2 26.1% 1500

M353 0 3 20 0 10 4 2 4 4 4 27.6% 1450

M354 0 3 20 0 10 4 4 0 0 0 20.7% 1400

M355 0 3 20 0 10 4 4 0 0 2 22.1% 1400

M356 0 3 20 0 10 4 4 0 0 4 23.5% 1400

M357 0 3 20 0 10 4 4 0 2 0 21.6% 1500

M358 0 3 20 0 10 4 4 0 2 2 23.0% 1500

M359 0 3 20 0 10 4 4 0 2 4 24.5% 1450

M360 0 3 20 0 10 4 4 0 4 2 24.0% 1500

M361 0 3 20 0 10 4 4 0 4 4 25.5% 1500 M362 0 3 20 0 10 4 4 2 0 0 22.9% 1400

M363 0 3 20 0 10 4 4 2 0 2 24.3% 1400

M364 0 3 20 0 10 4 4 2 0 4 25.7% 1400

M365 0 3 20 0 10 4 4 2 2 0 23.8% 1450

M366 0 3 20 0 10 4 4 2 2 2 25.2% 1450

M367 0 3 20 0 10 4 4 2 2 4 26.7% 1450

M368 0 3 20 0 10 4 4 2 4 0 24.8% 1500

M369 0 3 20 0 10 4 4 2 4 2 26.2% 1500

M370 0 3 20 0 10 4 4 2 4 4 27.7% 1500

M371 0 3 20 0 10 4 4 4 0 0 25.0% 1400

M372 0 3 20 0 10 4 4 4 0 2 26.4% 1400

M373 0 3 20 0 10 4 4 4 0 4 27.9% 1400

M374 0 3 20 0 10 4 4 4 2 0 26.0% 1450

M375 0 3 20 0 10 4 4 4 2 2 27.4% 1450

M376 0 3 20 0 10 4 4 4 2 4 28.9% 1450

M377 0 3 20 0 10 4 4 4 4 0 27.0% 1500

M378 0 3 20 0 10 4 4 4 4 2 28.5% 1500

M379 0 3 20 0 7 0 0 0 0 0 14.9% 1500

M380 0 3 20 0 9 0 0 0 0 0 14.6% 1450

M381 0 3 20 0 11 0 0 0 0 0 14.3% 1400

M382 0 3 20 0 13 0 0 0 0 0 14.1% 1400

M383 0 3 20 0 15 0 0 0 0 0 13.8% 1450

M384 0 3 20 1 7 0 0 0 0 0 15.6% 1450

M385 0 3 20 1 9 0 0 0 0 0 15.3% 1500

M386 0 3 20 1 11 0 0 0 0 0 15.0% 1500

M387 0 3 20 2 5 0 0 0 0 0 16.6% 1500

M388 0 0 11 0 10 0 0 0 0 0 6.1% 1500

M389 0 0 13 0 10 0 0 0 0 0 7.2% 1500

M390 0 0 15 0 9 0 0 0 0 0 8.5% 1500

M391 0 0 15 0 10 0 0 0 0 0 8.4% 1500

M392 0 0 17 0 8 0 0 0 0 0 9.8% 1500

M393 0 0 17 0 9 0 0 0 0 0 9.7% 1500

M394 0 0 17 0 10 0 0 0 0 0 9.6% 1450

M395 0 0 19 0 8 0 0 0 0 0 11.1% 1500

M396 0 0 19 0 9 0 0 0 0 0 11.0% 1500

M397 0 0 19 0 10 0 0 0 0 0 10.8% 1450

M398 0 0 21 0 7 0 0 0 0 0 12.5% 1500

M399 0 0 21 0 8 0 0 0 0 0 12.3% 1500

M400 0 0 21 0 9 0 0 0 0 0 12.2% 1450

M401 0 0 21 0 10 0 0 0 0 0 12.1% 1450

M402 0 0 23 0 7 0 0 0 0 0 13.8% 1500

M403 0 0 23 0 8 0 0 0 0 0 13.6% 1450

M404 0 0 23 0 9 0 0 0 0 0 13.5% 1450 M405 0 0 23 0 10 0 0 0 0 0 13.3% 1400

M406 0 0 25 0 6 0 0 0 0 0 15.2% 1500

M407 0 0 25 0 7 0 0 0 0 0 15.1% 1500

M408 0 0 25 0 8 0 0 0 0 0 14.9% 1450

M409 0 0 25 0 9 0 0 0 0 0 14.8% 1400

M410 0 0 25 0 10 0 0 0 0 0 14.6% 1400

M411 0 0 27 0 6 0 0 0 0 0 16.6% 1500

M412 0 0 27 0 7 0 0 0 0 0 16.4% 1450

M413 0 0 27 0 8 0 0 0 0 0 16.3% 1450

M414 0 0 27 0 9 0 0 0 0 0 16.1% 1400

M415 0 0 27 0 10 0 0 0 0 0 15.9% 1400

M416 0 0 29 0 5 0 0 0 0 0 18.2% 1500

M417 0 0 29 0 6 0 0 0 0 0 18.0% 1500

M418 0 0 29 0 7 0 0 0 0 0 17.8% 1450

M419 0 0 29 0 8 0 0 0 0 0 17.6% 1400

M420 0 0 29 0 9 0 0 0 0 0 17.4% 1400

M421 0 0 29 0 10 0 0 0 0 0 17.3% 1400

M422 0 1 11 0 10 0 0 0 0 0 7.0% 1500

M423 0 1 13 0 9 0 0 0 0 0 8.3% 1500

M424 0 1 13 0 10 0 0 0 0 0 8.2% 1500

M425 0 1 15 0 9 0 0 0 0 0 9.5% 1500

M426 0 1 15 0 10 0 0 0 0 0 9.4% 1500

M427 0 1 17 0 8 0 0 0 0 0 10.8% 1500

M428 0 1 17 0 9 0 0 0 0 0 10.7% 1500

M429 0 1 17 0 10 0 0 0 0 0 10.6% 1450

M430 0 1 19 0 7 0 0 0 0 0 12.2% 1500

M431 0 1 19 0 8 0 0 0 0 0 12.1% 1500

M432 0 1 19 0 9 0 0 0 0 0 12.0% 1450

M433 0 1 19 0 10 0 0 0 0 0 11.8% 1450

M434 0 1 21 0 7 0 0 0 0 0 13.5% 1500

M435 0 1 21 0 8 0 0 0 0 0 13.4% 1450

M436 0 1 21 0 9 0 0 0 0 0 13.2% 1450

M437 0 1 21 0 10 0 0 0 0 0 13.1% 1400

M438 0 1 23 0 6 0 0 0 0 0 14.9% 1500

M439 0 1 23 0 7 0 0 0 0 0 14.8% 1500

M440 0 1 23 0 8 0 0 0 0 0 14.6% 1450

M441 0 1 23 0 9 0 0 0 0 0 14.5% 1450

M442 0 1 23 0 10 0 0 0 0 0 14.4% 1400

M443 0 1 25 0 6 0 0 0 0 0 16.3% 1500

M444 0 1 25 0 7 0 0 0 0 0 16.1% 1450

M445 0 1 25 0 8 0 0 0 0 0 16.0% 1450

M446 0 1 25 0 9 0 0 0 0 0 15.8% 1400

M447 0 1 25 0 10 0 0 0 0 0 15.7% 1400 M448 0 1 27 0 5 0 0 0 0 0 17.9% 1500

M449 0 1 27 0 6 0 0 0 0 0 17.7% 1500

M450 0 1 27 0 7 0 0 0 0 0 17.5% 1450

M451 0 1 27 0 8 0 0 0 0 0 17.3% 1400

M452 0 1 27 0 9 0 0 0 0 0 17.1% 1400

M453 0 1 27 0 10 0 0 0 0 0 17.0% 1400

M454 0 1 29 0 5 0 0 0 0 0 19.3% 1500

M455 0 1 29 0 6 0 0 0 0 0 19.1% 1450

M456 0 1 29 0 7 0 0 0 0 0 18.9% 1450

M457 0 1 29 0 8 0 0 0 0 0 18.7% 1400

M458 0 1 29 0 9 0 0 0 0 0 18.5% 1400

M459 0 1 29 0 10 0 0 0 0 0 18.3% 1400

M460 0 2 9 0 10 0 0 0 0 0 6.8% 1500

M461 0 2 11 0 9 0 0 0 0 0 8.1% 1500

M462 0 2 11 0 10 0 0 0 0 0 8.0% 1500

M463 0 2 13 0 9 0 0 0 0 0 9.3% 1500

M464 0 2 13 0 10 0 0 0 0 0 9.2% 1500

M465 0 2 15 0 8 0 0 0 0 0 10.6% 1500

M466 0 2 15 0 9 0 0 0 0 0 10.5% 1500

M467 0 2 15 0 10 0 0 0 0 0 10.4% 1450

M468 0 2 17 0 7 0 0 0 0 0 11.9% 1500

M469 0 2 17 0 8 0 0 0 0 0 11.8% 1500

M470 0 2 17 0 9 0 0 0 0 0 11.7% 1450

M471 0 2 17 0 10 0 0 0 0 0 11.6% 1450

M472 0 2 19 0 7 0 0 0 0 0 13.2% 1500

M473 0 2 19 0 8 0 0 0 0 0 13.1% 1500

M474 0 2 19 0 9 0 0 0 0 0 13.0% 1450

M475 0 2 19 0 10 0 0 0 0 0 12.8% 1450

M476 0 2 21 0 6 0 0 0 0 0 14.7% 1500

M477 0 2 21 0 7 0 0 0 0 0 14.5% 1500

M478 0 2 21 0 8 0 0 0 0 0 14.4% 1450

M479 0 2 21 0 9 0 0 0 0 0 14.2% 1450

M480 0 2 21 0 10 0 0 0 0 0 14.1% 1400

M481 0 2 23 0 6 0 0 0 0 0 16.0% 1500

M482 0 2 23 0 7 0 0 0 0 0 15.8% 1450

M483 0 2 23 0 8 0 0 0 0 0 15.7% 1450

M484 0 2 23 0 9 0 0 0 0 0 15.5% 1400

M485 0 2 23 0 10 0 0 0 0 0 15.4% 1400

M486 0 2 25 0 5 0 0 0 0 0 17.5% 1500

M487 0 2 25 0 6 0 0 0 0 0 17.4% 1500

M488 0 2 25 0 7 0 0 0 0 0 17.2% 1450

M489 0 2 25 0 8 0 0 0 0 0 17.0% 1400

M490 0 2 25 0 9 0 0 0 0 0 16.8% 1400 M491 0 2 25 0 10 0 0 0 0 0 16.7% 1350

M492 0 2 27 0 5 0 0 0 0 0 18.9% 1500

M493 0 2 27 0 6 0 0 0 0 0 18.7% 1450

M494 0 2 27 0 7 0 0 0 0 0 18.6% 1450

M495 0 2 27 0 8 0 0 0 0 0 18.4% 1400

M496 0 2 27 0 9 0 0 0 0 0 18.2% 1400

M497 0 2 27 0 10 0 0 0 0 0 18.0% 1400

M498 0 2 29 0 5 0 0 0 0 0 20.4% 1500

M499 0 2 29 0 6 0 0 0 0 0 20.2% 1450

M500 0 2 29 0 7 0 0 0 0 0 19.9% 1400

M501 0 2 29 0 8 0 0 0 0 0 19.7% 1400

M502 0 2 29 0 9 0 0 0 0 0 19.5% 1400

M503 0 2 29 0 10 0 0 0 0 0 19.3% 1400

M504 0 3 7 0 10 0 0 0 0 0 6.7% 1500

M505 0 3 9 0 10 0 0 0 0 0 7.8% 1500

M506 0 3 11 0 9 0 0 0 0 0 9.1% 1500

M507 0 3 11 0 10 0 0 0 0 0 9.0% 1500

M508 0 3 13 0 8 0 0 0 0 0 10.4% 1500

M509 0 3 13 0 9 0 0 0 0 0 10.3% 1500

M510 0 3 13 0 10 0 0 0 0 0 10.2% 1450

M511 0 3 15 0 8 0 0 0 0 0 11.6% 1500

M512 0 3 15 0 9 0 0 0 0 0 11.5% 1500

M513 0 3 15 0 10 0 0 0 0 0 11.4% 1450

M514 0 3 17 0 7 0 0 0 0 0 13.0% 1500

M515 0 3 17 0 8 0 0 0 0 0 12.8% 1500

M516 0 3 17 0 9 0 0 0 0 0 12.7% 1450

M517 0 3 17 0 10 0 0 0 0 0 12.6% 1450

M518 0 3 19 0 6 0 0 0 0 0 14.4% 1500

M519 0 3 19 0 7 0 0 0 0 0 14.2% 1500

M520 0 3 19 0 8 0 0 0 0 0 14.1% 1450

M521 0 3 19 0 9 0 0 0 0 0 14.0% 1450

M522 0 3 19 0 10 0 0 0 0 0 13.8% 1400

M523 0 3 21 0 6 0 0 0 0 0 15.7% 1500

M524 0 3 21 0 7 0 0 0 0 0 15.6% 1500

M525 0 3 21 0 8 0 0 0 0 0 15.4% 1450

M526 0 3 21 0 9 0 0 0 0 0 15.2% 1400

M527 0 3 21 0 10 0 0 0 0 0 15.1% 1400

M528 0 3 23 0 5 0 0 0 0 0 17.2% 1500

M529 0 3 23 0 6 0 0 0 0 0 17.1% 1500

M530 0 3 23 0 7 0 0 0 0 0 16.9% 1450

M531 0 3 23 0 8 0 0 0 0 0 16.7% 1450

M532 0 3 23 0 9 0 0 0 0 0 16.5% 1400

M533 0 3 23 0 10 0 0 0 0 0 16.4% 1400 M534 0 3 25 0 5 0 0 0 0 0 18.6% 1500

M535 0 3 25 0 6 0 0 0 0 0 18.4% 1450

M536 0 3 25 0 7 0 0 0 0 0 18.2% 1450

M537 0 3 25 0 8 0 0 0 0 0 18.0% 1400

M538 0 3 25 0 9 0 0 0 0 0 17.9% 1400

M539 0 3 25 0 10 0 0 0 0 0 17.7% 1350

M540 0 3 27 0 5 0 0 0 0 0 20.0% 1500

M541 0 3 27 0 6 0 0 0 0 0 19.8% 1450

M542 0 3 27 0 7 0 0 0 0 0 19.6% 1400

M543 0 3 27 0 8 0 0 0 0 0 19.4% 1400

M544 0 3 27 0 9 0 0 0 0 0 19.2% 1350

M545 0 3 27 0 10 0 0 0 0 0 19.0% 1400

M546 0 3 29 0 4 0 0 0 0 0 21.7% 1500

M547 0 3 29 0 5 0 0 0 0 0 21.5% 1500

M548 0 3 29 0 6 0 0 0 0 0 21.2% 1450

M549 0 3 29 0 7 0 0 0 0 0 21.0% 1400

M550 0 3 29 0 8 0 0 0 0 0 20.8% 1400

M551 0 3 29 0 9 0 0 0 0 0 20.6% 1400

M552 0 3 29 0 10 0 0 0 0 0 20.4% 1400

M553 0 4 7 0 10 0 0 0 0 0 7.6% 1500

M554 0 4 9 0 9 0 0 0 0 0 8.8% 1500

M555 0 4 9 0 10 0 0 0 0 0 8.8% 1500

M556 0 4 11 0 9 0 0 0 0 0 10.0% 1500

M557 0 4 11 0 10 0 0 0 0 0 9.9% 1500

M558 0 4 13 0 8 0 0 0 0 0 11.3% 1500

M559 0 4 13 0 9 0 0 0 0 0 11.2% 1500

M560 0 4 13 0 10 0 0 0 0 0 11.1% 1450

M561 0 4 15 0 7 0 0 0 0 0 12.7% 1500

M562 0 4 15 0 8 0 0 0 0 0 12.6% 1500

M563 0 4 15 0 9 0 0 0 0 0 12.5% 1450

M564 0 4 15 0 10 0 0 0 0 0 12.3% 1450

M565 0 4 17 0 7 0 0 0 0 0 14.0% 1500

M566 0 4 17 0 8 0 0 0 0 0 13.8% 1450

M567 0 4 17 0 9 0 0 0 0 0 13.7% 1450

M568 0 4 17 0 10 0 0 0 0 0 13.6% 1400

M569 0 4 19 0 6 0 0 0 0 0 15.4% 1500

M570 0 4 19 0 7 0 0 0 0 0 15.3% 1500

M571 0 4 19 0 8 0 0 0 0 0 15.1% 1450

M572 0 4 19 0 9 0 0 0 0 0 15.0% 1450

M573 0 4 19 0 10 0 0 0 0 0 14.8% 1400

M574 0 4 21 0 6 0 0 0 0 0 16.8% 1500

M575 0 4 21 0 7 0 0 0 0 0 16.6% 1450

M576 0 4 21 0 8 0 0 0 0 0 16.4% 1450 M577 0 4 21 0 9 0 0 0 0 0 16.3% 1400

M578 0 4 21 0 10 0 0 0 0 0 16.1% 1400

M579 0 4 23 0 5 0 0 0 0 0 18.3% 1500

M580 0 4 23 0 6 0 0 0 0 0 18.1% 1500

M581 0 4 23 0 7 0 0 0 0 0 17.9% 1450

M582 0 4 23 0 8 0 0 0 0 0 17.7% 1400

M583 0 4 23 0 9 0 0 0 0 0 17.6% 1400

M584 0 4 23 0 10 0 0 0 0 0 17.4% 1350

M585 0 4 25 0 5 0 0 0 0 0 19.7% 1500

M586 0 4 25 0 6 0 0 0 0 0 19.5% 1450

M587 0 4 25 0 7 0 0 0 0 0 19.3% 1450

M588 0 4 25 0 8 0 0 0 0 0 19.1% 1400

M589 0 4 25 0 9 0 0 0 0 0 18.9% 1350

M590 0 4 25 0 10 0 0 0 0 0 18.7% 1350

M591 0 4 27 0 4 0 0 0 0 0 21.3% 1500

M592 0 4 27 0 5 0 0 0 0 0 21.1% 1500

M593 0 4 27 0 6 0 0 0 0 0 20.9% 1450

M594 0 4 27 0 7 0 0 0 0 0 20.7% 1400

M595 0 4 27 0 8 0 0 0 0 0 20.5% 1400

M596 0 4 27 0 9 0 0 0 0 0 20.2% 1350

M597 0 4 27 0 10 0 0 0 0 0 20.0% 1400

M598 0 4 29 0 4 0 0 0 0 0 22.8% 1500

M599 0 4 29 0 5 0 0 0 0 0 22.5% 1450

M600 0 4 29 0 6 0 0 0 0 0 22.3% 1450

M601 0 4 29 0 7 0 0 0 0 0 22.1% 1400

M602 0 4 29 0 8 0 0 0 0 0 21.8% 1400

M603 0 4 29 0 9 0 0 0 0 0 21.6% 1400

M604 0 4 29 0 10 0 0 0 0 0 21.4% 1400

M605 0 5 5 0 10 0 0 0 0 0 7.4% 1500

M606 0 5 7 0 10 0 0 0 0 0 8.6% 1500

M607 0 5 9 0 9 0 0 0 0 0 9.8% 1500

M608 0 5 9 0 10 0 0 0 0 0 9.7% 1500

M609 0 5 11 0 8 0 0 0 0 0 11.1% 1500

M610 0 5 11 0 9 0 0 0 0 0 11.0% 1500

M611 0 5 11 0 10 0 0 0 0 0 10.9% 1450

M612 0 5 13 0 7 0 0 0 0 0 12.5% 1500

M613 0 5 13 0 8 0 0 0 0 0 12.3% 1500

M614 0 5 13 0 9 0 0 0 0 0 12.2% 1450

M615 0 5 13 0 10 0 0 0 0 0 12.1% 1450

M616 0 5 15 0 7 0 0 0 0 0 13.7% 1500

M617 0 5 15 0 8 0 0 0 0 0 13.6% 1500

M618 0 5 15 0 9 0 0 0 0 0 13.4% 1450

M619 0 5 15 0 10 0 0 0 0 0 13.3% 1450 M620 0 5 17 0 6 0 0 0 0 0 15.1% 1500

M621 0 5 17 0 7 0 0 0 0 0 15.0% 1500

M622 0 5 17 0 8 0 0 0 0 0 14.8% 1450

M623 0 5 17 0 9 0 0 0 0 0 14.7% 1450

M624 0 5 17 0 10 0 0 0 0 0 14.6% 1400

M625 0 5 19 0 6 0 0 0 0 0 16.5% 1500

M626 0 5 19 0 7 0 0 0 0 0 16.3% 1450

M627 0 5 19 0 8 0 0 0 0 0 16.1% 1450

M628 0 5 19 0 9 0 0 0 0 0 16.0% 1400

M629 0 5 19 0 10 0 0 0 0 0 15.8% 1400

M630 0 5 21 0 5 0 0 0 0 0 18.0% 1500

M631 0 5 21 0 6 0 0 0 0 0 17.8% 1500

M632 0 5 21 0 7 0 0 0 0 0 17.6% 1450

M633 0 5 21 0 8 0 0 0 0 0 17.4% 1450

M634 0 5 21 0 9 0 0 0 0 0 17.3% 1400

M635 0 5 21 0 10 0 0 0 0 0 17.1% 1400

M636 0 5 23 0 5 0 0 0 0 0 19.4% 1500

M637 0 5 23 0 6 0 0 0 0 0 19.2% 1450

M638 0 5 23 0 7 0 0 0 0 0 19.0% 1450

M639 0 5 23 0 8 0 0 0 0 0 18.8% 1400

M640 0 5 23 0 9 0 0 0 0 0 18.6% 1400

M641 0 5 23 0 10 0 0 0 0 0 18.4% 1350

M642 0 5 25 0 4 0 0 0 0 0 21.0% 1500

M643 0 5 25 0 5 0 0 0 0 0 20.8% 1500

M644 0 5 25 0 6 0 0 0 0 0 20.5% 1450

M645 0 5 25 0 7 0 0 0 0 0 20.3% 1400

M646 0 5 25 0 8 0 0 0 0 0 20.1% 1400

M647 0 5 25 0 9 0 0 0 0 0 19.9% 1350

M648 0 5 25 0 10 0 0 0 0 0 19.7% 1350

M649 0 5 27 0 4 0 0 0 0 0 22.4% 1500

M650 0 5 27 0 5 0 0 0 0 0 22.2% 1450

M651 0 5 27 0 6 0 0 0 0 0 22.0% 1450

M652 0 5 27 0 7 0 0 0 0 0 21.7% 1400

M653 0 5 27 0 8 0 0 0 0 0 21.5% 1350

M654 0 5 27 0 9 0 0 0 0 0 21.3% 1350

M655 0 5 27 0 10 0 0 0 0 0 21.1% 1400

M656 0 5 29 0 4 0 0 0 0 0 23.9% 1500

M657 0 5 29 0 5 0 0 0 0 0 23.6% 1450

M658 0 5 29 0 6 0 0 0 0 0 23.4% 1400

M659 0 5 29 0 7 0 0 0 0 0 23.1% 1400

M660 0 5 29 0 8 0 0 0 0 0 22.9% 1400

M661 0 5 29 0 9 0 0 0 0 0 22.7% 1400

M662 0 5 29 0 10 0 0 0 0 0 22.4% 1400 M663 0 5 5 0 10 1 1 1 1 1 10.8% 1450

M664 0 5 5 0 10 0 0 0 1 0 7.7% 1500

M665 0 5 5 0 10 0 0 0 2 0 8.1% 1500

M666 0 5 5 0 10 0 0 0 3 0 8.4% 1500

M667 0 5 5 0 10 0 0 0 4 0 8.8% 1500

M668 0 5 5 0 10 0 0 1 0 0 8.4% 1500

M669 0 5 5 0 10 0 0 1 1 0 8.8% 1500

M670 0 5 5 0 10 0 0 1 2 0 9.1% 1500

M671 0 5 5 0 10 0 0 1 3 0 9.4% 1500

M672 0 5 5 0 10 0 0 1 4 0 9.8% 1500

M673 0 5 5 0 10 0 0 2 0 0 9.4% 1500

M674 0 5 5 0 10 0 0 2 1 0 9.8% 1500

M675 0 5 5 0 10 0 0 2 2 0 10.1% 1500

M676 0 5 5 0 10 0 0 2 3 0 10.5% 1500

M677 0 5 5 0 10 0 0 2 4 0 10.8% 1500

M678 0 5 5 0 10 0 0 3 0 0 10.4% 1500

M679 0 5 5 0 10 0 0 3 1 0 10.8% 1500

M680 0 5 5 0 10 0 0 3 2 0 11.1% 1500

M681 0 5 5 0 10 0 0 3 3 0 11.5% 1500

M682 0 5 5 0 10 0 0 3 4 0 11.9% 1500

M683 0 5 5 0 10 0 0 4 0 0 11.4% 1500

M684 0 5 5 0 10 0 0 4 1 0 11.8% 1500

M685 0 5 5 0 10 0 0 4 2 0 12.2% 1500

M686 0 5 5 0 10 0 0 4 3 0 12.5% 1500

M687 0 5 5 0 10 0 0 4 4 0 12.9% 1500

M688 0 5 5 0 10 0 1 0 0 0 8.5% 1500

M689 0 5 5 0 10 0 1 0 1 0 8.8% 1500

M690 0 5 5 0 10 0 1 0 2 0 9.2% 1500

M691 0 5 5 0 10 0 1 0 3 0 9.5% 1500

M692 0 5 5 0 10 0 1 0 4 0 9.9% 1500

M693 0 5 5 0 10 0 1 1 0 0 9.5% 1500

M694 0 5 5 0 10 0 1 1 1 0 9.8% 1500

M695 0 5 5 0 10 0 1 1 2 0 10.2% 1500

M696 0 5 5 0 10 0 1 1 3 0 10.5% 1500

M697 0 5 5 0 10 0 1 1 4 0 10.9% 1500

M698 0 5 5 0 10 0 1 2 0 0 10.5% 1500

M699 0 5 5 0 10 0 1 2 1 0 10.8% 1500

M700 0 5 5 0 10 0 1 2 2 0 11.2% 1500

M701 0 5 5 0 10 0 1 2 3 0 11.6% 1500

M702 0 5 5 0 10 0 1 2 4 0 11.9% 1500

M703 0 5 5 0 10 0 1 3 0 0 11.5% 1500

M704 0 5 5 0 10 0 1 3 1 0 11.8% 1500

M705 0 5 5 0 10 0 1 3 2 0 12.2% 1500 M706 0 5 5 0 10 0 1 3 3 0 12.6% 1500

M707 0 5 5 0 10 0 1 3 4 0 12.9% 1450

M708 0 5 5 0 10 0 1 4 0 0 12.5% 1500

M709 0 5 5 0 10 0 1 4 1 0 12.9% 1500

M710 0 5 5 0 10 0 1 4 2 0 13.2% 1500

M711 0 5 5 0 10 0 1 4 3 0 13.6% 1500

M712 0 5 5 0 10 0 1 4 4 0 14.0% 1450

M713 0 5 5 0 10 0 2 0 0 0 9.5% 1500

M714 0 5 5 0 10 0 2 0 1 0 9.9% 1500

M715 0 5 5 0 10 0 2 0 2 0 10.2% 1500

M716 0 5 5 0 10 0 2 0 3 0 10.6% 1450

M717 0 5 5 0 10 0 2 0 4 0 10.9% 1450

M718 0 5 5 0 10 0 2 1 0 0 10.5% 1500

M719 0 5 5 0 10 0 2 1 1 0 10.9% 1500

M720 0 5 5 0 10 0 2 1 2 0 11.3% 1500

M721 0 5 5 0 10 0 2 1 3 0 11.6% 1450

M722 0 5 5 0 10 0 2 1 4 0 12.0% 1450

M723 0 5 5 0 10 0 2 2 0 0 11.5% 1500

M724 0 5 5 0 10 0 2 2 1 0 11.9% 1500

M725 0 5 5 0 10 0 2 2 2 0 12.3% 1500

M726 0 5 5 0 10 0 2 2 3 0 12.6% 1450

M727 0 5 5 0 10 0 2 2 4 0 13.0% 1450

M728 0 5 5 0 10 0 2 3 0 0 12.5% 1500

M729 0 5 5 0 10 0 2 3 1 0 12.9% 1500

M730 0 5 5 0 10 0 2 3 2 0 13.3% 1450

M731 0 5 5 0 10 0 2 3 3 0 13.7% 1450

M732 0 5 5 0 10 0 2 3 4 0 14.0% 1450

M733 0 5 5 0 10 0 2 4 0 0 13.5% 1500

M734 0 5 5 0 10 0 2 4 1 0 13.9% 1500

M735 0 5 5 0 10 0 2 4 2 0 14.3% 1450

M736 0 5 5 0 10 0 2 4 3 0 14.7% 1450

M737 0 5 5 0 10 0 2 4 4 0 15.1% 1450

M738 0 5 5 0 10 0 3 0 0 0 10.6% 1500

M739 0 5 5 0 10 0 3 0 1 0 11.0% 1450

M740 0 5 5 0 10 0 3 0 2 0 11.3% 1450

M741 0 5 5 0 10 0 3 0 3 0 11.7% 1450

M742 0 5 5 0 10 0 3 0 4 0 12.0% 1450

M743 0 5 5 0 10 0 3 1 0 0 11.6% 1500

M744 0 5 5 0 10 0 3 1 1 0 12.0% 1450

M745 0 5 5 0 10 0 3 1 2 0 12.3% 1450

M746 0 5 5 0 10 0 3 1 3 0 12.7% 1450

M747 0 5 5 0 10 0 3 1 4 0 13.1% 1450

M748 0 5 5 0 10 0 3 2 0 0 12.6% 1450 M749 0 5 5 0 10 0 3 2 1 0 13.0% 1450

M750 0 5 5 0 10 0 3 2 2 0 13.3% 1450

M751 0 5 5 0 10 0 3 2 3 0 13.7% 1450

M752 0 5 5 0 10 0 3 2 4 0 14.1% 1450

M753 0 5 5 0 10 0 3 3 0 0 13.6% 1450

M754 0 5 5 0 10 0 3 3 1 0 14.0% 1450

M755 0 5 5 0 10 0 3 3 2 0 14.3% 1450

M756 0 5 5 0 10 0 3 3 3 0 14.7% 1450

M757 0 5 5 0 10 0 3 3 4 0 15.1% 1450

M758 0 5 5 0 10 0 3 4 0 0 14.6% 1450

M759 0 5 5 0 10 0 3 4 1 0 15.0% 1450

M760 0 5 5 0 10 0 3 4 2 0 15.4% 1450

M761 0 5 5 0 10 0 3 4 3 0 15.7% 1450

M762 0 5 5 0 10 0 3 4 4 0 16.1% 1450

M763 0 5 5 0 10 0 4 0 0 0 11.7% 1450

M764 0 5 5 0 10 0 4 0 1 0 12.0% 1450

M765 0 5 5 0 10 0 4 0 2 0 12.4% 1450

M766 0 5 5 0 10 0 4 0 3 0 12.7% 1450

M767 0 5 5 0 10 0 4 0 4 0 13.1% 1450

M768 0 5 5 0 10 0 4 1 0 0 12.7% 1450

M769 0 5 5 0 10 0 4 1 1 0 13.0% 1450

M770 0 5 5 0 10 0 4 1 2 0 13.4% 1450

M771 0 5 5 0 10 0 4 1 3 0 13.8% 1450

M772 0 5 5 0 10 0 4 1 4 0 14.1% 1450

M773 0 5 5 0 10 0 4 2 0 0 13.7% 1450

M774 0 5 5 0 10 0 4 2 1 0 14.0% 1450

M775 0 5 5 0 10 0 4 2 2 0 14.4% 1450

M776 0 5 5 0 10 0 4 2 3 0 14.8% 1450

M777 0 5 5 0 10 0 4 2 4 0 15.2% 1450

M778 0 5 5 0 10 0 4 3 0 0 14.7% 1450

M779 0 5 5 0 10 0 4 3 1 0 15.0% 1450

M780 0 5 5 0 10 0 4 3 2 0 15.4% 1450

M781 0 5 5 0 10 0 4 3 3 0 15.8% 1450

M782 0 5 5 0 10 0 4 3 4 0 16.2% 1450

M783 0 5 5 0 10 0 4 4 0 0 15.6% 1450

M784 0 5 5 0 10 0 4 4 1 0 16.0% 1450

M785 0 5 5 0 10 0 4 4 2 0 16.4% 1450

M786 0 5 5 0 10 0 4 4 3 0 16.8% 1450

M787 0 5 5 0 10 0 4 4 4 0 17.2% 1450

M788 0 5 7 0 10 0 0 0 1 0 8.9% 1500

M789 0 5 7 0 10 0 0 0 2 0 9.2% 1500

M790 0 5 7 0 10 0 0 0 3 0 9.6% 1500

M791 0 5 7 0 10 0 0 0 4 0 9.9% 1500 M792 0 5 7 0 10 0 0 1 0 0 9.6% 1500

M793 0 5 7 0 10 0 0 1 1 0 9.9% 1500

M794 0 5 7 0 10 0 0 1 2 0 10.3% 1500

M795 0 5 7 0 10 0 0 1 3 0 10.6% 1500

M796 0 5 7 0 10 0 0 1 4 0 11.0% 1500

M797 0 5 7 0 10 0 0 2 0 0 10.6% 1500

M798 0 5 7 0 10 0 0 2 1 0 10.9% 1500

M799 0 5 7 0 10 0 0 2 2 0 11.3% 1500

M800 0 5 7 0 10 0 0 2 3 0 11.7% 1500

M801 0 5 7 0 10 0 0 2 4 0 12.0% 1450

M802 0 5 7 0 10 0 0 3 0 0 11.6% 1500

M803 0 5 7 0 10 0 0 3 1 0 12.0% 1500

M804 0 5 7 0 10 0 0 3 2 0 12.3% 1500

M805 0 5 7 0 10 0 0 3 3 0 12.7% 1500

M806 0 5 7 0 10 0 0 3 4 0 13.1% 1450

M807 0 5 7 0 10 0 0 4 0 0 12.6% 1500

M808 0 5 7 0 10 0 0 4 1 0 13.0% 1500

M809 0 5 7 0 10 0 0 4 2 0 13.3% 1500

M810 0 5 7 0 10 0 0 4 3 0 13.7% 1450

M811 0 5 7 0 10 0 0 4 4 0 14.1% 1450

M812 0 5 7 0 10 0 1 0 0 0 9.6% 1500

M813 0 5 7 0 10 0 1 0 1 0 10.0% 1500

M814 0 5 7 0 10 0 1 0 2 0 10.3% 1500

M815 0 5 7 0 10 0 1 0 3 0 10.7% 1450

M816 0 5 7 0 10 0 1 0 4 0 11.0% 1450

M817 0 5 7 0 10 0 1 1 0 0 10.6% 1500

M818 0 5 7 0 10 0 1 1 1 0 11.0% 1500

M819 0 5 7 0 10 0 1 1 2 0 11.4% 1450

M820 0 5 7 0 10 0 1 1 3 0 11.7% 1450

M821 0 5 7 0 10 0 1 1 4 0 12.1% 1450

M822 0 5 7 0 10 0 1 2 0 0 11.7% 1500

M823 0 5 7 0 10 0 1 2 1 0 12.0% 1500

M824 0 5 7 0 10 0 1 2 2 0 12.4% 1450

M825 0 5 7 0 10 0 1 2 3 0 12.7% 1450

M826 0 5 7 0 10 0 1 2 4 0 13.1% 1450

M827 0 5 7 0 10 0 1 3 0 0 12.7% 1500

M828 0 5 7 0 10 0 1 3 1 0 13.0% 1500

M829 0 5 7 0 10 0 1 3 2 0 13.4% 1450

M830 0 5 7 0 10 0 1 3 3 0 13.8% 1450

M831 0 5 7 0 10 0 1 3 4 0 14.2% 1450

M832 0 5 7 0 10 0 1 4 0 0 13.7% 1500

M833 0 5 7 0 10 0 1 4 1 0 14.0% 1450

M834 0 5 7 0 10 0 1 4 2 0 14.4% 1450 M835 0 5 7 0 10 0 1 4 3 0 14.8% 1450

M836 0 5 7 0 10 0 1 4 4 0 15.2% 1450

M837 0 5 7 0 10 0 2 0 0 0 10.7% 1500

M838 0 5 7 0 10 0 2 0 1 0 11.1% 1450

M839 0 5 7 0 10 0 2 0 2 0 11.4% 1450

M840 0 5 7 0 10 0 2 0 3 0 11.8% 1450

M841 0 5 7 0 10 0 2 0 4 0 12.1% 1450

M842 0 5 7 0 10 0 2 1 0 0 11.7% 1450

M843 0 5 7 0 10 0 2 1 1 0 12.1% 1450

M844 0 5 7 0 10 0 2 1 2 0 12.4% 1450

M845 0 5 7 0 10 0 2 1 3 0 12.8% 1450

M846 0 5 7 0 10 0 2 1 4 0 13.2% 1450

M847 0 5 7 0 10 0 2 2 0 0 12.7% 1450

M848 0 5 7 0 10 0 2 2 1 0 13.1% 1450

M849 0 5 7 0 10 0 2 2 2 0 13.5% 1450

M850 0 5 7 0 10 0 2 2 3 0 13.8% 1450

M851 0 5 7 0 10 0 2 2 4 0 14.2% 1450

M852 0 5 7 0 10 0 2 3 0 0 13.7% 1450

M853 0 5 7 0 10 0 2 3 1 0 14.1% 1450

M854 0 5 7 0 10 0 2 3 2 0 14.5% 1450

M855 0 5 7 0 10 0 2 3 3 0 14.9% 1450

M856 0 5 7 0 10 0 2 3 4 0 15.2% 1450

M857 0 5 7 0 10 0 2 4 0 0 14.7% 1450

M858 0 5 7 0 10 0 2 4 1 0 15.1% 1450

M859 0 5 7 0 10 0 2 4 2 0 15.5% 1450

M860 0 5 7 0 10 0 2 4 3 0 15.9% 1450

M861 0 5 7 0 10 0 2 4 4 0 16.3% 1450

M862 0 5 7 0 10 0 3 0 0 0 11.8% 1450

M863 0 5 7 0 10 0 3 0 1 0 12.1% 1450

M864 0 5 7 0 10 0 3 0 2 0 12.5% 1450

M865 0 5 7 0 10 0 3 0 3 0 12.9% 1450

M866 0 5 7 0 10 0 3 0 4 0 13.2% 1450

M867 0 5 7 0 10 0 3 1 0 0 12.8% 1450

M868 0 5 7 0 10 0 3 1 1 0 13.1% 1450

M869 0 5 7 0 10 0 3 1 2 0 13.5% 1450

M870 0 5 7 0 10 0 3 1 3 0 13.9% 1450

M871 0 5 7 0 10 0 3 1 4 0 14.3% 1450

M872 0 5 7 0 10 0 3 2 0 0 13.8% 1450

M873 0 5 7 0 10 0 3 2 1 0 14.2% 1450

M874 0 5 7 0 10 0 3 2 2 0 14.5% 1450

M875 0 5 7 0 10 0 3 2 3 0 14.9% 1450

M876 0 5 7 0 10 0 3 2 4 0 15.3% 1450

M877 0 5 7 0 10 0 3 3 0 0 14.8% 1450 M878 0 5 7 0 10 0 3 3 1 0 15.2% 1450

M879 0 5 7 0 10 0 3 3 2 0 15.6% 1450

M880 0 5 7 0 10 0 3 3 3 0 15.9% 1450

M881 0 5 7 0 10 0 3 3 4 0 16.3% 1450

M882 0 5 7 0 10 0 3 4 0 0 15.8% 1450

M883 0 5 7 0 10 0 3 4 1 0 16.2% 1450

M884 0 5 7 0 10 0 3 4 2 0 16.6% 1450

M885 0 5 7 0 10 0 3 4 3 0 17.0% 1450

M886 0 5 7 0 10 0 3 4 4 0 17.4% 1450

M887 0 5 7 0 10 0 4 0 0 0 12.8% 1450

M888 0 5 7 0 10 0 4 0 1 0 13.2% 1450

M889 0 5 7 0 10 0 4 0 2 0 13.6% 1450

M890 0 5 7 0 10 0 4 0 3 0 14.0% 1450

M891 0 5 7 0 10 0 4 0 4 0 14.3% 1450

M892 0 5 7 0 10 0 4 1 0 0 13.8% 1450

M893 0 5 7 0 10 0 4 1 1 0 14.2% 1450

M894 0 5 7 0 10 0 4 1 2 0 14.6% 1450

M895 0 5 7 0 10 0 4 1 3 0 15.0% 1450

M896 0 5 7 0 10 0 4 1 4 0 15.4% 1450

M897 0 5 7 0 10 0 4 2 0 0 14.8% 1450

M898 0 5 7 0 10 0 4 2 1 0 15.2% 1450

M899 0 5 7 0 10 0 4 2 2 0 15.6% 1450

M900 0 5 7 0 10 0 4 2 3 0 16.0% 1450

M901 0 5 7 0 10 0 4 2 4 0 16.4% 1450

M902 0 5 7 0 10 0 4 3 0 0 15.8% 1450

M903 0 5 7 0 10 0 4 3 1 0 16.2% 1450

M904 0 5 7 0 10 0 4 3 2 0 16.6% 1450

M905 0 5 7 0 10 0 4 3 3 0 17.0% 1400

M906 0 5 7 0 10 0 4 3 4 0 17.4% 1450

M907 0 5 7 0 10 0 4 4 0 0 16.8% 1450

M908 0 5 7 0 10 0 4 4 1 0 17.2% 1450

M909 0 5 7 0 10 0 4 4 2 0 17.6% 1450

M910 0 5 7 0 10 0 4 4 3 0 18.0% 1400

M911 0 5 7 0 10 0 4 4 4 0 18.4% 1450

M912 0 5 9 0 10 0 0 0 1 0 10.1% 1500

M913 0 5 9 0 10 0 0 0 2 0 10.4% 1450

M914 0 5 9 0 10 0 0 0 3 0 10.8% 1450

M915 0 5 9 0 10 0 0 0 4 0 11.2% 1450

M916 0 5 9 0 10 0 0 1 0 0 10.7% 1500

M917 0 5 9 0 10 0 0 1 1 0 11.1% 1500

M918 0 5 9 0 10 0 0 1 2 0 11.5% 1450

M919 0 5 9 0 10 0 0 1 3 0 11.8% 1450

M920 0 5 9 0 10 0 0 1 4 0 12.2% 1450 M921 0 5 9 0 10 0 0 2 0 0 11.8% 1500

M922 0 5 9 0 10 0 0 2 1 0 12.1% 1450

M923 0 5 9 0 10 0 0 2 2 0 12.5% 1450

M924 0 5 9 0 10 0 0 2 3 0 12.9% 1450

M925 0 5 9 0 10 0 0 2 4 0 13.2% 1450

M926 0 5 9 0 10 0 0 3 0 0 12.8% 1500

M927 0 5 9 0 10 0 0 3 1 0 13.2% 1450

M928 0 5 9 0 10 0 0 3 2 0 13.5% 1450

M929 0 5 9 0 10 0 0 3 3 0 13.9% 1450

M930 0 5 9 0 10 0 0 3 4 0 14.3% 1450

M931 0 5 9 0 10 0 0 4 0 0 13.8% 1500

M932 0 5 9 0 10 0 0 4 1 0 14.2% 1450

[0047] In some embodiments, the alloy can possess a low FCC-BCC transition temperature. This criteria can be related to the likelihood of the alloy to retain an austenitic structure when deposited and thus be 'readable' by certain measuring devices, as discussed further below. Readable coatings can be non-magnetic and thus the thickness can be measured with standard paint thickness gauges. This can be advantageous for many thermal spray applications.

Performance Criteria:

[0048] In some embodiments, the alloy can be described by performance criteria. The performance criteria that can be advantageous to the field of thermal spray hardfacing is the hardness, wear resistance, coating adhesion, and corrosion resistance.

[0049] In some embodiments, the Vickers hardness of the coating can be 400 or above (or about 400 or above). In some embodiments, the Vickers hardness of the coating can be 500 or above (or about 500 or above). In some embodiments, the Vickers hardness can be 550 or above (or about 550 or above).In some embodiments, the Vickers hardness can be 600 or above (or about 600 or above). The specific microstructure disclosed herein can allow for embodiments of the alloys to have high hardness.

[0050] In some embodiments, the adhesion strength of the coating can be 5,000 psi or above (or about 5,000 psi or above). In some embodiments, the adhesion strength of the coating can be 7,500 psi or above (or about 7,500 psi or above). In some embodiments, the adhesion strength of the coating can be 10,000 psi or above (or about 10,000 psi or above).

[0051] In some embodiments, the abrasion resistance of the coating as measured via ASTM G65B testing can be 0.8 grams loss or below (or about 0.8 grams loss or below). In some embodiments, the abrasion resistance of the coating as measured via ASTM G65B testing can be 0.6 grams loss or below (or about 0.6 grams loss or below). In some embodiments, the abrasion resistance of the coating as measured via ASTM G65B testing can be 0.4 grams loss or below (or about 0.4 grams loss or below).

[0052] In some embodiments, the adhesive wear resistance of the coating as measured via ASTM G77 testing, hereby incorporated by reference in its entirety, can be 2 mm 3 volume loss or below (or about 2 mm 3 volume loss or below). In some embodiments, the adhesive wear resistance of the coating as measured via ASTM Gil testing can be 0.5 mm 3 volume loss or below (or about 0.5 mm 3 volume loss or below). In some embodiments, the adhesive wear resistance of the coating as measured via ASTM Gil testing can be 0.1 mm 3 volume loss or below (or about 0.1 mm 3 volume loss or below).

[0053] In some embodiments, the alloy can exhibit similar performance to conventional Cr-bearing thermal spray materials used for hardfacing. The most exemplary and well used thermal spray hardfacing material possesses a chemical composition of Fe: BAL, Cr: 29, Si: 1, Mn: 2, B: 4, which is generally referred to in the industry as Armacor M. Armacor M possesses the following properties which are relevant to thermal spray hardfacing: adhesion of about 8,000 psi, ASTM G65B mass loss of about 0.37 grams, ASTM G77 volume loss of about 0.07 mm , and position in the galvanic series in saltwater of about -500 mV. Armacor M is primarily made of Fe, Cr, and B, has a high melting temperature, and has no large atoms.

[0054] In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion and abrasive wear resistance as Armacor, where 'similar' equates to within 25% (or within about 25%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, and adhesive wear resistance as Armacor, where 'similar' equates to within 25% (or within about 25%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, adhesive wear resistance, and corrosion resistance as Armacor, where 'similar' equates to within 25% (or within about 25%) of the measured performance properties of Armacor M or better.

[0055] In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion and abrasive wear resistance as Armacor, where 'similar' equates to within 10% (or within about 10%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, and adhesive wear resistance as Armacor, where 'similar' equates to within 10% (or within about 10%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, adhesive wear resistance, and corrosion resistance as Armacor, where 'similar' equates to within 10% (or within about 10%) of the measured performance properties of Armacor M or better.

[0056] In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion and abrasive wear resistance as Armacor, where 'similar' equates to within 1% (or within about 1%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, and adhesive wear resistance as Armacor, where 'similar' equates to within 1% (or within about 1%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, adhesive wear resistance, and corrosion resistance as Armacor, where 'similar' equates to within 1% (or within about 1%) of the measured performance properties of Armacor M or better.

[0057] In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion and abrasive wear resistance as Armacor, where 'similar' equates to within 0% (or within about 0%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, and adhesive wear resistance as Armacor, where 'similar' equates to within 0% (or within about 0%) of the measured performance properties of Armacor M or better. In some embodiments of this disclosure, the alloys can exhibit similar coating adhesion, abrasive wear resistance, adhesive wear resistance, and corrosion resistance as Armacor, where 'similar' equates to within 0% (or within about 0%) of the measured performance properties of Armacor M or better.

[0058] In some embodiments, the thermal spray coating can be 'readable'. A readable coating produces consistent thickness measurements with an Elcometer™ thickness gauge, or similar device, when properly calibrated. Armacor M is not a readable alloy, unlike embodiments of the disclosure, as it is magnetic.

[0059] As a standard to verify 'readability', a 25 mil standard thermal spray coupon is used for measurements. In some embodiments, the coating thickness measurement can be accurate to within 5 mils (or within about 5 mils) of the actual physical thickness. In some embodiments, the coating thickness measurement can be accurate to within 3.5 mils (or within about 3.5 mils) of the actual physical thickness. In some embodiments, the coating thickness measurement can be accurate to within 2 mils (or within about 2 mils) of the actual physical thickness.

[0060] In some embodiments, consistent measurements according to the above criteria, + 5 mils to actual physical thickness, can be made after the coating has been exposed to heat for an extended period of time. This can be advantageous because when the alloy is heated, there is a potential for a magnetic phase to precipitate out, which would make the alloy non-readable. This can be especially true for amorphous alloys which may be readable in amorphous form, but may crystallize in a different environment due to heat. Thus, in some embodiments, the alloy can remain non-magnetic even after being exposed to heat for a substantial time period.

[0061] In some embodiments, the coating can be 'readable' after exposure to HOOK (or about HOOK) for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S (or less than about 10K/S). In some embodiments, the coating can be 'readable' after exposure to 1300K (or about 1300K) for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S (or less than 10K/S). In some embodiments, the coating can be 'readable' after exposure to 1500K (r about 1500K) for 2 hours (or about 2 hours) and cooled at a rate of less than 10K/S (or less than about 10K/S). It is expected that increased exposure times above 2 hours will not continue to affect the final 'readability' of these materials.

Table 3: List of alloy compositions and thermodynamic and kinetic parameters which meet the criteria described in this disclosure, including the criteria pertained to coating non- magnetism and readability. Large atom % is the total atom % of elements larger than iron, Trans T is the FCC-BCC transition temperature and melt T is the melting temperature of the alloy.

No. C Mn Mo Ni Si Large Atom % Trans T Melt T

M934 0 19 20 0 10 30% 1000 1300

M935 0 20 19 0 10 31% 1000 1300

M936 0 20 20 0 10 31% 900 1300

M937 0 13 11 4 5 20% 800 1500

M938 0 13 11 5 5 20% 800 1500

M939 0 13 13 3 5 21% 800 1500

M940 0 13 13 4 5 21% 800 1500

M941 0 13 13 5 5 21% 800 1500

M942 0 13 13 5 6 21% 850 1450

M943 0 13 15 2 5 22% 800 1500

M944 0 13 15 3 5 22% 800 1500

M945 0 13 15 4 5 22% 800 1500

M946 0 13 15 4 6 22% 850 1450

M947 0 13 15 5 5 22% 800 1500

M948 0 13 15 5 6 22% 850 1450

M949 0 16 7 1 6 20% 850 1500

M950 0 16 7 2 6 20% 850 1500

M951 0 16 7 3 6 20% 850 1500

M952 0 16 7 3 7 20% 900 1500

M953 0 16 7 4 6 20% 800 1500

M954 0 16 7 4 7 20% 900 1500

M955 0 16 7 5 6 20% 800 1500

M956 0 16 7 5 7 20% 900 1500

M957 0 16 9 1 6 21% 850 1500

M958 0 16 9 2 6 21% 800 1500

M959 0 16 9 2 7 21% 900 1450

M960 0 16 9 3 6 21% 800 1500

M961 0 16 9 3 7 21% 900 1450

M962 0 16 9 4 6 21% 800 1500

M963 0 16 9 4 7 21% 900 1450 M964 0 16 9 4 8 21% 1000 1450

M965 0 16 9 5 5 21% 750 1500

M966 0 16 9 5 6 21% 800 1500

M967 0 16 9 5 7 21% 850 1450

M968 0 16 9 5 8 21% 1000 1450

M969 0 16 11 0 5 23% 800 1500

M970 0 16 11 1 5 23% 800 1500

M971 0 16 11 1 6 22% 850 1500

M972 0 16 11 1 7 22% 900 1450

M973 0 16 11 2 5 23% 750 1500

M974 0 16 11 2 6 22% 800 1500

M975 0 16 11 2 7 22% 900 1450

M976 0 16 11 3 5 23% 750 1500

M977 0 16 11 3 6 22% 800 1500

M978 0 16 11 3 7 22% 850 1450

M979 0 16 11 3 8 22% 1000 1400

M980 0 16 11 4 5 23% 750 1500

M981 0 16 11 4 6 22% 800 1500

M982 0 16 11 4 7 22% 850 1450

M983 0 16 11 4 8 22% 950 1400

M984 0 16 11 5 5 23% 750 1500

M985 0 16 11 5 6 22% 800 1500

M986 0 16 11 5 7 22% 850 1450

M987 0 16 13 0 5 24% 800 1500

M988 0 16 13 1 5 24% 750 1500

M989 0 16 13 1 6 24% 800 1450

M990 0 16 13 1 7 23% 900 1450

M991 0 16 13 2 5 24% 750 1500

M992 0 16 13 2 6 24% 800 1450

M993 0 16 13 2 7 23% 850 1450

M994 0 16 13 2 8 23% 950 1400

M995 0 16 13 3 5 24% 750 1500

M996 0 16 13 3 6 24% 800 1450

M997 0 16 13 3 7 23% 850 1450

M998 0 16 13 4 5 24% 750 1500

M999 0 16 13 4 6 24% 750 1450

M 1000 0 16 13 5 5 24% 750 1500

M 1001 0 16 15 0 5 25% 750 1450

M 1002 0 16 15 0 6 25% 800 1450

M 1003 0 16 15 0 7 25% 900 1400

M 1004 0 16 15 1 5 25% 750 1450

M 1005 0 16 15 1 6 25% 800 1450

M 1006 0 16 15 1 7 25% 850 1400 M1007 0 16 15 2 5 25% 750 1450

M1008 0 16 15 2 6 25% 750 1450

M1009 0 16 15 3 5 25% 750 1450

M1010 0 16 15 3 6 25% 750 1450

M1011 0 16 15 4 5 25% 750 1450

M1012 0 19 7 0 6 23% 800 1500

M1013 0 19 7 0 7 22% 900 1450

M1014 0 19 7 1 6 23% 800 1500

M1015 0 19 7 1 7 22% 900 1450

M1016 0 19 7 2 6 23% 750 1500

M1017 0 19 7 2 7 22% 850 1450

M1018 0 19 7 2 8 22% 1000 1450

M1019 0 19 7 3 6 23% 750 1500

M1020 0 19 7 3 7 22% 850 1450

M1021 0 19 7 3 8 22% 950 1450

M1022 0 19 7 4 6 23% 750 1500

M1023 0 19 7 4 7 22% 850 1450

M1024 0 19 7 4 8 22% 950 1450

M1025 0 19 7 5 5 23% 750 1500

M1026 0 19 7 5 6 23% 750 1500

M1027 0 19 7 5 7 22% 800 1450

M1028 0 19 7 5 8 22% 950 1450

M1029 0 19 9 0 5 24% 750 1500

M1030 0 19 9 0 6 24% 800 1500

M1031 0 19 9 0 7 24% 900 1450

M1032 0 19 9 1 5 24% 750 1500

M1033 0 19 9 1 6 24% 750 1500

M1034 0 19 9 1 7 24% 850 1450

M1035 0 19 9 1 8 24% 1000 1400

M1036 0 19 9 2 5 24% 750 1500

M1037 0 19 9 2 6 24% 750 1500

M1038 0 19 9 2 7 24% 800 1450

M1039 0 19 9 2 8 24% 950 1400

M1040 0 19 9 3 5 24% 700 1500

M1041 0 19 9 3 6 24% 750 1500

M1042 0 19 9 3 7 24% 800 1450

M1043 0 19 9 3 8 24% 900 1400

M1044 0 19 9 4 5 24% 700 1500

M1045 0 19 9 4 6 24% 750 1500

M1046 0 19 9 4 7 24% 800 1450

M1047 0 19 9 5 5 24% 700 1500

M1048 0 19 9 5 6 24% 750 1500

M1049 0 19 11 0 5 26% 700 1500 M1050 0 19 11 0 6 25% 750 1450

M1051 0 19 11 0 7 25% 850 1450

M1052 0 19 11 0 8 25% 1000 1400

M1053 0 19 11 1 5 26% 700 1500

M1054 0 19 11 1 6 25% 750 1450

M1055 0 19 11 1 7 25% 800 1450

M1056 0 19 11 1 8 25% 950 1400

M1057 0 19 11 2 5 26% 700 1500

M1058 0 19 11 2 6 25% 750 1450

M1059 0 19 11 2 7 25% 800 1450

M1060 0 19 11 3 5 26% 700 1500

M1061 0 19 11 3 6 25% 750 1450

M1062 0 19 11 3 7 25% 800 1450

M1063 0 19 11 4 5 26% 700 1500

M1064 0 19 11 4 6 25% 750 1450

M1065 0 19 11 5 5 26% 700 1500

M1066 0 19 13 0 5 27% 700 1500

M1067 0 19 13 0 6 27% 750 1450

M1068 0 19 13 0 7 26% 800 1400

M1069 0 19 13 1 5 27% 700 1450

M1070 0 19 13 1 6 27% 750 1450

M1071 0 19 13 2 5 27% 700 1450

M1072 0 19 13 3 5 27% 700 1450

M1073 0 19 15 0 5 28% 700 1450

M1074 0 19 15 0 6 28% 750 1400

M1075 0 19 15 1 5 28% 700 1450

M1076 0 22 7 0 5 26% 700 1500

M1077 0 22 7 0 6 26% 750 1500

M1078 0 22 7 0 7 25% 850 1450

M1079 0 22 7 0 8 25% 1000 1400

M1080 0 22 7 1 5 26% 700 1500

M1081 0 22 7 1 6 26% 700 1500

M1082 0 22 7 1 7 25% 800 1450

M1083 0 22 7 1 8 25% 950 1400

M1084 0 22 7 2 5 26% 700 1500

M1085 0 22 7 2 6 26% 700 1500

M1086 0 22 7 2 7 25% 800 1450

M1087 0 22 7 2 8 25% 900 1400

M1088 0 22 7 3 5 26% 700 1500

M1089 0 22 7 3 6 26% 700 1500

M1090 0 22 7 3 7 25% 750 1450

M1091 0 22 7 4 5 26% 700 1500

M1092 0 22 7 4 6 26% 700 1500 M1093 0 22 7 5 5 26% 700 1500

M1094 0 22 9 0 5 27% 700 1500

M1095 0 22 9 0 6 27% 700 1450

M1096 0 22 9 0 7 27% 800 1450

M1097 0 22 9 0 8 26% 950 1400

M1098 0 22 9 1 5 27% 700 1500

M1099 0 22 9 1 6 27% 700 1450

M1100 0 22 9 1 7 27% 750 1450

M1101 0 22 9 2 5 27% 700 1500

M1102 0 22 9 2 6 27% 700 1450

M1103 0 22 9 3 5 27% 700 1500

M1104 0 22 9 3 6 27% 700 1450

M1105 0 22 9 4 5 27% 700 1500

M1106 0 22 11 0 5 29% 700 1500

M1107 0 22 11 0 6 28% 700 1450

M1108 0 22 11 1 5 29% 650 1500

M1109 0 22 13 0 5 30% 650 1450

M1110 0 25 7 0 5 29% 650 1500

Mllll 0 25 7 0 6 29% 700 1450

M1112 0 25 7 0 7 28% 750 1450

M1113 0 25 7 1 5 29% 650 1500

M1114 0 25 7 1 6 29% 650 1450

M1115 0 25 7 2 5 29% 650 1500

M1116 0 25 7 3 5 29% 650 1500

M1117 0 25 9 0 5 30% 650 1500

M1118 0 25 9 0 6 30% 650 1450

M1119 0 25 9 1 5 30% 650 1500

M1120 0.25 16 7 3 5 20% 750 1500

M1121 0.25 16 7 4 5 20% 750 1500

M1122 0.25 16 7 5 5 20% 750 1500

M1123 0.25 16 9 0 5 21% 800 1500

M1124 0.25 19 7 0 5 23% 750 1500

M1125 0.25 19 7 1 5 23% 750 1500

M1126 0.25 19 7 2 5 23% 750 1500

M1127 0.25 19 7 3 5 23% 750 1500

M1128 0.25 19 7 4 5 23% 700 1500

M1129 0.25 19 7 5 5 23% 700 1500

M1130 0.25 19 9 0 5 24% 750 1500

M1131 0.25 22 7 0 5 26% 700 1500

M1132 0.25 22 7 1 5 26% 700 1500

M1133 0.25 22 7 2 5 26% 700 1500

Ml 134 0.25 22 7 3 5 26% 700 1500

M1135 0.25 22 7 4 5 26% 700 1500 M 1136 0.25 22 7 5 5 26% 700 1500

M 1137 0.25 22 9 0 5 27% 700 1500

M 1138 0.25 25 7 0 5 29% 650 1500

M 1139 0.25 25 7 1 5 29% 650 1500

M l 140 0.25 25 7 2 5 29% 650 1500

M 1141 0.25 25 9 0 5 30% 650 1500

Applications and processes for use:

[0062] Embodiments of alloys disclosed herein can be used in a variety of applications and industries. Some non-limiting examples of applications of use include:

[0063] Surface mining applications including but not limited to the following components and coatings for the following components: wear resistant sleeves and/or wear resistant hardfacing for slurry pipelines, mud pump components including pump housing or impeller or hardfacing for mud pump components, ore feed chute components including chute blocks or hardfacing of chute blocks, separation screens including but not limited to rotary breaker screens, banana screens, and shaker screens, liners for autogenous grinding mills and semi-autogenous grinding mills, ground engaging tools and hardfacing for ground engaging tools, wear plate for buckets and dumptruck liners, heel blocks and hardfacing for heel blocks on mining shovels, grader blades and hardfacing for grader blades, stacker reclaimers, siazer crushers, general wear packages for mining components and other communition components.

[0064] Upstream oil and gas applications including but not limited to the following components and coatings for the following components: Downhole casing and downhole casing, drill pipe and coatings for drill pipe including hardbanding, mud management components, mud motors, tracking pump sleeves, tracking impellers, tracking blender pumps, stop collars, drill bits and drill bit components, directional drilling equipment and coatings for directional drilling equipment including stabilizers and centralizers, blow out preventers and coatings for blow out preventers and blow out preventer components including the shear rams, oil country tubular goods and coatings for oil country tubular goods.

[0065] Downstream oil and gas applications including but not limited to the following components and coatings for the following components: Process vessels and coating for process vessels including steam generation equipment, amine vessels, distillation towers, cyclones, catalytic crackers, general refinery piping, corrosion under insulation protection, sulfur recovery units, convection hoods, sour stripper lines, scrubbers, hydrocarbon drums, and other refinery equipment and vessels.

[0066] Pulp and paper applications including but not limited to the following components and coatings for the following components: Rolls used in paper machines including yankee dryers and other dryers, calendar rolls, machine rolls, press rolls, digesters, pulp mixers, pulpers, pumps, boilers, shredders, tissue machines, roll and bale handling machines, doctor blades, evaporators, pulp mills, head boxes, wire parts, press parts, M.G. cylinders, pope reels, winders, vacuum pumps, deflakers, and other pulp and paper equipment.

[0067] Power generation applications including but not limited to the following components and coatings for the following components: boiler tubes, precipitators, fireboxes, turbines, generators, cooling towers, condensers, chutes and troughs, augers, bag houses, ducts, ID fans, coal piping, and other power generation components.

[0068] Agriculture applications including but not limited to the following components and coatings for the following components: chutes, base cutter blades, troughs, primary fan blades, secondary fan blades, augers and other agricultural applications.

[0069] Construction applications including but not limited to the following components and coatings for the following components: cement chutes, cement piping, bag houses, mixing equipment and other construction applications.

[0070] Machine element applications including but not limited to the following components and coatings for the following components: Shaft journals, paper rolls, gear boxes, drive rollers, impellers, general reclamation and dimensional restoration applications and other machine element applications.

[0071] Steel applications including but not limited to the following components and coatings for the following components: cold rolling mills, hot rolling mills, wire rod mills, galvanizing lines, continue pickling lines, continuous casting rolls and other steel mill rolls, and other steel applications. [0072] Embodiments of alloys disclosed herein can be produced and or deposited in a variety of techniques effectively. Some non-limiting examples of processes include:

[0073] Thermal spray process including but not limited to those using a wire feedstock such as twin wire arc, spray, high velocity arc spray, combustion spray and those using a powder feedstock such as high velocity oxygen fuel, high velocity air spray, plasma spray, detonation gun spray, and cold spray. Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire. Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.

[0074] Welding processes including but not limited to those using a wire feedstock including but not limited to metal inert gas (MIG) welding, tungsten inert gas (TIG) welding, arc welding, submerged arc welding, open arc welding, bulk welding, laser cladding, and those using a powder feedstock including but not limited to laser cladding and plasma transferred arc welding. Wire feedstock can be in the form of a metal core wire, solid wire, or flux core wire. Powder feedstock can be either a single homogenous alloy or a combination of multiple alloy powder which result in the desired chemistry when melted together.

[0075] Casting processes including but not limited to processes typical to producing cast iron including but not limited to sand casting, permanent mold casting, chill casting, investment casting, lost foam casting, die casting, centrifugal casting, glass casting, slip casting and process typical to producing wrought steel products including continuous casting processes.

[0076] Post processing techniques including but not limited to but not limited to rolling, forging, surface treatments such as carburizing, nitriding, carbonitriding, heat treatments including but not limited to austenitizing, normalizing, annealing, stress relieving, tempering, aging, quenching, cryogenic treatments, flame hardening, induction hardening, differential hardening, case hardening, decarburization, machining, grinding, cold working, work hardening, and welding.

[0077] One of the more applicable uses of this technology is in applications where coatings are deposited on-site, in the field, or in locations where proper ventilation, dust collection, and other safety measures cannot be easily met. Some well-known non-limiting examples of these applications include power generation applications such as the coating of boiler tubes, upstream refinery applications such as the coating of refinery vessels, and pulp and paper applications such as the coating and grinding of yankee dryers.

Examples:

[0078] The following examples are intended to be illustrative and non-limiting. Example 1)

[0079] The previously disclosed alloy #4, Fe: BAL, Mn: about 5, Mo: about 13, Si: about 10 was produced in the form of a 40 gram trial ingot to verify hardness and thermal spray vitrification potential. The ingot hardness was measured to be 534 Vickers (converting from a Rockwell C measurement). The microstructure of the ingot showed a fully eutectic structure indicating a strong possibility for amorphous or nanocrystalline structure under the rapid cooling rate of the spray process. This material has been selected for manufacture into 1/16" cored thermal spray wire for twin wire arc spray trials after slight modification to the alloy #14, Fe: BAL, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2.

Example 2)

[0080] The previously presented alloy #5, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a 40 gram trial ingot to verify hardness and thermal spray vitrification potential. The ingot hardness was measured to be 534 Vickers (converting from a Rockwell C measurement). The microstructure of the ingot showed a fully eutectic structure indicating a strong possibility for amorphous or nanocrystalline structure under the rapid cooling rate of the spray process. This material has been selected for manufacture into 1/16" cored thermal spray wire for twin wire arc spray trials after slight modification to alloy #15, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.

Example 3)

[0081] The previously disclosed alloy #8, Fe: BAL, C: about 0.25, Mn: about 19, Mo: about 7, Si: about 5 was produced in the form of a 40 gram ingot to verify hardness, thermal spray vetrification potential and magnetic permeability. In this example, the alloy candidate is being developed as a 'readable' coating which requires the alloy to be nonmagnetic in the sprayed form. The ingot hardness was measured to be 300 Vickers (converting from a Rockwell C measurement). While this is below the desired hardness threshold, it is well known by those skilled in the art that the rapid cooling process achieved in thermal spray will increase the hardness of the alloy in this form. Thus, it is not unreasonable to expect an increase in hardness in the sprayed form up to the desired level of 400 Vickers. The relative magnetic permeability was measured via a Low-Mu Magnetic Permeability Tester and was determined to be less than 1.01, well below the threshold required to ensure 'readability' .

Example 4)

[0082] The previously disclosed alloy #5, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a cored thermal spray wire. This alloy was sprayed using the twin wire arc spray technique, specifically using the parameters shown in

Table 3. A series of tests were run to evaluate the alloys performance in reference to standard Cr-bearing thermal spray materials used for hardfacing. The specific alloy of reference is known by the commercial names, Armacor M, TAFA 95MXC, PMet 273, etc. and has an alloy composition of about Fe: BAL, Cr: 29, Si: 1, Mn: 2, B: 4. Table 2 highlights the result of the testing. As shown in Table 4, Alloy #5 has comparable adhesion and abrasion resistance as measure via ASTM G65B testing.

Table 2: List of properties of disclosed alloys in relation to Armacor M

Table 3: Spray parameters used in Example 4 and 5 testing

Example 5)

[0083] The previously disclosed alloy #4, Fe: BAL, Mn: about 5, Mo: about 7, Si: about 10 was produced in the form of a cored thermal spray wire. This alloy was sprayed using the twin wire arc spray technique using the parameters shown in

Table 3. Yankee dryers are typically sprayed using this parameter set. A series of tests were run to evaluate the alloys performance in reference to standard Cr-bearing thermal spray materials used for hardfacing similar to that described in Example 4. The preliminary results of this testing are shown in Table 2.

[0084] As shown, Alloy #4 replicates the key performance criteria of Armacor M in all key criteria. As Alloy #4 represents an exemplary embodiment of this disclosure, additional testing was performed in order to compare other performance criteria specifically as it relates to the coating of yankee dryers, a specific article of manufacture used in paper machines. This testing including corrosion testing, grinding studies, spray characteristics, thorough metallographic evaluation, and evaluation of surface properties as related to surface tension. In all cases, alloy #4 was deemed to have similar or better performance than the Armacor M coating.

[0085] Corrosion testing was conducted by exposing the coating to saltwater and measuring the voltage against a reference bare steel plate, which could be then used to place the material on the Galvanic Series. Both the Armacor M and Alloy #4 coatings showed significant rust on the coating surface after the 2 week test exposure. The position of the Armacor M coating on the galvanic series is -450 to -567 and the position of Alloy #4 is -510 to -640. Increasingly negative values reflect more active potentials, which is less desirable as it indicates reduced corrosion resistance. This represents a 'similarity' in that the quantified performance does not vary by more than 25%.

[0086] Grinding studies were performed due to its specific relevance to the yankee dryer application. In this application it is desirable for the coating to exhibit faster grinding times, as it reduces the downtime of the paper machine. Grinding times were quantified by removing a specific material thickness and measuring the tie to do so, as shown in

Table 4. As shown, Alloy #4 showed reduced grinding time, which is advantageous. Table 4: Grinding Study Measurements

Thickness Removed Time to Grind (sec)

Alloy #4 ARM-M % Change

5 mil 140s 150s 7.14%

10 mil 210s 210s 0%

15 mil 310s 345s 11.29%

20 mil 398s 488s 22.61%

[0087] The characteristics of the spray for both materials was also studied. It was evident that Alloy #4 produced significantly less dust during spraying than Armacor M, which is desirable. Metallographic examination also showed that less oxides were present in the Alloy #4 coating, 7% versus 13% in the Armacor M coating.

[0088] Finally the surface tension properties of each coating were evaluated. In the Yankee dryer application it is desirable for the coating to be hydrophilic, which enables the adsorption of water based organic compounds used in paper making into the surface. The contact angle that a water droplet makes on the surface can be used to quantify the surface tension of the material. The Armacor M water droplet formed a 63.9° angle, and Alloy #4 formed a 41.5° angle. A smaller angle indicates increased hydrophillicity, which is advantageous because in Yankee dryer applications, a monoammonium phosphate (MAP) water-based solution is typically sprayed onto the coating for paper release properties. It can be advantageous for this water-based solution to immerse itself into the coating structure and stick well to the coating surface, which can be enhanced by having a hydrophilic coating.

[0089] From the foregoing description, it will be appreciated that an inventive chromium free hardfacing alloy and method of manufacturing are disclosed. While several components, techniques and aspects have been described with a certain degree of particularity, it is manifest that many changes can be made in the specific designs, constructions and methodology herein above described without departing from the spirit and scope of this disclosure.

[0090] Certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Moreover, although features may be described above as acting in certain combinations, one or more features from a claimed combination can, in some cases, be excised from the combination, and the combination may be claimed as any subcombination or variation of any subcombination.

[0091] Moreover, while methods may be depicted in the drawings or described in the specification in a particular order, such methods need not be performed in the particular order shown or in sequential order, and that all methods need not be performed, to achieve desirable results. Other methods that are not depicted or described can be incorporated in the example methods and processes. For example, one or more additional methods can be performed before, after, simultaneously, or between any of the described methods. Further, the methods may be rearranged or reordered in other implementations. Also, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products. Additionally, other implementations are within the scope of this disclosure.

[0092] Conditional language, such as "can," "could," "might," or "may," unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include or do not include, certain features, elements, and/or steps. Thus, such conditional language is not generally intended to imply that features, elements, and/or steps are in any way required for one or more embodiments.

[0093] Conjunctive language such as the phrase "at least one of X, Y, and Z," unless specifically stated otherwise, is otherwise understood with the context as used in general to convey that an item, term, etc. may be either X, Y, or Z. Thus, such conjunctive language is not generally intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.

[0094] Language of degree used herein, such as the terms "approximately," "about," "generally," and "substantially" as used herein represent a value, amount, or characteristic close to the stated value, amount, or characteristic that still performs a desired function or achieves a desired result. For example, the terms "approximately", "about", "generally," and "substantially" may refer to an amount that is within less than or equal to 10% of, within less than or equal to 5% of, within less than or equal to 1% of, within less than or equal to 0.1% of, and within less than or equal to 0.01% of the stated amount. If the stated amount is 0 (e.g., none, having no), the above recited ranges can be specific ranges, and not within a particular % of the value. For example, within less than or equal to 10 wt./vol. % of, within less than or equal to 5 wt./vol. % of, within less than or equal to 1 wt./vol. % of, within less than or equal to 0.1 wt./vol. % of, and within less than or equal to 0.01 wt./vol. % of the stated amount.

[0095] Some embodiments have been described in connection with the accompanying drawings. The figures are drawn to scale, but such scale should not be limiting, since dimensions and proportions other than what are shown are contemplated and are within the scope of the disclosed inventions. Distances, angles, etc. are merely illustrative and do not necessarily bear an exact relationship to actual dimensions and layout of the devices illustrated. Components can be added, removed, and/or rearranged. Further, the disclosure herein of any particular feature, aspect, method, property, characteristic, quality, attribute, element, or the like in connection with various embodiments can be used in all other embodiments set forth herein. Additionally, it will be recognized that any methods described herein may be practiced using any device suitable for performing the recited steps.

[0096] While a number of embodiments and variations thereof have been described in detail, other modifications and methods of using the same will be apparent to those of skill in the art. Accordingly, it should be understood that various applications, modifications, materials, and substitutions can be made of equivalents without departing from the unique and inventive disclosure herein or the scope of the claims.

Claims

WHAT IS CLAIMED IS:

1. A work piece having at least one surface, the work piece comprising:

a coating applied to the at least one surface, the coating comprising an Fe- based alloy having substantially no chromium, having substantially no carbides, and having substantially no borides;

wherein the alloy comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.

2. The work piece of Claim 1 , wherein the coating comprises Fe and, in weight percent:

B: about 0-4;

C: about 0-0.25;

Si: about 0-15;

Mn: about 0 to 25;

Mo: about 0-29;

Nb: about 0-2;

Ta: about 0-4;

Ti: about 0-4;

V: about 0-10;

W: about 0-6;

Zr: about 0-10;

wherein B + C + Si is about 4-15; and

wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.

3. The work piece of Claim 1, wherein the coating comprises Fe and in weight percent:

C: about 0 to 0.25;

Mn: about 5 to 19;

Mo: about 7 to 23;

Ni: about 0 to 4; and

Si: about 5 to 10.

4. The work piece of Claim 1, wherein the coating comprises one or more of the following compositions in weight percent:

Fe, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2; or

Fe, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.

5. The work piece of Claim 1, wherein the coating is non-magnetic and the coating thickness can be accurately measured with an Elcometer™ thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less.

6. The work piece of Claim 1, wherein the coating is amorphous.

7. The work piece of Claim 1, wherein the coating is nanocrystalline, as defined by having a grain size of 100 nm or less.

8. The work piece of Claim 1, wherein the coating is applied via a thermal spray process.

9. The work piece of Claim 1, wherein the coating is applied via a twin wire arc spray process.

10. The work piece of Claim 1, wherein the work piece is a yankee dryer.

11. The work piece of Claim 1 , wherein the work piece is a roller used in a paper making machine.

12. An article of manufacture comprising:

an Fe-based coating having substantially no chromium;

wherein the coating possesses a melting temperature of 1500K or below;

wherein the coating possesses a large atom concentration of at least 5 atom %, large atoms being of the group consisting of Mn, Mo, Nb, Ta, Ti, V, W, and Zr; and wherein the coating is a primarily single phase fine-grained structure of either martensite, ferrite, or austenite.

13. The article of manufacture of Claim 12, wherein the coating comprises, in weight percent:

B: about 0-4;

C: about 0-0.25;

Si: about 0-15; Mn: about 0 to 25;

Mo: about 0-29;

Nb: about 0-2;

Ta: about 0-4;

Ti: about 0-4;

V: about 0-10;

W: about 0-6;

Zr: about 0-10;

wherein B + C + Si is about 4-15; and

wherein (Mo + Mn + Nb + Ta + Ti + V + W + Zr) is about 5 to 38.

14. The article of manufacture of Claim 12, wherein the coating comprises Fe and in weight percent:

C: about 0 to 0.25;

Mn: about 5 to 19;

Mo: about 7 to 23;

Ni: about 0 to 4; and

Si: about 5 to 10.

15. The work piece of Claim 12, wherein the coating comprises one or more of the following compositions in weight percent:

Fe, Mn: about 5, Mo: about 13, Si: about 10, Al: about 2; or

Fe, Mn: about 5, Mo: about 7, Si: about 10, Al: about 2.

16. The article of manufacture of Claim 12, wherein the coating is non-magnetic and the coating thickness can be accurately measured with an Elcometer™ thickness gauge or similar device after it has been exposed to temperatures exceeding about 1100 K for 2 hours or more and then slow cooled at a rate of lOK/s or less.

17. The article of manufacture of Claim 12, wherein the coating comprises a Vickers hardness of at least 500 and an adhesion strength of at least 5,000 psi.

18. The article of manufacture of Claim 12, wherein the coating is applied via the twin wire arc spray process.

19. The article of manufacture of Claim 12, wherein the coating is amorphous.

20. The article of manufacture of Claim 12, wherein the coating is nanocrystalline, as defined by having a grain size of 100 nm or less.

21. The article of manufacture of Claim 12, wherein the coating is applied via a thermal spray process.

22. The article of manufacture of Claim 12, wherein the coating is applied onto a roller used in a paper making machine.

23. The article of manufacture of Claim 12, wherein the coating is applied onto a Yankee Dryer.

24. The article of manufacture of Claim 12, wherein the coating is applied onto a boiler tube.

25. A work piece having at least one surface, the work piece comprising:

a coating applied to the at least one surface, the coating comprising an Fe- based alloy having less than 1 wt. % chromium, less than 5 vol. % carbides, and less than 5 vol. % borides;

26. The work piece of Claim 25, wherein the alloy has less than 1 vol. % carbides and less than 1 vol. % borides.