U.S. patent application number 14/434664 was filed with the patent office on 2015-10-01 for non-magnetic metal alloy compositions and applications.
The applicant listed for this patent is SCOPERTA, INC.. Invention is credited to Justin Lee Cheney, John Hamilton Madok, Kyle Walter Rafa.
Application Number | 20150275341 14/434664 |
Document ID | / |
Family ID | 50475474 |
Filed Date | 2015-10-01 |
United States Patent
Application |
20150275341 |
Kind Code |
A1 |
Cheney; Justin Lee ; et
al. |
October 1, 2015 |
NON-MAGNETIC METAL ALLOY COMPOSITIONS AND APPLICATIONS
Abstract
Disclosed are non-magnetic metal alloy compositions and
applications that relate to non-magnetic metal alloys with
excellent wear properties for use in dynamic three-body
tribological wear environments. In some embodiments, the disclosure
can relate to a drilling component for use in directional drilling
applications capable of withstanding service abrasion. In some
embodiments, a hardbanding for protecting a drilling component for
use in directional drilling can be provided. In some embodiments,
thermodynamic, microstructure, and performance criteria can be
determined for hardbanding alloys.
Inventors: |
Cheney; Justin Lee;
(Encinitas, CA) ; Madok; John Hamilton; (San
Diego, CA) ; Rafa; Kyle Walter; (Fremont,
CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SCOPERTA, INC. |
San Diego |
CA |
US |
|
|
Family ID: |
50475474 |
Appl. No.: |
14/434664 |
Filed: |
October 10, 2013 |
PCT Filed: |
October 10, 2013 |
PCT NO: |
PCT/US13/64391 |
371 Date: |
April 9, 2015 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61712716 |
Oct 11, 2012 |
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|
Current U.S.
Class: |
420/12 ; 420/10;
420/100; 420/54; 420/57; 420/73 |
Current CPC
Class: |
C22C 38/12 20130101;
C22C 38/36 20130101; C22C 38/46 20130101; C22C 38/18 20130101; C22C
38/44 20130101; C09D 1/00 20130101; B23K 35/004 20130101; C22C
29/14 20130101; C22C 38/28 20130101; C22C 32/0073 20130101; C22C
29/06 20130101; C22C 38/48 20130101; C22C 38/04 20130101; C22C
38/54 20130101; C22C 38/32 20130101; C22C 38/26 20130101; C22C
37/10 20130101; C22C 32/0052 20130101; C22C 38/38 20130101; C22C
38/22 20130101; C22C 38/02 20130101; C22C 38/24 20130101; C22C
38/58 20130101; B23K 35/308 20130101; C22C 38/56 20130101; C09D
5/00 20130101; C22C 38/14 20130101; C22C 37/08 20130101; C22C
38/002 20130101; C23C 30/00 20130101; C22C 38/50 20130101; C22C
38/08 20130101 |
International
Class: |
C22C 38/58 20060101
C22C038/58; C22C 37/10 20060101 C22C037/10; C22C 38/56 20060101
C22C038/56; C22C 38/54 20060101 C22C038/54; C22C 38/50 20060101
C22C038/50; C22C 38/48 20060101 C22C038/48; C22C 38/46 20060101
C22C038/46; C22C 38/44 20060101 C22C038/44; C22C 38/38 20060101
C22C038/38; C22C 38/36 20060101 C22C038/36; C22C 38/32 20060101
C22C038/32; C22C 38/28 20060101 C22C038/28; C22C 38/26 20060101
C22C038/26; C22C 38/24 20060101 C22C038/24; C22C 38/22 20060101
C22C038/22; C22C 38/14 20060101 C22C038/14; C22C 38/12 20060101
C22C038/12; C22C 38/08 20060101 C22C038/08; C22C 38/04 20060101
C22C038/04; C22C 38/02 20060101 C22C038/02; C22C 38/00 20060101
C22C038/00; C23C 30/00 20060101 C23C030/00; C22C 37/08 20060101
C22C037/08 |
Claims
1. A work piece having at least a portion of its surface covered by
a layer comprising an austenitic matrix microstructure containing
fine-scaled hard particles comprising one or more of boride,
carbide, borocarbide, nitride, carbonitride, aluminide, oxide,
intermetallic, and laves phase, wherein the layer comprises a
macro-hardness of 40 HRC or more and a relative magnetic
permeability of 1.02 or less.
2. The work piece of claim 1, wherein the macro-hardness of the
layer is 45 HRC or more.
3. The work piece of claim 2, wherein the macro-hardness of the
layer is between 45 and 60 HRC.
4. The work piece of claim 1, wherein the relative magnetic
permeability of the layer is 1.01 or less.
5. The work piece claim 1, wherein a surface of the of the layer
exhibits high wear resistance as characterized by an ASTM G65 dry
sand wear test mass loss of 1.5 grams or less.
6. The work piece of claim 5, wherein the surface of the layer
exhibits high wear resistance as characterized by an ASTM G65 dry
sand wear test mass loss of 0.35 grams or less.
7. The work piece of claim 1, wherein the surface of the layer has
a mass loss measured by ASTM G105 testing of below 0.5 grams.
8. The work piece of claim 1, wherein the austenitic matrix
contains fine-scaled hard particles up to 50 vol. % with average
sizes between 100 nm-20 .mu.m.
9. The work piece of claim 8, wherein the austenitic matrix
contains fine-scaled hard particles up to 30 vol. % with average
sizes between 1-5 .mu.m.
10. The work piece of claim 1, wherein the layer comprises in wt. %
of Mn: 8-20, Cr: 0-6, Nb: 2-8, V: 0-3, C: 1-6, B: 0-1.5, W: 0-10,
Ti: 0-0.5.
11. The work piece of claim 1, wherein the layer comprises in wt. %
of B: 0-1, C: 0.85-3, Cr: 0-20, Mn: 0-12, Nb: 0-4, Ni: 0-10, Ti:
0-6, V: 0-6, and W: 0-15.
12. The work piece of claim 1, wherein the alloy composition is
selected from group consisting of alloys comprising in wt. %: Fe:
bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 4, W: 5, Ti: 0.25; Fe: bal,
Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3.5, W: 5, Ti: 0.20; Fe: bal, Mn:
16, Cr: 5, Nb: 4, V: 0.5, C: 3.25, W: 5, Ti: 0.20; Fe: bal, Mn: 10,
Cr: 5, Nb: 4, V: 0.5, C: 3, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5,
Nb: 4, V: 0.5, C: 2.75, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb:
4, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb: 4,
Ni: 1, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb:
4, Ni: 3, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5,
Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr:
9, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10,
Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn:
10, Cr: 18, Nb: 4, Ni: 5, V: 0.5, C: 2, W: 5, Ti: 0.20; Fe: bal, B:
1, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 1, W: 5, Ti: 0.20; Fe:
bal, B: 1, Mn: 10, Cr: 18, Nb: 4, Ni: 10, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, B: 1, Mn: 10, Cr: 10, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, Mn: 4.7, Mo: 1.4, Ni: 7.2, Si: 1.1, Cr: 26.4, C:
1.9; Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 2.5, V: 0.5, C;
1.5, W: 4; Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 1, V: 0.5,
C: 1.5, W: 4; Fe: bal, C: 2.25, Cr: 20, Mn: 5, Nb: 4, Ni: 10, Ti:
0.2, V: 0.5, W: 4; Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 4; Fe:
bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4; Fe: bal, B: 0.5,
C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4; Fe: bal, C: 2, Cr: 18, Mn: 10,
Nb: 4, V: 6, W: 2; Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, V: 2; Fe:
bal, C: 3, Cr: 18, Mn: 10, Nb: 4, Ti: 2, V: 2, W: 4; and
combinations thereof.
13. The work piece of claim 1, wherein the layer does not contain
preformed carbides.
14. The work piece of claim 1, where the layer is used as a
hardfacing layer configured to protect oilfield components used in
directional drilling applications against abrasive wear.
15. A method of forming a coated work piece comprising: depositing
a layer on at least a portion of a surface of a work piece; wherein
the layer comprises an austenitic matrix microstructure containing
fine-scaled hard particles comprising one or more of boride,
carbide, borocarbide, nitride, carbonitride, aluminide, oxide,
intermetallic, and laves phase; and wherein the layer comprises a
macro-hardness of 40 HRC or more and a relative magnetic
permeability of 1.02 or less.
16. The method of claim 15, wherein the relative magnetic
permeability of the layer is 1.01 or less.
17. The method of claim 15, wherein the portion of the surface is
preheated to a temperature of 200.degree. C. or greater prior to
deposition of the layer.
18. The method of claim 15, wherein the layer is deposited in a
thickness of 1 mm to 10 mm.
19. The method of claim 15, further comprising cooling the layer at
a rate ranging from 50 to 5000 K/s.
20. The method of claim 15, wherein the layer comprises in wt. % of
Mn: 8-20, Cr: 0-6, Nb: 2-8, V: 0-3, C: 1-6, B: 0-1.5, W: 0-10, Ti:
0-0.5.
21. The method of claim 15, wherein the layer comprises in wt. % of
B: 0-1, C: 0.85-3, Cr: 0-20, Mn: 0-12, Nb: 0-4, Ni: 0-10, Ti: 0-6,
V: 0-6, and W: 0-15.
22. The method of claim 15, wherein the alloy composition is
selected from group consisting of alloys comprising in wt. %: Fe:
bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 4, W: 5, Ti: 0.25; Fe: bal,
Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3.5, W: 5, Ti: 0.20; Fe: bal, Mn:
16, Cr: 5, Nb: 4, V: 0.5, C: 3.25, W: 5, Ti: 0.20; Fe: bal, Mn: 10,
Cr: 5, Nb: 4, V: 0.5, C: 3, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5,
Nb: 4, V: 0.5, C: 2.75, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb:
4, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb: 4,
Ni: 1, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb:
4, Ni: 3, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5,
Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr:
9, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10,
Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn:
10, Cr: 18, Nb: 4, Ni: 5, V: 0.5, C: 2, W: 5, Ti: 0.20; Fe: bal, B:
1, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 1, W: 5, Ti: 0.20; Fe:
bal, B: 1, Mn: 10, Cr: 18, Nb: 4, Ni: 10, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, B: 1, Mn: 10, Cr: 10, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, Mn: 4.7, Mo: 1.4, Ni: 7.2, Si: 1.1, Cr: 26.4, C:
1.9; Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 2.5, V: 0.5, C;
1.5, W: 4; Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 1, V: 0.5,
C: 1.5, W: 4; Fe: bal, C: 2.25, Cr: 20, Mn: 5, Nb: 4, Ni: 10, Ti:
0.2, V: 0.5, W: 4; Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 4; Fe:
bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4; Fe: bal, B: 0.5,
C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4; Fe: bal, C: 2, Cr: 18, Mn: 10,
Nb: 4, V: 6, W: 2; Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, V: 2; Fe:
bal, C: 3, Cr: 18, Mn: 10, Nb: 4, Ti: 2, V: 2, W: 4; and
combinations thereof.
23. The method of claim 15, wherein the macro-hardness of the layer
is 40 HRC or more, the relative magnetic permeability of the layer
is 1.01 or less, a surface of the layer exhibits high wear
resistance as characterized by an ASTM G65 dry sand wear test mass
loss of 0.35 grams or less, and the austenitic matrix contains
fine-scaled hard boride, carbide, or boro-carbide particles up to
30 vol. % with average sizes between 1-5 .mu.m.
24. The method of claim 15, wherein the layer does not contain
preformed carbides.
25. A work piece having at least a portion of its surface covered
by a layer comprising an alloy having an FCC-BCC transition
temperature equal to or below 900-950K and an equilibrium total
concentration of hard precipitates greater than 20-30 mole percent
at a temperature of 1300K.
26. The work piece of claim 25, wherein the hard precipitates
comprise at least one of cementite, iron boride, (W,Fe)B, NbC,
(Nb,Ti)C, Ti.sub.2B, (Cr,Mn).sub.23(C,B).sub.6, Cr.sub.3C.sub.2,
Cr.sub.5Si, Cr.sub.2B, SiC, Mn.sub.7C.sub.3, W.sub.6C, WC, FeNbNi
laves, WFe laves and combinations thereof.
27. The work piece of claim 25, wherein the layer comprises in wt.
% of Mn: 8-20, Cr: 0-6, Nb: 2-8, V: 0-3, C: 1-6, B: 0-1.5, W: 0-10,
Ti: 0-0.5.
28. The work piece of claim 25, wherein the layer comprises in wt.
% of B: 0-1, C: 0.85-3, Cr: 0-20, Mn: 0-12, Nb: 0-6, Ni: 0-10, Ti:
0-6, V: 0-6, and W: 0-15.
29. The work piece of claim 25, wherein the FCC-BCC transition
temperature is equal to or below 850K.
30. The work piece of claim 25, wherein the equilibrium total
concentration of hard precipitates is great than 20 and less than
30 mole percent at a temperature of 1300K.
31. The work piece of claim 25, wherein the layer exhibits a
corrosion rate of less than 2 mils per year in water having 100,000
ppm NaCl, 500 ppm acetic acid, and 500 ppm sodium acetate in tap
water under ASTM G31.
32. The work piece of claim 25, wherein the layer comprises a
macro-hardness of 40 HRC or more, a relative magnetic permeability
of 1.01 or more, and exhibits high wear resistance as characterized
by ASTM G65 dry sand wear test mass loss of 0.35 grams or less.
33. An alloy comprising, in weight %: Fe: bal, B: 0-1, C: 0.85-3,
Cr: 0-20, Mn: 0-12, Nb: 0-4, Ni: 0-10, Ti: 0-6, V: 0-6, and W:
0-15; wherein the alloy comprises the following properties when
present in an undiluted form and cooled from a liquid state at a
rate of 50K/s or greater: a macro-hardness of 40 HRC or greater;
and a relative magnetic permeability of 1.02 or less.
34. The alloy of claim 33, wherein the alloy composition is
selected from group consisting of alloys comprising in wt. %: Fe:
bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 4, W: 5, Ti: 0.25; Fe: bal,
Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3.5, W: 5, Ti: 0.20; Fe: bal, Mn:
16, Cr: 5, Nb: 4, V: 0.5, C: 3.25, W: 5, Ti: 0.20; Fe: bal, Mn: 10,
Cr: 5, Nb: 4, V: 0.5, C: 3, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5,
Nb: 4, V: 0.5, C: 2.75, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb:
4, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb: 4,
Ni: 1, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5, Nb:
4, Ni: 3, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr: 5,
Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10, Cr:
9, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn: 10,
Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5, Ti: 0.20; Fe: bal, Mn:
10, Cr: 18, Nb: 4, Ni: 5, V: 0.5, C: 2, W: 5, Ti: 0.20; Fe: bal, B:
1, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 1, W: 5, Ti: 0.20; Fe:
bal, B: 1, Mn: 10, Cr: 18, Nb: 4, Ni: 10, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, B: 1, Mn: 10, Cr: 10, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20; Fe: bal, Mn: 4.7, Mo: 1.4, Ni: 7.2, Si: 1.1, Cr: 26.4, C:
1.9; Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 2.5, V: 0.5, C;
1.5, W: 4; Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 1, V: 0.5,
C: 1.5, W: 4; Fe: bal, C: 2.25, Cr: 20, Mn: 5, Nb: 4, Ni: 10, Ti:
0.2, V: 0.5, W: 4; Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 4; Fe:
bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4; Fe: bal, B: 0.5,
C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4; Fe: bal, C: 2, Cr: 18, Mn: 10,
Nb: 4, V: 6, W: 2; Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, V: 2; Fe:
bal, C: 3, Cr: 18, Mn: 10, Nb: 4, Ti: 2, V: 2, W: 4; and
combinations thereof.
35. The alloy of claim 33, wherein the alloy composition is tested
from a sample produced in an arc melting furnace with a chilled
copper base.
36. The method of claim 33, wherein the alloy composition is tested
from a sample sectioned from the top layer of a six layer weld.
Description
INCORPORATION BY REFERENCE TO ANY PRIORITY APPLICATIONS
[0001] Any and all applications for which a foreign or domestic
priority claim is identified in the Application Data Sheet as filed
with the present application are hereby incorporated by reference
under 37 CFR 1.57.
BACKGROUND
[0002] 1. Field
[0003] The disclosure relates to non-magnetic metal alloys with
excellent wear properties for use in dynamic three-body
tribological wear environments.
[0004] 2. Description of the Related Art
[0005] Conditions of abrasive wear can be damaging as they often
involve sand, rock particles, or other extremely hard media wearing
away against a surface. Applications which see severe abrasive wear
typically utilize materials of high hardness, 40 R.sub.c+,
encompassing hard metals or carbides.
[0006] In certain wear applications, e.g., exploration wells in
crude oil or natural gas fields such as directional bores and the
like, it is advantageous for drilling string components including
drill stems to be made of materials with magnetic permeability
values below 1.02 or possibly even less than 1.01 (API
Specification 7 regarding drill string components), in order to be
able to follow the exact position of the bore hole and to ascertain
and correct deviations from its projected course.
[0007] A number of disclosures are directed to non-magnetic alloys
for use in forming drilling components including U.S. Pat. No.
4,919,728 which details a method for manufacturing non-magnetic
drilling string components, and U.S. Patent Publication No.
2005/0047952 which describes a non-magnetic corrosion resistant
high strength steel, although both the patent and application
describe magnetic permeability of less than 1.01. Both the patent
and application are hereby incorporated by reference in their
entirety. The compositions described have a maximum of 0.15 wt. %
carbon, 1 wt. % silicon and no boron. The low levels and absence of
the above mentioned hard particle forming elements suggests that
the alloys would not precipitate sufficient, if any, hard
particles. It can be further expected that inadequate wear
resistance and hardness for high wear environments would be
provided.
[0008] Further, U.S. Pat. No. 4,919,728 describes alloys which
contain carbon levels below 0.25 wt. % while U.S. Patent
Publication No. 2005/0047952 details carbon levels below 0.1 wt. %.
With these levels of carbon in conjunction with the absence of
boron, few hard particles can form which impart wear resistance to
a hardband.
[0009] Also in U.S. Pat. No. 4,919,728, a method for cold working
at various temperatures is used to achieve the desired properties.
Cold working is not possible in coating applications such as
hardfacing. The size and geometry of the parts would require
excessive deformations loads as well as currently unknown methods
to uniformly cold work specialized parts such as tool joints.
[0010] Additionally, U.S. Patent Publication No. 2010/0009089,
hereby incorporated by reference in its entirety, details a
non-magnetic for coatings adapted for high wear applications where
non-magnetic properties are required. The alloys listed in this
publication are nickel-based with preformed tungsten carbide hard
spherical particles poured into the molten weld material during
welding in the amount of 30-60 wt. %.
[0011] Disclosures offering alloying solutions for competing wear
mechanisms in oil & gas drilling hardfacing applications
include but are not limited to U.S. Pat. Nos. 4,277,108; 4,666,797;
6,117,493; 6,326,582; 6,582,126; 7,219,727; and U.S. Patent
Publication No. 2002/0054972. U.S. Publication Nos. 2011/0220415
and 2011/004069 disclose an ultra-low friction coating for drill
stem assemblies. U.S. Pat. Nos. 6,375,895, 7,361,411, 7,569,286,
20040206726, 20080241584, and 2011/0100720 disclose the use of hard
alloys for the competing wear mechanisms. The patents and patent
applications listed in this paragraph are hereby incorporated by
reference in their entirety.
[0012] There is still a need for non-magnetic alloy compositions
for hardbanding components for use in directional drilling
applications that have resistance to abrasion. There is also a need
for an improved method to protect drill collars from heavy abrasion
during drilling operations.
SUMMARY
[0013] Disclosed herein are metallic alloys, work pieces having a
least a portion of its surface covered by a layer of a metallic
alloy, methods of manufacturing the alloys, methods of applying the
alloys to a work piece or other components, and uses of such alloys
in different applications. In one embodiment, a work piece can have
at least a portion of its surface covered by a layer which can
comprise an austenitic matrix microstructure containing fine-scaled
hard particles comprising one or more of boride, carbide,
borocarbide, nitride, carbonitride, aluminide, oxide,
intermetallic, or laves phase, wherein the layer comprises a
macro-hardness of 40 HRC or above and a relative magnetic
permeability of 1.02 or less.
[0014] In some embodiments, the macro-hardness of the layer can be
45 HRC or more. In some embodiments, the macro-hardness of the
layer can be between 45 and 60 HRC, or between 50 and 60 HRC. In
some embodiments, the relative magnetic permeability of the layer
can be 1.01 or less.
[0015] In some embodiments, a surface of the of the layer can
exhibit high wear resistance as characterized by an ASTM G65 dry
sand wear test mass loss of 1.5 grams or less. In some embodiments,
the surface of the layer can exhibit high wear resistance as
characterized by an ASTM G65 dry sand wear test mass loss of 0.35
grams or less. In some embodiments, the surface of the layer can
have a mass loss measured by ASTM G105 testing of below 0.5
grams.
[0016] In some embodiments, the austenitic matrix can contain
fine-scaled hard particles up to 50 vol. % with average sizes
between 100 nm-20 .mu.m. In some embodiments, the austenitic matrix
can contain fine-scaled hard particles up to 30 vol. % (or up to
about 30 vol. %) with average sizes between 1-5 .mu.m.
[0017] In some embodiments, the layer can comprise in wt. % of Fe:
bal, Mn: 8-20, Cr: 0-6, Nb: 2-8, V: 0-3, C: 1-6, B: 0-1.5, W: 0-10,
Ti: 0-0.5. In some embodiments, the layer can comprise in wt. % of
Fe: bal, B: 0-1, C: 0.85-3, Cr: 0-20, Mn: 0-12, Nb: 0-4, Ni: 0-10,
Ti: 0-6, V: 0-6, and W: 0-15. In some embodiments, the alloy
composition can be selected from group consisting of alloys
comprising in wt. %:
[0018] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 4, W: 5, Ti:
0.25;
[0019] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3.5, W: 5, Ti:
0.20;
[0020] Fe: bal, Mn: 16, Cr: 5, Nb: 4, V: 0.5, C: 3.25, W: 5, Ti:
0.20;
[0021] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20;
[0022] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 2.75, W: 5, Ti:
0.20;
[0023] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 2.5, W: 5, Ti:
0.20;
[0024] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 1, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0025] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 3, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0026] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0027] Fe: bal, Mn: 10, Cr: 9, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0028] Fe: bal, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0029] Fe: bal, Mn: 10, Cr: 18, Nb: 4, Ni: 5, V: 0.5, C: 2, W: 5,
Ti: 0.20;
[0030] Fe: bal, B: 1, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 1,
W: 5, Ti: 0.20;
[0031] Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, Ni: 10, V: 0.5, C: 3,
W: 5, Ti: 0.20;
[0032] Fe: bal, B: 1, Mn: 10, Cr: 10, Nb: 4, V: 0.5, C: 3, W: 5,
Ti: 0.20;
[0033] Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, V: 0.5, C: 3, W: 5,
Ti: 0.20;
[0034] Fe: bal, Mn: 4.7, Mo: 1.4, Ni: 7.2, Si: 1.1, Cr: 26.4, C:
1.9;
[0035] Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 2.5, V: 0.5, C;
1.5, W: 4;
[0036] Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 1, V: 0.5, C:
1.5, W: 4;
[0037] Fe: bal, C: 2.25, Cr: 20, Mn: 5, Nb: 4, Ni: 10, Ti: 0.2, V:
0.5, W: 4;
[0038] Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 4;
[0039] Fe: bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4;
[0040] Fe: bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4;
[0041] Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 6, W: 2;
[0042] Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, V: 2;
[0043] Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, Ti: 2, V: 2, W: 4; and
combinations thereof.
[0044] In some embodiments, the layer does not contain preformed
carbides. In some embodiments, the layer can be used as a
hardfacing layer configured to protect oilfield components used in
directional drilling applications against abrasive wear.
[0045] Disclosed is a method of forming a coated work piece which
can comprise depositing a layer on at least a portion of a surface
of a work piece, wherein the layer comprises an austenitic matrix
microstructure containing fine-scaled hard particles comprising one
or more of boride, carbide, borocarbide, nitride, carbonitride,
aluminide, oxide, intermetallic, and laves phase, and wherein the
layer comprises a macro-hardness of 40 HRC or above and a relative
magnetic permeability of 1.02 or less.
[0046] In some embodiments, the relative magnetic permeability of
the layer can be 1.01 or less. In some embodiments, the portion of
the surface can be preheated to a temperature of 200.degree. C. or
greater prior to deposition of the layer. In some embodiments, the
layer can be deposited in a thickness of 1 mm to 10 mm. In some
embodiments, the method can further comprise cooling the layer at a
rate ranging from 50 to 5000 K/s. In some embodiments, the layer
can comprise in wt. % of Fe: bal, Mn: 8-20, Cr: 0-6, Nb: 2-8, V:
0-3, C: 1-6, B: 0-1.5, W: 0-10, Ti: 0-0.5. In some embodiments, the
layer can comprise in wt. % of Fe: bal, B: 0-1, C: 0.85-3, Cr:
0-20, Mn: 0-12, Nb: 0-4, Ni: 0-10, Ti: 0-6, V: 0-6, and W: 0-15. In
some embodiments, the alloy composition can be selected from group
consisting of alloys comprising in wt. %:
[0047] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 4, W: 5, Ti:
0.25;
[0048] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3.5, W: 5, Ti:
0.20;
[0049] Fe: bal, Mn: 16, Cr: 5, Nb: 4, V: 0.5, C: 3.25, W: 5, Ti:
0.20;
[0050] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20;
[0051] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 2.75, W: 5, Ti:
0.20;
[0052] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 2.5, W: 5, Ti:
0.20;
[0053] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 1, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0054] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 3, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0055] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0056] Fe: bal, Mn: 10, Cr: 9, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0057] Fe: bal, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0058] Fe: bal, Mn: 10, Cr: 18, Nb: 4, Ni: 5, V: 0.5, C: 2, W: 5,
Ti: 0.20;
[0059] Fe: bal, B: 1, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 1,
W: 5, Ti: 0.20;
[0060] Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, Ni: 10, V: 0.5, C: 3,
W: 5, Ti: 0.20;
[0061] Fe: bal, B: 1, Mn: 10, Cr: 10, Nb: 4, V: 0.5, C: 3, W: 5,
Ti: 0.20;
[0062] Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, V: 0.5, C: 3, W: 5,
Ti: 0.20;
[0063] Fe: bal, Mn: 4.7, Mo: 1.4, Ni: 7.2, Si: 1.1, Cr: 26.4, C:
1.9;
[0064] Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 2.5, V: 0.5, C;
1.5, W: 4;
[0065] Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 1, V: 0.5, C:
1.5, W: 4;
[0066] Fe: bal, C: 2.25, Cr: 20, Mn: 5, Nb: 4, Ni: 10, Ti: 0.2, V:
0.5, W: 4;
[0067] Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 4;
[0068] Fe: bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4;
[0069] Fe: bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4;
[0070] Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 6, W: 2;
[0071] Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, V: 2;
[0072] Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, Ti: 2, V: 2, W: 4;
[0073] and combinations thereof.
[0074] In some embodiments, the macro-hardness of the layer can be
50 HRC or more, the relative magnetic permeability of the layer can
be 1.01 or less, a surface of the layer can exhibit high wear
resistance as characterized by an ASTM G65 dry sand wear test mass
loss of 0.35 grams or less, and the austenitic matrix can contain
fine-scaled hard boride, carbide, or boro-carbide particles up to
30 vol. % with average sizes between 1-5 .mu.m. In some
embodiments, the layer does not contain preformed carbides.
[0075] Also disclosed is a work piece which can have at least a
portion of its surface covered by a layer which can comprise an
alloy having an FCC-BCC transition temperature equal to or below
900-950K and an equilibrium total concentration of hard
precipitates greater than 20-30 mole percent at a temperature of
1300K.
[0076] In some embodiments, the hard precipitates can comprise at
least one of cementite, iron boride, (W,Fe)B, NbC, (Nb,Ti)C,
Ti.sub.2B, (Cr,Mn).sub.23(C,B).sub.6, Cr.sub.3C.sub.2, Cr.sub.5Si,
Cr.sub.2B, SiC, Mn.sub.7C.sub.3, W.sub.6C, WC, FeNbNi laves, WFe
laves and combinations thereof. In some embodiments, the layer can
comprise in wt. % of Fe: bal, Mn: 8-20, Cr: 0-6, Nb: 2-8, V: 0-3,
C: 1-6, B: 0-1.5, W: 0-10, Ti: 0-0.5. In some embodiments, the
layer can comprise in wt. % of Fe: bal, B: 0-1, C: 0.85-3, Cr:
0-20, Mn: 0-12, Nb: 0-4, Ni: 0-10, Ti: 0-6, V: 0-6, and W:
0-15.
[0077] In some embodiments, the FCC-BCC transition temperature can
be equal to or below 850K. In some embodiments, the equilibrium
total concentration of hard precipitates can be greater than 20 and
less than 30 mole percent at a temperature of 1300K. In some
embodiments, the layer exhibits a corrosion rate of 2 mils per year
or less in water having 100,000 ppm NaCl, 500 ppm acetic acid, and
500 ppm sodium acetate in tap water under ASTM G31. In some
embodiments, the layer can comprise a macro-hardness of 40 HRC or
more, a relative magnetic permeability of 1.01 or less, and can
exhibit high wear resistance as characterized by ASTM G65 dry sand
wear test mass loss of 0.35 grams or less.
[0078] Also disclosed is an alloy comprising, in weight %. Fe: bal,
B: 0-1, C: 0.85-3, Cr: 0-20, Mn: 0-12, Nb: 0-4, Ni: 0-10, Ti: 0-6,
V: 0-6, and W: 0-15, wherein the alloy comprises the following
properties when present in an undiluted form and cooled from a
liquid state at a rate of 50K/s or greater: a macro-hardness of 40
HRC or greater, and a relative magnetic permeability of 1.02 or
less.
[0079] In some embodiments, the alloy composition can be selected
from group consisting of alloys comprising in wt. %:
[0080] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 4, W: 5, Ti:
0.25;
[0081] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3.5, W: 5, Ti:
0.20;
[0082] Fe: bal, Mn: 16, Cr: 5, Nb: 4, V: 0.5, C: 3.25, W: 5, Ti:
0.20;
[0083] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 3, W: 5, Ti:
0.20;
[0084] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 2.75, W: 5, Ti:
0.20;
[0085] Fe: bal, Mn: 10, Cr: 5, Nb: 4, V: 0.5, C: 2.5, W: 5, Ti:
0.20;
[0086] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 1, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0087] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 3, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0088] Fe: bal, Mn: 10, Cr: 5, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0089] Fe: bal, Mn: 10, Cr: 9, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0090] Fe: bal, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 2.5, W: 5,
Ti: 0.20;
[0091] Fe: bal, Mn: 10, Cr: 18, Nb: 4, Ni: 5, V: 0.5, C: 2, W: 5,
Ti: 0.20;
[0092] Fe: bal, B: 1, Mn: 10, Cr: 12, Nb: 4, Ni: 5, V: 0.5, C: 1,
W: 5, Ti: 0.20;
[0093] Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, Ni: 10, V: 0.5, C: 3,
W: 5, Ti: 0.20;
[0094] Fe: bal, B: 1, Mn: 10, Cr: 10, Nb: 4, V: 0.5, C: 3, W: 5,
Ti: 0.20;
[0095] Fe: bal, B: 1, Mn: 10, Cr: 18, Nb: 4, V: 0.5, C: 3, W: 5,
Ti: 0.20;
[0096] Fe: bal, Mn: 4.7, Mo: 1.4, Ni: 7.2, Si: 1.1, Cr: 26.4, C:
1.9;
[0097] Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 2.5, V: 0.5, C;
1.5, W: 4
[0098] Fe: bal, Mn: 10, Cr: 16.5, Mo: 0, Nb: 3, Ni: 1, V: 0.5, C:
1.5, W: 4
[0099] Fe: bal, C: 2.25, Cr: 20, Mn: 5, Nb: 4, Ni: 10, Ti: 0.2, V:
0.5, W: 4
[0100] Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 4
[0101] Fe: bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4
[0102] Fe: bal, B: 0.5, C: 1.5, Cr: 18, Mn: 10, Nb: 4, W: 4
[0103] Fe: bal, C: 2, Cr: 18, Mn: 10, Nb: 4, V: 6, W: 2
[0104] Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, V: 2
[0105] Fe: bal, C: 3, Cr: 18, Mn: 10, Nb: 4, Ti: 2, V: 2, W: 4
[0106] and combinations thereof.
[0107] In some embodiments, the alloy composition can be tested
from a sample produced in an arc melting furnace with a chilled
copper base. In some embodiments, the alloy composition is tested
from a sample sectioned from the top layer of a six layer weld.
BRIEF DESCRIPTION OF THE DRAWINGS
[0108] FIG. 1A illustrates a scanning electron micrograph at
500.times. magnification of an austenitic alloy demonstrating
large, interconnected carbides providing paths for crack
propagation.
[0109] FIG. 1B illustrates an optical micrograph of an embodiment
of the alloy in the disclosure which demonstrates finely
distributed hard particles in a soft austenitic matrix.
[0110] FIG. 2 illustrates a magnetic permeability survey showing
the permeability of an embodiment of the present disclosure.
[0111] FIG. 3 illustrates a magnetic field gradient survey showing
the uniformity of the magnetic field of an embodiment of the
present disclosure.
[0112] FIG. 4 illustrates a stainless steel tool joint welded with
an embodiment of the present disclosure with 3 parallel beads.
[0113] FIG. 5 illustrates the microstructure of an embodiment of a
weld bead of FIG. 4 examined with optical micrographs at 500.times.
magnification.
[0114] FIG. 6 illustrates a solidification diagram of Alloy 1
showing the FCC to BCC transition temperature.
[0115] FIG. 7 illustrates a scanning electron micrograph of Alloy
17 deposited as a single layer MIG weld on a stainless steel
plate.
[0116] FIG. 8 illustrates a scanning electron micrograph of Alloy
18 deposited as a single layer MIG weld on a stainless steel
plate.
DETAILED DESCRIPTION
[0117] The present disclosure relates to a non-magnetic metal alloy
for use in single or multi-stage tribological processes involving
multiple bodies of varying hardness, and applications employing the
metal alloy, e.g., hardbanding (or hardfacing) applications. For
example, the disclosure can be used to manufacture a coating for a
drilling component for use in directional drilling applications
capable of withstanding service abrasion. The drilling component
can have at least one surface protected by, for example, a welded
layer comprising one of the metal alloy compositions disclosed
below. In some embodiments, the disclosure can be defined by the
alloy compositions and compositional ranges which meet certain
thermodynamic, microstructural, and performance criteria.
[0118] The following terms will be used throughout the
specification and will have the following meanings unless otherwise
indicated.
[0119] "Casing" as used herein is defined as a metal pipe or tube
used as a lining for water, oil, or gas well.
[0120] "Coating" as used herein is comprised of one or more
adjacent layers and any included interfaces. Coating also refers to
a layer placed directly on the substrate of a base body assembly to
be protected, or the hardbanding placed on a base substrate
material. In another embodiment, "coating" refers to the top
protective layer. "Coating" may be used interchangeably with
"hardbanding," as defined below.
[0121] A "layer" as used herein is a thickness of a material that
may serve a specific functional purpose such as reduced coefficient
of friction, high stiffness, or mechanical support for overlying
layers or protection of underlying layers.
[0122] "Hardband" (or "hardface") as used herein refers to a
process to deposit a layer of a special material, e.g., super hard
metal, onto drill pipe tool joints, collars and heavy weight pipe
in order to protect both the casing and drill string components
from wear associated with drilling practices. "Hardbanding" (or
"hardband" or "hardfacing") as used herein refers to a layer of
superhard material to protect at least a portion of the underlying
equipment or work piece, e.g., tool joint, from wear such as casing
wear. Hardbanding can be applied as an outermost protective layer,
or an intermediate layer interposed between the outer surface of
the body assembly substrate material and the buttering layer(s),
buffer layer, or a coating.
[0123] "Hard particles" as used herein include but are not limited
to any single or combination of hard boride, carbide, borocarbide,
nitride, carbonitride, aluminide, oxide, intermetallic, or laves
phase. In some embodiments, hard particles can be one of cementite,
iron boride, (W,Fe)B, NbC, (Nb,Ti)C, Ti.sub.2B,
(Cr,Mn).sub.23(C,B).sub.6, Cr.sub.3C.sub.2, Cr.sub.5Si, Cr.sub.2B,
SiC, Mn.sub.7C.sub.3, W.sub.6C, WC, FeNbNi laves, WFe laves and
combinations thereof.
[0124] "As-welded" as used herein refers to the condition of a weld
without work hardening, heat treating, etc. or any other process
which alter the properties or microstructure through post-welding
processing.
[0125] The terms "approximately", "about", and "substantially" as
used herein represent an amount close to the stated amount that
still performs a desired function or achieves a desired result. For
example, the terms "approximately", "about", and "substantially"
may refer to an amount that is within less than 10% of, within less
than 5% of, within less than 1% of, within less than 0.1% of, and
within less than 0.01% of the stated amount.
Metal Alloy Composition
[0126] Embodiments of a metal alloy for hardfacing can be
characterized as having an austenitic microstructure (face centered
cubic gamma phase) and comprising, in wt. %: Mn: 8-20 (or about 8
to about 20), Cr: 0-6 (or about 0 to about 6), Nb: 2-8 (or about 2
to about 8), V: 0-3 (or about 0 to about 3), C: 1-6 (or about 1 to
about 6), B: 0-1.5 (or about 0 to about 1.5), W: 0-10 (or about 0
to about 10), Ti: 0-0.5 (or about 0 to about 0.5), balance Fe and
impurities as trace elements. The alloy may comprise Mn, Cr, Nb, V,
C, B, W, Ti, Fe, and impurities. Embodiments of a non-magnetic
composition can have minimal, if any, cracking in the coating and a
high resistance to abrasive wear.
[0127] In some embodiments, the alloy can be composed of the
followings in wt. %:
[0128] Fe: bal, Mn: 10 (or about 10), Cr: 5 (or about 5), Nb: 4 (or
about 4), V: 0.5 (or about 0.5), C: 4 (or about 4), W: 5 (or about
5), Ti: 0.25 (or about 0.25);
[0129] Fe: bal, Mn: 10 (or about 10), Cr: 5 (or about 5), Nb: 4 (or
about 4), V: 0.5 (or about 0.5), C: 3.5 (or about 3.5), W: 5 (or
about 5), Ti: 0.20 (or about 0.20);
[0130] Fe: bal, Mn: 16 (or about 16), Cr: 5 (or about 5), Nb: 4 (or
about 4), V: 0.5 (or about 0.5), C: 3.25 (or about 3.25), W: 5 (or
about 5), Ti: 0.20 (or about 0.20);
[0131] Fe: bal, Mn: 10 (or about 10), Cr: 5 (or about 5), Nb: 4 (or
about 4), V: 0.5 (or about 0.5), C: 3 (or about 3), W: 5 (or about
5), Ti: 0.20 (or about 0.20);
[0132] Mn: 8-16 (or about 8 to about 16), Cr: 3-6 (or about 3 to
about 6), Nb: 3-6 (or about 3 to about 6), V: 0-1 (or about 0 to
about 1), C: 1.5-5 (or about 1.5 to about 5), B: 0-1.5 (or about 0
to about 1.5), W: 3-6 (or about 3 to about 6), Ti: 0-0.5 (or about
0 to about 0.5), balance Fe and impurities as trace elements;
and
[0133] B: 0-1 (or about 0 to about 1), C: 1.5-3 (or about 1.5 to
about 3), Cr: 0-20 (or about 0 to about 20), Mn: 0-10 (or about 0
to about 10), Nb: 0-4 (or about 0 to about 4), Ni: 0-10 (or about 0
to about 10), Ti: 0-5 (or about 0 to about 5), V: 0-5 (or about 0
to about 5), W: 0-15 (or about 0 to about 15). The above alloys may
comprise Mn, Cr, Nb, Ni, V, C, W, Ti, B, Fe, and impurities, and
combinations thereof.
[0134] In some embodiments, combinations of the above described
alloy compositions can be used. Embodiments of alloys described
above can incorporate the above elemental constituents a total of
100 wt. %. In some embodiments, the alloy may include, may be
limited to, or may consist essentially of the above named elements.
In some embodiments, the alloy may include 2% (or about 2%) or less
of impurities. Impurities may be understood as elements or
compositions that may be included in the alloys due to inclusion in
the feedstock components, through introduction in the manufacturing
process. In another embodiment, the feedstock can contain silicon
in the amount such that the final alloy contains 0.15 wt. % (or
about 0.15 wt. %) although the ingot form did not contain any.
[0135] In some embodiments of the present disclosure, hard
particles can be precipitated from molten metal during
solidification of the alloy. In some embodiments, the austenitic
microstructure of the above described alloys can contain embedded
hard particles in an amount of 50 vol. % (or about 50 vol. %) or
less. Accordingly, the soft austenite matrix of the alloy can
provide toughness and ductility, while the precipitated hard
particles can impart wear resistance. The soft matrix can further
prevent spalling of the hard particles. The fine distribution of
hard particles can also allow for uniform wear and prevents
selective wear of the soft matrix.
[0136] Other alloys, such as those listed in U.S. Patent
Publication No. 2010/0009089, hereby incorporated by reference in
its entirety, use preformed carbides or borides which are poured
into the solidifying metal during welding. These carbides and
borides are larger where the particle size ranges from 50-180 (or
about 50 to about 180) .mu.m. Particles this large often spall due
to poor adhesion with the matrix and break leading to reduced wear
resistance. Further, using preformed carbides requires a large
hopper directly above the welding arc in order to feed the
particles into the molten weld. In this process, feeding the
carbides into the weld too quickly or too slowly can be detrimental
to the performance of the weld. Also, not only does the welding
wire need to be purchased, but preformed carbides as well
increasing the overall cost of applying the hardface. On the other
hand, embodiments of alloys described in the present disclosure can
be deposited using standard welding process without feeding
preformed carbides into the weld. This simplifies the application
process allowing for more uniform and repeatable hardfaced layers
both on a single part and between multiple parts.
[0137] In some embodiments, the metal alloy can be applied as a
coating of Fe-based (austenitic) matrix containing fine-scaled hard
boride, carbide, and complex carbide or boro-carbide particles,
e.g., borocarbide particles (e.g., M.sub.2B or MC, where M is a
transition metal) having average particle sizes of 100 nm-20 .mu.m
(or about 100 nm to about 20 .mu.m), in an amount of 50 vol. % (or
about 50 vol. %) or less. In another embodiment, the hard particles
are present in an amount of 30 vol. % (or about 30 vol. %) or less.
In some embodiments, the carbide particles have an average particle
size of 1-5 (or about 1 to about 5) .mu.m.
[0138] In some embodiments, the boride phase can be represented as
M.sub.2B, wherein M is a transition metal. In some embodiments, the
embedded hard particles in the austenitic Fe-based matrix can
contain Nb, Cr, and W with both carbon and/or boron. In some
embodiments, the particles can be in the form of embedded Nb
carbide and Fe--W-boro carbide precipitates. In another embodiment,
the Nb carbide precipitates are 5 .mu.m (or about 5 .mu.m) or less
in size. In some embodiments, the Nb carbide precipitates first at
higher temperatures, acting as a site for lower temperature forming
carbides to nucleate.
Method for Designing Hardbanding
[0139] In some embodiments, the alloy may be formed by blending
various feedstock materials together, which may then be melted in a
hearth or furnace and formed into ingots. The ingots can be
re-melted and flipped one or more times, which may increase
homogeneity of the ingots.
[0140] Each ingot produced was evaluated by examining its
microstructure, hardness and magnetic permeability. Incremental
changes in composition were made in each successive ingot, leading
to the final alloys. The compositions of the ingots made are listed
in Table I.
TABLE-US-00001 TABLE I Ingot Compositions amounts in weight percent
Alloy Name Fe Mn Cr Nb V C B W Si Ti Ni A1 54.5 2 18 4 2 1.25 0.85
7 0.15 0.25 10 A2 60.5 2 15 4 2 1.25 0.85 7 0.15 0.25 7 A3 60.25 2
15 4 2 1.5 0.85 7 0.15 0.25 7 A4 60.5 2 15 4 2 1 1.1 7 0.15 0.25 7
A5 60.25 2 15 4 2 1 1.35 7 0.15 0.25 7 A6 60 2 15 4 2 1 1.6 7 0.15
0.25 7 A7 59.2 2 15 4.3 2 1.5 1.6 7 0.15 0.25 7 A8 79.1 1.5 5 4 0.5
1.5 1 5 0.15 0.25 2 A9 78.31 2.50 4.95 3.96 0.50 1.49 1.00 4.95
0.15 0.25 2.00 A10 76.74 2.45 4.85 3.88 0.49 1.46 0.98 4.85 0.15
0.24 4 A11 75.21 2.40 4.75 3.80 0.48 1.43 0.96 4.75 0.14 0.24 6.00
A12 72.58 6.00 4.59 3.67 0.46 1.38 0.93 4.59 0.14 0.23 5.79 A13
65.25 10.00 5 4 0.5 1.5 1 5 1.5 0.25 6.00 A14 72.75 10 5 4 0.5 1.5
1 5 0 0.25 0 A15 72.25 10 5 4 0.5 1 1 5 1 0.25 0 A16 72.00 10 5 4
0.5 1.25 1 5 1 0.25 0 A17 71.28 11.00 4.95 3.96 0.50 1.24 0.99 4.95
0.99 0.25 0.00 A18 69.85 13.00 4.85 3.88 0.49 1.21 0.97 4.85 0.97
0.24 0.00 A19 69.25 12 5 4 0.5 1.5 1 5 1.5 0.25 0 A20 68.75 12 5 4
0.5 1.5 1.5 5 1.5 0.25 0 A21 70.25 12 5 4 0.5 2 1 5 0 0.25 0 A22
68.8 14.0 4.9 3.9 0.5 2.0 1.0 4.9 0.0 0.2 0.0 A23 67.00 16.00 4.80
3.84 0.48 1.92 0.96 4.80 0.00 0.24 0.00 A24 67.80 16.00 5.00 4.00
0.50 1.50 0.00 5.00 0.00 0.20 0.00 A25 66.80 16.00 5.00 4.00 0.50
2.50 0.00 5.00 0.00 0.20 0.00 A26 66.30 16.00 5.00 4.00 0.50 3.00
0.00 5.00 0.00 0.20 0.00 A27 72.80 10.00 5.00 4.00 0.50 2.50 0.00
5.00 0.00 0.20 0.00 A28 72.30 10.00 5.00 4.00 0.50 2.50 0.50 5.00
0.00 0.20 0.00 A29 69.41 9.60 4.80 3.84 0.48 2.40 0.48 9.00 0.00
0.19 0.00 A30 72.80 10.00 5.00 4.00 0.50 0.50 2.00 5.00 0.00 0.20
0.00 A31 68.23 16.00 4.60 3.66 0.47 0.47 1.88 4.70 0.00 0.19 0.00
A32 65.30 16.00 5.00 4.00 0.50 4.00 0.00 5.00 0.00 0.20 0.00 A33
71.30 10 5.00 4.00 0.50 4.00 0.00 5.00 0.00 0.20 0.00 A34 71.80 10
5.00 4.00 0.50 3.50 0.00 5.00 0.00 0.20 0.00 A35 72.30 10 5.00 4.00
0.50 3.00 0.00 5.00 0.00 0.20 0.00 A36 72.05 10 5.00 4.00 0.50 3.25
0.00 5.00 0.00 0.20 0.00 A37 65.80 10.00 12.00 4.00 0.50 2.50 0.00
5.00 0.00 0.20 0.00
[0141] Each composition after melting into ingot form was sectioned
on a wet abrasive saw as to avoid heating the ingot and
subsequently altering the microstructure. The magnetic permeability
was measured using a Low-Mu Magnetic Permeability Tester
manufactured by Severn Engineering. A reference standard with a
known magnetic permeability was placed in the tester. The tester
was comprised of the reference standard and a pivoting magnet. The
magnet extended from the side of the tester opposite the reference
standard. The magnet tip was brought into contact with the surface
of the ingot. If the magnet was not attracted to the ingot, then
the magnetic permeability was less than that of the reference
standard being used. The magnetic permeability of each ingot
composition is listed in Table II.
TABLE-US-00002 TABLE II Magnetic Permeability and Hardness Alloy
Name Magnetic Permeability. Hardness (HRc) A1 no 24 A2 no 29 A3 no
33 A4 yes 27.5 A5 no 31 A6 no 32 A7 no 35 A8 Yes NA A9 Yes NA A10
Yes NA A11 Yes NA A12 >1.04 NA A13 <1.03 34 A14 <1.02 53.5
A15 >1.04 47 A16 >1.04 NA A17 >1.04 43 A18 <1.02 38 A19
>1.04 46.5 A20 >1.04 NA A21 >1.04 56 A22 <1.03 57.5 A23
>1.04 60 A24 <1.01 29 A25 <1.01 37 A26 <1.01 40 A27
<1.01 35 A28 <1.01 48 A29 <1.01 36 A30 >1.04 54 A31
>1.04 35 A32 <1.01 50 A33 <1.01 52 A34 <1.02 41 A35
<1.01 41.5 A36 <1.01 46 A37 <1.01 39
[0142] After magnetic permeability was measured, each ingot
composition was tested for hardness using a Rockwell C hardness
tester. An average of 5 hardness measurements was recorded as the
hardness of that ingot. The hardness of each ingot composition is
detailed in Table II. Ingots A1-A11 were made prior to having a
magnetic permeability test method. Therefore, they were evaluated
using a hand-magnet as either magnetic or non-magnetic, and only
those alloys showing no magnetism using the hand magnet were
hardness tested.
[0143] Achieving both a sufficiently low magnetic permeability and
high as-welded hardness can be difficult, as non-magnetic austenite
is softer than the magnetic ferrite. For example, if a magnetic and
a non-magnetic alloy with the same volume percentage of hard
particles is examined, the non-magnetic alloy will be significantly
softer. However, as shown in Table II, embodiments of the present
disclosure can achieve both high hardness and low magnetic
permeability.
[0144] The microstructure of each ingot was evaluated by optical
microscopy. Embodiments of the disclosed alloys can contain a
sufficient amount of the ductile austenite matrix along with
embedded hard particles. Furthermore, a large volume fraction of
finely distributed hard particles can be found in embodiments of
the disclosed alloys. Large interconnected hard particles can be
undesirable due to increasing the brittleness of the ingot, as
shown in FIG. 1A. Fine disconnected hard particles, as shown in
FIG. 1B which is an embodiment of the disclosed alloys, can reduce
or eliminate paths for crack propagation, thereby decreasing the
likelihood of cracking during the welding process or in
service.
Properties
[0145] A work piece having at least a portion of its surface coated
or having a welded layer of the austenitic alloy composition, e.g.,
a hardbanding layer, can be characterized as having an as-welded
macro-hardness as measured via standard Rockwell C test of 40
R.sub.c, 45 R.sub.c, or 50 R.sub.c (or about 40 R.sub.c, about 45
R.sub.c, or about 50 R.sub.c) or greater.
[0146] The alloy composition as deposited on the surface of a work
piece can be characterized as being crack-free, as inspected by any
of magnetic particle inspection, eddy current inspection, etching,
visual inspection, hardness checking, dye penetration inspection,
or ultrasound inspection. The absence of cracks in the coating can
protect the underlying part from exposure to any corrosive media
present.
[0147] When applied as coatings, e.g., hardbanding, for protection
of work pieces, the fine-grained microstructural features in
embodiments of the above disclosed alloy can provide durability and
prevent wear on secondary "softer" bodies which come into contact
with the work piece protected by the coatings. However, when the
hardbanding material comes into contact with some softer materials,
such as mild steel, the hardbanding alloy may not aggressively
grind away the mild steel. This grinding away commonly happens in
drilling environments where a hardbanded pipe is run inside a mild
steel casing. Hardbands with preformed carbides, due to the large
size of the carbides, can aggressively cut away at the casing,
creating problems.
[0148] According to embodiments of the disclosure, the component
protected by the alloy can be characterized as having elevated wear
resistance with a dry sand abrasion mass loss (ASTM G65-04
procedure A, hereby incorporated by reference in its entirety) of
0.6 grams (or about 0.6 grams) or less, or 0.35 grams (or about
0.35 grams) or less. Further, under a modified ASTM G77 test, where
the load is increased up to 5000 lb./ft. (or about 5000 lb./ft.),
and mineral oil is used as a lubricant, embodiments of the present
disclosure can generate 1 mg (or about 1 mg) or less of material
loss on casing steel.
[0149] Embodiments of the above disclosed alloys can have low
magnetic permeability as well. Magnetic permeability is the measure
of how well a material can support a magnetic field within it. The
relative magnetic permeability of a vacuum is 1. For example, an
austenite phase described as a component of this disclosure can be
naturally paramagnetic. However, ferrite, which composes typical
hardbanding applications, is ferromagnetic. When a magnet is
brought into close proximity or contact with a ferromagnetic
hardband, it exhibits attractive forces. A magnet exhibits no
detectable attraction to an entirely austenitic material.
[0150] The definition of a non-magnetic material suitable for use
on a drill collar is <1.01 according to API Specification 7.
Even slight amounts of ferrite or martensite in a mainly austenitic
material can cause the magnetic permeability to exceed 1.01, and
therefore embodiments of the disclosed alloy can avoid the
formation of ferrite or martensite in a mainly austenitic material.
Ferrite and martensite can increased the overall permeability as
they have a magnetic permeability greater than 50 depending on the
alloy composition.
[0151] The alloy composition in some embodiments can be further
characterized as having magnetic permeability values (using a
Low-Mu Permeability Tester) of 1.02 or less, 1.01 or less, or 1.005
or less (or about 1.02 or less, about 1.01 or less, or about 1.005
or less). The alloy when applied as hardbanding on drill stem
components can provide paramagnetic behavior for the operator to be
able to monitor the progress of the bore hole required in
directional drillings. In some embodiments, the magnetic
permeability was measured at a commercial testing facility and the
results are illustrated in FIG. 2. As shown in FIG. 2, the results
stayed below 1.01 (or below about 1.01).
[0152] A magnetic field gradient is a measure of the uniformity of
the magnetic field. In some embodiments, embodiments of the above
described alloys can maintain a magnetic field gradient of .+-.0.05
(or .+-.about 0.05) microtesla which can meet the requirements of
API Specification 7, hereby incorporated by reference in its
entirety. In some embodiments, the commercially measured magnetic
field gradient was <0.05 microtesla (or <about 0.05
microtesla). In some embodiments, no hot spots exceeding the 0.05
microtesla (or about 0.05 microtesla) range were found. This
indicates a uniform magnetic field, as shown in FIG. 3. In some
embodiments, alloys can have a magnetic field strength of 0.95 (or
about 0.95 microtesla) or above.
Example
[0153] The following example is intended to be non-limiting.
[0154] An alloy composition of Alloy 1 (Mn: 10%, Cr: 5%, Nb: 4%, V:
0.5%, C: 3.5%, W: 5%, Ti: 0.25%, Fe: balance) was produced in the
form of a 1/16'' cored wire. The alloy was arc-welded onto a 65/8''
outer diameter box Stainless Steel tool joint pre-heated to
450.degree. F. The joint was rotated at a rotation rate of one full
rotation every 2 min and 30 sec. The welding parameters are 290
amps, 29.5 volts and a 1'' wire stickout. The welding head was
moved through the action of an oscillator at a rate of 58
cycle/min, resulting in a weld bead approximately 1'' wide and
4/32'' thick. Three consecutive beads were made, one next to
another to produce three adjacent 1'' beads for a total width of
roughly 3''. The joint was wrapped in insulation to reduce the
cooling rate and allowed to cool to room temperature. The as-welded
tool joint can be seen in FIG. 4
[0155] The microstructure of the weld bead was examined with
optical micrographs as shown in FIG. 5. A section of a weld was
taken and wear tested producing an ASTM G65 wear loss of 0.35 g (or
about 0.35 g). Relative magnetic permeability was measured with a
probe and provided a value of less than 1.01 (or less than about
1.01). Rockwell C hardness was measured at 43 (or about 43).
Thermodynamic, Microstructural, and Performance Criteria
Analysis
[0156] In some embodiments, alloys, such as the ones disclosed
above, can be defined by the specific compositions and
compositional ranges which meet certain thermodynamic,
microstructural, and performance criteria outlined in the below
disclosure. A listing of potential alloy compositions can be
created that comply partially or fully with different
thermodynamic, microstructural, and performance criteria.
Metal Alloy Composition
[0157] Certain metal alloy compositions can be achieved that result
in certain desired performances. These metal alloys can be created,
for example, by looking at thermodynamic and microstructural
criteria. While the explicit criteria are further defined below,
this section discusses the alloy compositions that at least
partially meet those criteria.
[0158] Table III shows a series of alloy compositions evaluated
using both modeling and experimental techniques. As discussed
below, T.sub..gamma..fwdarw..alpha. is the FCC to BCC transition
temperature, .SIGMA..sub.hard is the summed fraction of hard phases
at 1300K (or about 1300K), .mu. is the relative magnetic
permeability, and HRC is the Rockwell C hardness.
[0159] The 33 alloys shown in Table III meet at least some of the
performance, microstructural, and thermodynamic criteria further
described below (64.5% meet all criteria). Because there is such a
high correlation between the alloys meeting all of the criteria
(64.5%), if an alloy meets one of these criteria classes, it is
highly likely that it meets all the described criteria,
thermodynamic, microstructural, and performance.
[0160] After producing a table meeting the below described
criteria, a general alloy composition can be determined. For
example, based at least in part on Table III, and the manufacturing
variances of selected wires, an alloy composition that will meet
the described criteria can comprise B, C, Cr, Mn, Nb, Ni, Ti, V, W,
Fe, and impurities, and combinations thereof, and can contain in
wt. %:
[0161] B: 0-1 (or about 0 to about 1), C: 0.85-3 (or about 0.85 to
about 3), Cr: 2-27 (or about 2 to about 27), Mn: 0-12 (or about 0
to about 12), Nb: 0-4 (or about 0 to about 4), Ni: 0-10 (or about 0
to about 10), Ti: 0-2 (or about 0 to about 2), V: 0-6 (or about 0
to about 6), W: 0-5 (or about 0 to about 5), and Fe: bal.
[0162] In some embodiments, the alloy can be described by a series
of compositional ranges which meet the specified thermodynamic
criteria. A listing of specific alloy compositions which meet the
specified thermodynamic criteria, described below, are listed in
Table IV. Based at least in part on Table IV, an alloy composition
can comprise C, Cr, Mn, Nb, Ni, Ti, V, W, Fe, and impurities, and
combinations thereof, and can contain in wt. %:
[0163] C: 1.5-3 (or about 1.5 to about 3), Cr: 0-20 (or about 0 to
about 20), Mn: 0-10 (or about 0 to about 10), Nb: 0-4 (or about 0
to about 4), Ni: 0-10 (or about 0 to about 10), Ti: 0-0.2 (or about
0 to about 0.2), V: 0-0.5 (or about 0 to about 0.5), W: 0-5 (or
about 0 to about 5), and Fe: bal.
[0164] In some embodiments, B can be added to the composition for
the purposes of increasing hardness and wear resistance, while not
affecting the magnetic properties of the material. Based at least
in part on Table IV, an alloy composition having B can comprise B,
C, Cr, Mn, Nb, Ni, Ti, V, W, Fe, and impurities, and combinations
thereof, and can contain in wt. %:
[0165] B: 0-1 (or about 0 to about 1), C: 1.5-3 (or about 1.5 to
about 3), Cr: 0-20 (or about 0 to about 20), Mn: 0-10 (or about 0
to about 10), Nb: 0-4 (or about 0 to about 4), Ni: 0-10 (or about 0
to about 10), Ti: 0-0.2 (or about 0 to about 0.2), V: 0-0.5 (or
about 0 to about 0.5), W: 0-5 (or about 0 to about 5), and Fe:
bal.
[0166] In some embodiments, the summed Mn+Ni concentration does not
fall below 10 wt. % (or below about 10 wt. %).
[0167] Further described are certain compositional ranges using
Table IV that can meet the below described criteria. Non-limiting
examples of such alloy compositions can comprise C, Cr, Mn, Nb, Ni,
Ti, V, W, Fe, and impurities, and combinations thereof, and can
contain in wt. %:
[0168] C: 1.5-3 (or about 1.5 to about 3), Cr: 0-20 (or about 0 to
about 20), Mn: 10 (or about 10), Nb: 0-4 (or about 0 to about 4),
Ni: 0-10 (or about 0 to about 10), Ti: 0-0.2 (or about 0 to about
0.2), V: 0-0.5 (or about 0 to about 0.5), W: 0-5 (or about 0 to
about 5), and Fe: bal.
[0169] C: 1.5-3 (or about 1.5 to about 3), Cr: 0-20 (or about 0 to
about 20), Mn: 5 (or about 5), Nb: 0-4 (or about 0 to about 4), Ni:
5-10 (or about 5 to about 10), Ti: 0-0.2 (or about 0 to about 0.2),
V: 0-0.5 (or about 0 to about 0.5), W: 0-5 (or about 0 to about 5),
and Fe: bal.
[0170] C: 1.5-2.25 (or about 1.5 to about 2.25), Cr 0-20 (or about
0 to about 20), Nb: 0-4 (or about 0 to about 4), Ni: 10 (or about
10), Ti: 0-0.2 (or about 0 to about 0.2), V: 0-0.5 (or about 0 to
about 0.5), W: 0-5 (or about 0 to about 5), and Fe: bal.
[0171] In some embodiments, the Ti, V, and/or W concentration can
be increased for the purposes of increasing the hard particle
fraction, while not affecting the magnetic properties of the
material. Based at least in part on Table III, Table IV, and the
manufacturing variances of selected wires the alloy can comprise B,
C, Cr, Mn, Nb, Ni, Ti, V, W, Fe, and impurities, and can contain,
in wt. %:
[0172] B: 0-1 (or about 0 to about 1), C: 0.85-3 (or about 0.85 to
about 3), Cr: 0-20 (or about 0 to about 20), Mn: 0-10 (or about 0
to about 10), Nb: 0-4 (or about 0 to about 4), Ni: 0-10 (or about 0
to about 10), Ti: 0-6 (or about 0 to about 6), V: 0-6 (or about 0
to about 6), W: 0-15 (or about 0 to about 15), and Fe: bal.
[0173] In some embodiments the alloys can be described by the
measured chemical compositions of manufactured 1/16'' metal cored
wires. Alloys 1, 8, 14, 15, 22, and 23 were produced in the form of
1/16'' metal cored wires for the purposes of weld testing. Each
wire chemistry was measured using inductively coupled plasma
optical emission spectroscopy and a LECO carbon analyzer. The
results of the analysis for each material are described below in
weight %:
[0174] Alloy 1: Al: 0.09, B: 0.01, C: 3.13, Cr: 5.52, Cu: 0.03, Mo:
0.02, Mn: 9.58, Nb: 3.85,
[0175] Ni: 0.01, P: 0.016, S: 0.006, Si: 0.17, Ti: 0.18, V: 0.51,
W: 4.88;
[0176] Alloy 8: Al: 0.08, B: 0.01, C: 2.61, Cr: 11.95, Cu: 0.09,
Mo: 0.03, Mn: 9.97, Nb: 4.00,
[0177] Ni: 4.84, P: 0.016, S: 0.007, Si: 0.49, Ti: 0.29, V: 0.61,
W: 4.36;
[0178] Alloy 14 (run 1): Al: 0.04, B: 0.01, C: 1.75, Cr: 14.60, Cu:
0.21, Mo: 0.13, Mn: 7.66,
[0179] Nb: 2.81, Ni: 5.22, P: 0.019, S: 0.007, Si: 0.64, Ti: 0.12,
V: 0.39, W: 3.58;
[0180] Alloy 14 (run 2): B: 0.01, C: 2.06, Co: 0.29, Cr: 14.93, Cu:
0.32, Mo: 0.24, Mn: 9.28,
[0181] Nb: 3.89, Ni: 5.69, P: 0.260, S: 0.006, Si: 0.41, Ti: 0.27,
V: 0.46, W: 5.84;
[0182] Alloy 15: Al: 0.05, B: 0.98, C: 0.85, Co: 0.03, Cr: 12.38,
Cu: 0.12, Mo: 0.03, Mn: 9.36,
[0183] Nb: 3.79, Ni: 5.40, P: 0.030, S: 0.006, Si: 0.39, Ti: 0.18,
V: 0.77, W: 4.55;
[0184] Alloy 22: B: 0.02, C: 1.87, Co: 0.09, Cr: 26.44, Cu: 0.27,
Mo: 4.68, Mn: 4.68, Ni: 7.19,
[0185] P: 0.024, S: 0.007, Si: 1.09, Ti: 0.01, V: 0.08, W:
0.04;
[0186] Alloy 23: B: 0.01, C: 1.74, Co: 0.02, Cr: 18.6, Cu: 0.20,
Mo: 0.04, Mn: 11.16, Nb: 3.63,
[0187] Ni: 1.02, P: 0.270, S: 0.006, Si: 0.39, Ti: 0.17, V: 0.77,
W: 4.55
[0188] In all cases, the balance is Fe. Due to the manufacturing
process, Al, B, Co, Cu, Mo, Ni, P, S, and W have been added in
measurable quantities in alloys where the nominal composition does
not contain these elements. In some embodiments, the alloys were
present in their undiluted form and cooled from a liquid state at a
rate of 50K/s or greater. In all cases, the alloys were welded onto
test coupons and were shown to exhibit at least the minimum
performance criteria of 40 HRC or greater and a relative magnetic
permeability of below 1.02. In some embodiments, the alloy
composition was tested from a sample produced in an arc melting
furnace with a chilled copper base. In some embodiments, the alloy
composition was tested from a sample sectioned from the top layer
of a six layer weld.
TABLE-US-00003 TABLE III Comparison of Performance Criteria with
Thermodynamic Criteria for Selected Alloy Chemistries Alloys which
do not meet the performance criteria have been indicated with an
(*). Fe represents the balance of all alloy chemistries Alloy B C
Cr Mn Mo Nb Ni Si Ti V W T.sub..gamma..fwdarw..alpha.
.SIGMA..sub.hard .mu. HRC 1 0 3 5 10 0 4 0 0 0.2 0.5 5 870 31.86%
<1.01 46.0 2 0 2.75 5 10 0 4 0 0 0.2 0.5 5 850 32.43% <1.01
40.0 3 0 2.5 5 10 0 4 0 0 0.2 0.5 5 910 40.66% <1.01 41.0 4 0
2.5 5 10 0 4 1 0 0.2 0.5 5 920 33.10% <1.01 41.7 5 0 2.5 5 10 0
4 3 0 0.2 0.5 5 920 30.09% <1.01 40.0 6 0 2.5 5 10 0 4 5 0 0.2
0.5 5 920 30.77% <1.01 40.0 7 0 2.5 9 10 0 4 5 0 0.2 0.5 5 830
12.82% <1.01 42.7 8 0 2.5 12 10 0 4 5 0 0.2 0.5 5 870 28.37%
<1.01 43.2 9* 0 2 12 10 0 4 5 0 0.2 0.5 5 860 25.64% <1.01
35.7 10* 0 1.5 12 10 0 4 5 0 0.2 0.5 5 840 12.50% <1.01 36.2 11*
0 1 12 10 0 4 5 0 0.2 0.5 5 860 20.59% <1.01 27.8 12* 0 1 12 10
0 4 5 0.5 0.2 0.5 5 860 22.93% <1.01 28.5 13* 0 1 12 10 0 4 5 1
0.2 0.5 5 840 12.07% <1.01 31.2 14 0 2 18 10 0 4 5 0 0.2 0.5 5
860 20.13% <1.01 41.2 15 1 1 12 10 0 4 5 0 0.2 0.5 5 880 27.87%
<1.01 45.2 16* 0 2 18 10 0 0 5 0 0 0 0 870 23.71% <1.01 35.8
17 1 3 18 10 0 4 10 0 0.2 0.5 5 833 51.69% <1.02 50.4 18* 1 1.5
2 10 0 4 2 0 0.2 0.5 5 917 21.42% >1.04 41.8 19 1 3 10 10 0 4 0
0 0.2 0.5 5 953 49.42% <1.01 60.0 20 1 3 18 10 0 4 0 0 0.2 0.5 5
941 56.21% <1.02 59.8 21* 1 1.5 2 10 0 4 10 0 0.2 0.5 5 863
22.23% >1.04 36.0 22 0 1.9 26.4 4.7 1.4 0 7.2 1.1 0 0 0 873
31.61% <1.01 47.0 23 0 1.5 16.5 10 0 3 2.5 0 0.2 0.5 4 800 31%
<1.01 43.0 24 0 1.5 16.5 10 0 3 1 0 0.2 0.5 4 850 26% <1.01
41.0 25 0 2.25 20 5 0 4 10 0 0.2 0.5 4 900 37% <1.01 41.0 26* 0
1.5 20 0 0 0 10 0 0.2 0.5 4 900 29% <1.01 32.6 27 1 2.5 18 10 0
4 0 0 0 4 4 900 48% <1.01 51.3 28 0 2 18 10 0 4 0 0 0 4 0 900
28% <1.01 45.3 29 0.5 1.5 18 10 0 4 0 0 0 0 4 900 29% <1.01
49.3 30 0 2 18 10 0 4 0 0 0 6 2 750 28% <1.01 47.5 31* 0.5 1.5
18 10 0 4 0 0 0 0 0 900 22% >1.04 35.3 32 0 3 18 10 0 4 0 0 0 2
0 900 34% <1.01 45.3 33 0 3 18 10 0 4 0 0 2 2 4 900 43% <1.01
44.7
TABLE-US-00004 TABLE IV Disclosed Alloy Chemistries which Meet
Thermodynamic Criteria Alloy Fe B C Cr Mn Nb Ni Ti V W
T.gamma..fwdarw..alpha. .SIGMA..sub.hard 34 48.3 0 3 20 10 4 10 0.2
0.5 4 850 42% 35 50.3 0 3 20 10 2 10 0.2 0.5 4 850 41% 36 52.3 0 3
20 10 0 10 0.2 0.5 4 850 41% 37 49.05 0 2.25 20 10 4 10 0.2 0.5 4
850 38% 38 54.3 0 3 20 10 0 10 0.2 0.5 2 850 38% 39 50.3 0 3 20 10
4 10 0.2 0.5 2 850 37% 40 52.3 0 3 20 10 2 10 0.2 0.5 2 850 37% 41
56.3 0 3 20 10 0 10 0.2 0.5 0 850 37% 42 51.05 0 2.25 20 10 2 10
0.2 0.5 4 850 37% 43 54.3 0 3 20 10 2 10 0.2 0.5 0 850 37% 44 52.3
0 3 20 10 4 10 0.2 0.5 0 850 36% 45 53.05 0 2.25 20 10 0 10 0.2 0.5
4 850 36% 46 51.05 0 2.25 20 10 4 10 0.2 0.5 2 850 34% 47 53.05 0
2.25 20 10 2 10 0.2 0.5 2 850 32% 48 58.3 0 3 10 10 4 10 0.2 0.5 4
850 32% 49 55.05 0 2.25 20 10 0 10 0.2 0.5 2 850 31% 50 53.8 0 1.5
20 10 0 10 0.2 0.5 4 850 29% 51 57.05 0 2.25 20 10 0 10 0.2 0.5 0
850 28% 52 55.8 0 1.5 20 10 0 10 0.2 0.5 2 850 28% 53 55.05 0 2.25
20 10 2 10 0.2 0.5 0 850 28% 54 53.05 0 2.25 20 10 4 10 0.2 0.5 0
850 27% 55 51.8 0 1.5 20 10 2 10 0.2 0.5 4 850 27% 56 56.8 0 1.5 20
10 2 5 0.2 0.5 4 850 26% 57 53.8 0 1.5 20 10 2 10 0.2 0.5 2 850 26%
58 59.05 0 2.25 10 10 4 10 0.2 0.5 4 850 25% 59 58.8 0 1.5 20 10 2
5 0.2 0.5 2 850 25% 60 49.8 0 1.5 20 10 4 10 0.2 0.5 4 850 24% 61
54.8 0 1.5 20 5 4 10 0.2 0.5 4 850 24% 62 55.8 0 1.5 20 10 2 10 0.2
0.5 0 850 24% 63 54.8 0 1.5 20 10 4 5 0.2 0.5 4 850 24% 64 51.8 0
1.5 20 10 4 10 0.2 0.5 2 850 23% 65 53.8 0 1.5 20 10 4 10 0.2 0.5 0
850 23% 66 58.8 0 1.5 20 10 4 5 0.2 0.5 0 850 22% 67 53.3 0 3 20 10
4 5 0.2 0.5 4 900 44% 68 55.3 0 3 20 10 2 5 0.2 0.5 4 900 43% 69
57.3 0 3 20 10 0 5 0.2 0.5 4 900 42% 70 56.05 0 2.25 20 10 2 5 0.2
0.5 4 900 39% 71 55.3 0 3 20 10 4 5 0.2 0.5 2 900 38% 72 57.3 0 3
20 10 2 5 0.2 0.5 2 900 38% 73 58.05 0 2.25 20 10 0 5 0.2 0.5 4 900
38% 74 54.05 0 2.25 20 10 4 5 0.2 0.5 4 900 37% 75 59.3 0 3 20 10 0
5 0.2 0.5 2 900 37% 76 54.05 0 2.25 20 5 4 10 0.2 0.5 4 900 37% 77
61.3 0 3 20 10 0 5 0.2 0.5 0 900 36% 78 59.05 0 2.25 20 10 4 0 0.2
0.5 4 900 36% 79 56.05 0 2.25 20 10 4 5 0.2 0.5 2 900 36% 80 56.05
0 2.25 20 5 2 10 0.2 0.5 4 900 36% 81 59.3 0 3 20 10 2 5 0.2 0.5 0
900 36% 82 59.05 0 2.25 20 0 4 10 0.2 0.5 4 900 35% 83 57.3 0 3 20
10 4 5 0.2 0.5 0 900 35% 84 61.05 0 2.25 20 10 4 0 0.2 0.5 2 900
35% 85 58.05 0 2.25 20 5 0 10 0.2 0.5 4 900 35% 86 61.05 0 2.25 20
0 2 10 0.2 0.5 4 900 35% 87 63.05 0 2.25 20 0 0 10 0.2 0.5 4 900
34% 88 58.05 0 2.25 20 10 2 5 0.2 0.5 2 900 34% 89 62.3 0 3 10 10 0
10 0.2 0.5 4 900 33% 90 60.3 0 3 10 10 2 10 0.2 0.5 4 900 32% 91
60.05 0 2.25 20 10 0 5 0.2 0.5 2 900 32% 92 64.3 0 3 10 10 0 10 0.2
0.5 2 900 32% 93 56.05 0 2.25 20 5 4 10 0.2 0.5 2 900 32% 94 62.3 0
3 10 10 2 10 0.2 0.5 2 900 31% 95 67.3 0 3 10 10 0 5 0.2 0.5 4 900
31% 96 66.3 0 3 10 10 0 10 0.2 0.5 0 900 31% 97 60.3 0 3 10 10 4 10
0.2 0.5 2 900 31% 98 65.3 0 3 10 10 2 5 0.2 0.5 4 900 31% 99 58.05
0 2.25 20 5 2 10 0.2 0.5 2 900 31% 100 63.3 0 3 10 10 4 5 0.2 0.5 4
900 31% 101 64.3 0 3 10 10 2 10 0.2 0.5 0 900 31% 102 69.3 0 3 10
10 0 5 0.2 0.5 2 900 31% 103 61.05 0 2.25 20 0 4 10 0.2 0.5 2 900
30% 104 62.3 0 3 10 10 4 10 0.2 0.5 0 900 30% 105 60.05 0 2.25 20 5
0 10 0.2 0.5 2 900 30% 106 67.3 0 3 10 10 2 5 0.2 0.5 2 900 30% 107
79.3 0 3 0 10 0 5 0.2 0.5 2 900 30% 108 63.05 0 2.25 20 0 2 10 0.2
0.5 2 900 30% 109 81.3 0 3 0 10 0 5 0.2 0.5 0 900 30% 110 71.3 0 3
10 10 0 5 0.2 0.5 0 900 30% 111 65.05 0 2.25 20 0 0 10 0.2 0.5 2
900 30% 112 65.3 0 3 10 10 4 5 0.2 0.5 2 900 30% 113 69.3 0 3 10 10
2 5 0.2 0.5 0 900 30% 114 77.3 0 3 0 10 0 5 0.2 0.5 4 900 30% 115
67.3 0 3 10 10 4 5 0.2 0.5 0 900 29% 116 58.8 0 1.5 20 5 0 10 0.2
0.5 4 900 29% 117 63.8 0 1.5 20 0 0 10 0.2 0.5 4 900 29% 118 62.05
0 2.25 20 5 0 10 0.2 0.5 0 900 28% 119 58.8 0 1.5 20 10 0 5 0.2 0.5
4 900 28% 120 60.05 0 2.25 20 5 2 10 0.2 0.5 0 900 28% 121 77.3 0 3
0 10 2 5 0.2 0.5 2 900 28% 122 58.05 0 2.25 20 10 4 5 0.2 0.5 0 900
27% 123 79.3 0 3 0 10 2 5 0.2 0.5 0 900 27% 124 62.05 0 2.25 20 10
0 5 0.2 0.5 0 900 27% 125 63.05 0 2.25 20 0 4 10 0.2 0.5 0 900 27%
126 58.05 0 2.25 20 5 4 10 0.2 0.5 0 900 27% 127 75.3 0 3 0 10 2 5
0.2 0.5 4 900 27% 128 60.8 0 1.5 20 10 0 5 0.2 0.5 2 900 27% 129
63.8 0 1.5 20 10 0 0 0.2 0.5 4 900 27% 130 60.05 0 2.25 20 10 2 5
0.2 0.5 0 900 27% 131 56.8 0 1.5 20 5 2 10 0.2 0.5 4 900 26% 132
61.8 0 1.5 20 0 2 10 0.2 0.5 4 900 26% 133 61.8 0 1.5 20 5 2 5 0.2
0.5 4 900 26% 134 65.8 0 1.5 20 10 0 0 0.2 0.5 2 900 26% 135 64.05
0 2.25 10 5 4 10 0.2 0.5 4 900 26% 136 58.8 0 1.5 20 5 2 10 0.2 0.5
2 900 26% 137 60.8 0 1.5 20 5 0 10 0.2 0.5 2 900 26% 138 66.05 0
2.25 10 5 2 10 0.2 0.5 4 900 25% 139 64.05 0 2.25 10 10 4 5 0.2 0.5
4 900 25% 140 63.8 0 1.5 20 0 2 10 0.2 0.5 2 900 25% 141 68.05 0
2.25 10 5 0 10 0.2 0.5 4 900 25% 142 66.05 0 2.25 10 10 2 5 0.2 0.5
4 900 25% 143 61.8 0 1.5 20 10 2 0 0.2 0.5 4 900 25% 144 67.8 0 1.5
20 10 0 0 0.2 0.5 0 900 25% 145 61.05 0 2.25 10 10 2 10 0.2 0.5 4
900 25% 146 77.3 0 3 0 10 4 5 0.2 0.5 0 900 24% 147 75.3 0 3 0 10 4
5 0.2 0.5 2 900 24% 148 68.05 0 2.25 10 10 0 5 0.2 0.5 4 900 24%
149 63.05 0 2.25 10 10 0 10 0.2 0.5 4 900 24% 150 59.8 0 1.5 20 0 4
10 0.2 0.5 4 900 24% 151 60.8 0 1.5 20 10 2 5 0.2 0.5 0 900 24% 152
65.8 0 1.5 20 0 0 10 0.2 0.5 2 900 24% 153 63.8 0 1.5 20 10 2 0 0.2
0.5 2 900 24% 154 73.3 0 3 0 10 4 5 0.2 0.5 4 900 24% 155 59.8 0
1.5 20 5 4 5 0.2 0.5 4 900 24% 156 65.05 0 2.25 10 10 0 10 0.2 0.5
2 900 24% 157 70.05 0 2.25 10 5 0 10 0.2 0.5 2 900 23% 158 63.05 0
2.25 10 10 2 10 0.2 0.5 2 900 23% 159 75.05 0 2.25 10 0 0 10 0.2
0.5 2 900 23% 160 56.8 0 1.5 20 5 4 10 0.2 0.5 2 900 23% 161 68.05
0 2.25 10 5 2 10 0.2 0.5 2 900 23% 162 61.8 0 1.5 20 0 4 10 0.2 0.5
2 900 23% 163 61.05 0 2.25 10 10 4 10 0.2 0.5 2 900 23% 164 66.05 0
2.25 10 5 4 10 0.2 0.5 2 900 23% 165 67.05 0 2.25 10 10 0 10 0.2
0.5 0 900 23% 166 62.8 0 1.5 20 10 0 5 0.2 0.5 0 900 23% 167 72.05
0 2.25 10 5 0 10 0.2 0.5 0 900 23% 168 59.8 0 1.5 20 10 4 0 0.2 0.5
4 900 23% 169 65.05 0 2.25 10 10 2 10 0.2 0.5 0 900 23% 170 70.05 0
2.25 10 5 2 10 0.2 0.5 0 900 23% 171 65.8 0 1.5 20 10 2 0 0.2 0.5 0
900 23% 172 77.05 0 2.25 10 0 0 10 0.2 0.5 0 900 23% 173 61.8 0 1.5
20 5 4 5 0.2 0.5 2 900 23% 174 63.05 0 2.25 10 10 4 10 0.2 0.5 0
900 22% 175 68.05 0 2.25 10 5 4 10 0.2 0.5 0 900 22% 176 58.8 0 1.5
20 5 4 10 0.2 0.5 0 900 22% 177 70.05 0 2.25 10 10 0 5 0.2 0.5 2
900 22% 178 68.05 0 2.25 10 10 2 5 0.2 0.5 2 900 22% 179 66.05 0
2.25 10 10 4 5 0.2 0.5 2 900 22% 180 72.05 0 2.25 10 10 0 5 0.2 0.5
0 900 22% 181 61.8 0 1.5 20 10 4 0 0.2 0.5 2 900 22% 182 63.8 0 1.5
20 5 4 5 0.2 0.5 0 900 22% 183 70.05 0 2.25 10 10 2 5 0.2 0.5 0 900
22% 184 68.05 0 2.25 10 10 4 5 0.2 0.5 0 900 21% 185 63.8 0 1.5 20
10 4 0 0.2 0.5 0 900 21% 186 58.3 0 3 20 10 4 0 0.2 0.5 4 950 48%
187 60.3 0 3 20 10 2 0 0.2 0.5 4 950 46% 188 62.3 0 3 20 10 0 0 0.2
0.5 4 950 44% 189 60.3 0 3 20 10 4 0 0.2 0.5 2 950 41% 190 63.05 0
2.25 20 10 0 0 0.2 0.5 4 950 40% 191 62.3 0 3 20 10 2 0 0.2 0.5 2
950 39% 192 64.3 0 3 20 10 0 0 0.2 0.5 2 950 38% 193 61.05 0 2.25
20 10 2 0 0.2 0.5 4 950 38% 194 61.05 0 2.25 20 5 2 5 0.2 0.5 4 950
37% 195 59.05 0 2.25 20 5 4 5 0.2 0.5 4 950 37% 196 63.05 0 2.25 20
10 2 0 0.2 0.5 2 950 37% 197 63.05 0 2.25 20 5 0 5 0.2 0.5 4 950
36% 198 66.3 0 3 20 10 0 0 0.2 0.5 0 950 35% 199 65.05 0 2.25 20 10
0 0 0.2 0.5 2 950 35% 200 64.3 0 3 20 10 2 0 0.2 0.5 0 950 34% 201
62.3 0 3 20 10 4 0 0.2 0.5 0 950 34% 202 61.05 0 2.25 20 5 4 5 0.2
0.5 2 950 33% 203 63.05 0 2.25 20 10 4 0 0.2 0.5 0 950 33% 204 72.3
0 3 10 10 0 0 0.2 0.5 4 950 32% 205 70.3 0 3 10 10 2 0 0.2 0.5 4
950 32% 206 68.3 0 3 10 10 4 0 0.2 0.5 4 950 32% 207 63.05 0 2.25
20 5 2 5 0.2 0.5 2 950 32% 208 65.05 0 2.25 20 5 0 5 0.2 0.5 2 950
31% 209 84.3 0 3 0 10 0 0 0.2 0.5 2 950 30% 210 86.3 0 3 0 10 0 0
0.2 0.5 0 950 30% 211 82.3 0 3 0 10 0 0 0.2 0.5 4 950 29% 212 74.3
0 3 10 10 0 0 0.2 0.5 2 950 29% 213 72.3 0 3 10 10 2 0 0.2 0.5 2
950 29% 214 76.3 0 3 10 10 0 0 0.2 0.5 0 950 29% 215 70.3 0 3 10 10
4 0 0.2 0.5 2 950 29% 216 67.05 0 2.25 20 0 0 10 0.2 0.5 0 950 28%
217 74.3 0 3 10 10 2 0 0.2 0.5 0 950 28% 218 72.3 0 3 10 10 4 0 0.2
0.5 0 950 28% 219 63.8 0 1.5 20 5 0 5 0.2 0.5 4 950 28% 220 65.05 0
2.25 20 0 2 10 0.2 0.5 0 950 28% 221 67.05 0 2.25 20 5 0 5 0.2 0.5
0 950 28% 222 82.3 0 3 0 10 2 0 0.2 0.5 2 950 27% 223 84.3 0 3 0 10
2 0 0.2 0.5 0 950 27% 224 65.05 0 2.25 20 10 2 0 0.2 0.5 0 950 27%
225 65.05 0 2.25 20 5 2 5 0.2 0.5 0 950 27% 226 65.8 0 1.5 20 5 0 5
0.2 0.5 2 950 27% 227 80.3 0 3 0 10 2 0 0.2 0.5 4 950 27% 228 80.3
0 3 0 5 2 5 0.2 0.5 4 950 27% 229 73.05 0 2.25 10 0 0 10 0.2 0.5 4
950 26% 230 71.05 0 2.25 10 0 2 10 0.2 0.5 4 950 26% 231 67.05 0
2.25 20 10 0 0 0.2 0.5 0 950 26% 232 82.3 0 3 0 5 2 5 0.2 0.5 2 950
26% 233 69.05 0 2.25 10 0 4 10 0.2 0.5 4 950 26% 234 63.05 0 2.25
20 5 4 5 0.2 0.5 0 950 26% 235 69.05 0 2.25 10 10 4 0 0.2 0.5 4 950
26% 236 69.05 0 2.25 10 5 4 5 0.2 0.5 4 950 26% 237 71.05 0 2.25 10
5 2 5 0.2 0.5 4 950 26% 238 71.05 0 2.25 10 10 2 0 0.2 0.5 4 950
26% 239 73.05 0 2.25 10 5 0 5 0.2 0.5 4 950 26% 240 73.05 0 2.25 10
10 0 0 0.2 0.5 4 950 25% 241 63.8 0 1.5 20 5 2 5 0.2 0.5 2 950 25%
242 80.3 0 3 0 10 4 0 0.2 0.5 2 950 24% 243 82.3 0 3 0 10 4 0 0.2
0.5 0 950 24% 244 78.3 0 3 0 5 4 5 0.2 0.5 4 950 24% 245 80.3 0 3 0
5 4 5 0.2 0.5 2 950 24% 246 82.3 0 3 0 5 0 5 0.2 0.5 4 950 24% 247
78.3 0 3 0 10 4 0 0.2 0.5 4 950 24% 248 84.3 0 3 0 5 0 5 0.2 0.5 2
950 23% 249 73.05 0 2.25 10 0 2 10 0.2 0.5 2 950 23% 250 71.05 0
2.25 10 0 4 10 0.2 0.5 2 950 23% 251 84.3 0 3 0 5 2 5 0.2 0.5 0 950
23% 252 75.05 0 2.25 10 0 2 10 0.2 0.5 0 950 23% 253 73.05 0 2.25
10 0 4 10 0.2 0.5 0 950 22% 254 65.8 0 1.5 20 5 2 5 0.2 0.5 0 950
22% 255 75.05 0 2.25 10 5 0 5 0.2 0.5 2 950 22% 256 73.05 0 2.25 10
5 2 5 0.2 0.5 2 950 22% 257 71.05 0 2.25 10 5 4 5 0.2 0.5 2 950 22%
258 77.05 0 2.25 10 5 0 5 0.2 0.5 0 950 22% 259 75.05 0 2.25 10 5 2
5 0.2 0.5 0 950 22% 260 73.05 0 2.25 10 5 4 5 0.2 0.5 0 950 21% 261
75.05 0 2.25 10 10 0 0 0.2 0.5 2 950 21% 262 71.05 0 2.25 10 10 4 0
0.2 0.5 2 950 21% 263 73.05 0 2.25 10 10 2 0 0.2 0.5 2 950 21% 264
82.3 0 3 0 5 4 5 0.2 0.5 0 950 21% 265 77.05 0 2.25 10 10 0 0 0.2
0.5 0 950 20% 266 75.05 0 2.25 10 10 2 0 0.2 0.5 0 950 20% 267
73.05 0 2.25 10 10 4 0 0.2 0.5 0 950 20% 268 62 0 2 18 10 4 0 4 0 0
900 20% 269 64.5 0 1.5 18 10 4 0 0 2 0 900 21% 270 64.5 0 1.5 18 10
4 0 0 0 2 900 21% 271 62.5 0 1.5 18 10 4 0 0 2 2 900 22% 272 64 0.5
1.5 18 10 4 0 2 0 0 900 22% 273 62.5 0 1.5 18 10 4 0 0 0 4 900 22%
274 60.5 0 1.5 18 10 4 0 0 2 4 900 23% 275 62 0.5 1.5 18 10 4 0 2 0
2 800 24% 276 64 0 2 18 10 4 0 2 0 0 900 24% 277 59.5 0 2.5 18 10 4
0 6 0 0 900 25% 278 60 0.5 1.5 18 10 4 0 2 0 4 850 25%
279 62 0 2 18 10 4 0 2 2 0 900 25% 280 64 0 2 18 10 4 0 0 2 0 900
25% 281 62 0 2 18 10 4 0 2 0 2 900 26% 282 60 0 2 18 10 4 0 2 2 2
900 26% 283 62 0.5 1.5 18 10 4 0 0 4 0 900 26% 284 66 0.5 1.5 18 10
4 0 0 0 0 900 27% 285 61.5 0.5 2 18 10 4 0 4 0 0 900 27% 286 60 0 2
18 10 4 0 2 0 4 900 27% 287 58 0 2 18 10 4 0 2 2 4 900 27% 288 65.5
0 2.5 18 10 4 0 0 0 0 950 27% 289 64 0.5 1.5 18 10 4 0 0 2 0 900
27% 290 58 0 2 18 10 4 0 0 6 2 750 28% 291 59.5 0.5 2 18 10 4 0 4 0
2 900 28% 292 64 0.5 1.5 18 10 4 0 0 0 2 900 28% 293 66 0 2 18 10 4
0 0 0 0 950 28% 294 62 0 2 18 10 4 0 0 4 0 900 28% 295 65.5 0.5 2
18 10 4 0 0 0 0 950 28% 296 63.5 0 2.5 18 10 4 0 0 2 0 950 28% 297
59.5 0 2.5 18 10 4 0 4 2 0 900 28% 298 63.5 1 1.5 18 10 4 0 2 0 0
900 28% 299 62 0.5 1.5 18 10 4 0 0 2 2 900 28% 300 61.5 0 2.5 18 10
4 0 4 0 0 900 29% 301 61.5 0 2.5 18 10 4 0 0 4 0 900 29% 302 63.5
0.5 2 18 10 4 0 0 2 0 900 29% 303 61.5 1 1.5 18 10 4 0 2 2 0 900
29% 304 62 0.5 1.5 18 10 4 0 0 0 4 900 29% 305 56 0 2 18 10 4 0 0 6
4 800 29% 306 60 0 2 18 10 4 0 0 4 2 900 30% 307 60 0.5 1.5 18 10 4
0 0 2 4 900 30% 308 57.5 0 2.5 18 10 4 0 4 2 2 900 30% 309 59.5 0
2.5 18 10 4 0 4 0 2 900 30% 310 64 0 2 18 10 4 0 0 0 2 900 30% 311
61.5 1 1.5 18 10 4 0 2 0 2 900 30% 312 59.5 0.5 2 18 10 4 0 2 4 0
800 30% 313 62 0 2 18 10 4 0 0 2 2 900 30% 314 61.5 0 2.5 18 10 4 0
2 2 0 900 31% 315 63.5 0.5 2 18 10 4 0 2 0 0 900 31% 316 59 0.5 2.5
18 10 4 0 6 0 0 900 31% 317 61.5 0.5 2 18 10 4 0 0 4 0 900 31% 318
55.5 0 2.5 18 10 4 0 4 2 4 900 31% 319 57.5 0 2.5 18 10 4 0 4 0 4
900 31% 320 61.5 0.5 2 18 10 4 0 2 2 0 900 31% 321 58 0 2 18 10 4 0
0 4 4 900 31% 322 63 0 3 18 10 4 0 2 0 0 950 31% 323 62 0 2 18 10 4
0 0 0 4 900 31% 324 63.5 1 1.5 18 10 4 0 0 2 0 900 31% 325 59.5 1
1.5 18 10 4 0 2 0 4 900 31% 326 59.5 0.5 2 18 10 4 0 0 6 0 900 31%
327 55.5 0 2.5 18 10 4 0 2 6 2 750 31% 328 61.5 1 1.5 18 10 4 0 0 4
0 900 31% 329 60 0 2 18 10 4 0 0 2 4 900 32% 330 59.5 0 2.5 18 10 4
0 0 6 0 900 32% 331 59.5 0 2.5 18 10 4 0 2 4 0 900 32% 332 61 0 3
18 10 4 0 2 2 0 950 32% 333 57 0.5 2.5 18 10 4 0 6 0 2 800 32% 334
61.5 0.5 2 18 10 4 0 2 0 2 900 32% 335 57 0 3 18 10 4 0 6 2 0 900
32% 336 59 0 3 18 10 4 0 2 4 0 900 32% 337 59 1 2 18 10 4 0 4 2 0
900 32% 338 59.5 0.5 2 18 10 4 0 2 2 2 900 32% 339 61 1 2 18 10 4 0
4 0 0 900 33% 340 59 0 3 18 10 4 0 6 0 0 900 33% 341 63.5 0 2.5 18
10 4 0 2 0 0 950 33% 342 65.5 1 1.5 18 10 4 0 0 0 0 950 33% 343 61
0.5 2.5 18 10 4 0 2 2 0 900 33% 344 65 0 3 18 10 4 0 0 0 0 950 33%
345 63 0.5 2.5 18 10 4 0 2 0 0 950 33% 346 57.5 0.5 2 18 10 4 0 0 6
2 900 33% 347 57 0.5 2.5 18 10 4 0 4 4 0 600 33% 348 59.5 0.5 2 18
10 4 0 2 0 4 900 33% 349 57.5 0 2.5 18 10 4 0 2 4 2 900 33% 350 55
0 3 18 10 4 0 6 2 2 900 33% 351 59.5 1 1.5 18 10 4 0 0 4 2 900 33%
352 59 0 3 18 10 4 0 0 6 0 900 33% 353 57.5 0.5 2 18 10 4 0 2 2 4
900 33% 354 65 0.5 2.5 18 10 4 0 0 0 0 950 34% 355 61.5 0 2.5 18 10
4 0 0 2 2 900 34% 356 57 0 3 18 10 4 0 6 0 2 900 34% 357 61.5 0 2.5
18 10 4 0 2 0 2 900 34% 358 63 0 3 18 10 4 0 0 2 0 900 34% 359 59 1
2 18 10 4 0 4 0 2 900 34% 360 59.5 0 2.5 18 10 4 0 2 2 2 900 34%
361 65 1 2 18 10 4 0 0 0 0 950 34% 362 63.5 1 1.5 18 10 4 0 0 0 2
900 34% 363 59 0.5 2.5 18 10 4 0 4 2 0 900 34% 364 59 0.5 2.5 18 10
4 0 0 6 0 900 34% 365 59.5 0 2.5 18 10 4 0 0 4 2 900 34% 366 53 0 3
18 10 4 0 6 2 4 850 34% 367 57.5 0 2.5 18 10 4 0 0 6 2 900 35% 368
61 0 3 18 10 4 0 0 4 0 950 35% 369 63 0.5 2.5 18 10 4 0 0 2 0 950
35% 370 55.5 0 2.5 18 10 4 0 2 4 4 850 35% 371 61 0.5 2.5 18 10 4 0
4 0 0 900 35% 372 55 0.5 2.5 18 10 4 0 4 4 2 800 35% 373 55.5 0.5 2
18 10 4 0 0 6 4 900 35% 374 61.5 1 1.5 18 10 4 0 0 2 2 900 35% 375
61 1 2 18 10 4 0 0 4 0 900 35% 376 53 0 3 18 10 4 0 4 6 2 750 35%
377 61 0.5 2.5 18 10 4 0 0 4 0 900 35% 378 57 0 3 18 10 4 0 4 4 0
900 35% 379 55 0 3 18 10 4 0 6 0 4 900 35% 380 57 0.5 2.5 18 10 4 0
2 6 0 900 35% 381 59 1 2 18 10 4 0 2 4 0 900 35% 382 59.5 0.5 2 18
10 4 0 0 4 2 900 35% 383 63 1 2 18 10 4 0 0 2 0 950 35% 384 57 1 2
18 10 4 0 4 0 4 900 35% 385 57.5 1 1.5 18 10 4 0 0 4 4 900 35% 386
59.5 0 2.5 18 10 4 0 2 0 4 900 35% 387 57.5 0 2.5 18 10 4 0 2 2 4
900 35% 388 61.5 1 1.5 18 10 4 0 0 0 4 900 36% 389 57 0.5 2.5 18 10
4 0 4 2 2 900 36% 390 59 0.5 2.5 18 10 4 0 4 0 2 900 36% 391 55.5 0
2.5 18 10 4 0 0 6 4 900 36% 392 61.5 0.5 2 18 10 4 0 0 2 2 900 36%
393 59.5 1 1.5 18 10 4 0 0 2 4 900 36% 394 59 0 3 18 10 4 0 4 2 0
900 36% 395 59 0.5 2.5 18 10 4 0 2 4 0 900 36% 396 53 0.5 2.5 18 10
4 0 4 4 4 800 36% 397 63.5 0.5 2 18 10 4 0 0 0 2 950 36% 398 55 0 3
18 10 4 0 4 4 2 750 36% 399 59 1 2 18 10 4 0 0 6 0 900 36% 400 61 1
2 18 10 4 0 2 2 0 900 36% 401 61 0 3 18 10 4 0 4 0 0 900 36% 402 61
0 3 18 10 4 0 0 2 2 950 37% 403 57.5 0.5 2 18 10 4 0 0 4 4 900 37%
404 57 0 3 18 10 4 0 2 6 0 900 37% 405 63 1 2 18 10 4 0 2 0 0 950
37% 406 55 0.5 2.5 18 10 4 0 2 6 2 900 37% 407 55 0.5 2.5 18 10 4 0
4 2 4 900 37% 408 59 0 3 18 10 4 0 0 4 2 900 37% 409 63.5 0 2.5 18
10 4 0 0 0 2 950 37% 410 57 1 2 18 10 4 0 2 4 2 900 37% 411 57 0.5
2.5 18 10 4 0 4 0 4 900 37% 412 57 0 3 18 10 4 0 4 2 2 900 37% 413
62.5 0.5 3 18 10 4 0 2 0 0 950 37% 414 61.5 0.5 2 18 10 4 0 0 0 4
950 38% 415 53 0 3 18 10 4 0 4 4 4 850 38% 416 56.5 0.5 3 18 10 4 0
6 2 0 900 38% 417 60.5 0.5 3 18 10 4 0 4 0 0 950 38% 418 59 0 3 18
10 4 0 4 0 2 900 38% 419 62.5 1 2.5 18 10 4 0 2 0 0 950 38% 420
59.5 0.5 2 18 10 4 0 0 2 4 900 38% 421 57.5 0 2.5 18 10 4 0 0 4 4
900 38% 422 59 0 3 18 10 4 0 2 2 2 900 38% 423 63 0 3 18 10 4 0 0 0
2 950 38% 424 61 1 2 18 10 4 0 2 0 2 900 38% 425 60.5 0.5 3 18 10 4
0 2 2 0 950 38% 426 55 0 3 18 10 4 0 2 6 2 900 38% 427 59 1 2 18 10
4 0 2 2 2 900 38% 428 58.5 0.5 3 18 10 4 0 2 4 0 900 38% 429 58.5 1
2.5 18 10 4 0 2 4 0 900 38% 430 58.5 0.5 3 18 10 4 0 4 2 0 850 38%
431 57 1 2 18 10 4 0 0 6 2 900 38% 432 57 0 3 18 10 4 0 0 6 2 900
38% 433 54.5 0.5 3 18 10 4 0 4 6 0 900 38% 434 61 0.5 2.5 18 10 4 0
0 2 2 950 38% 435 58.5 0.5 3 18 10 4 0 6 0 0 900 38% 436 55 0 3 18
10 4 0 4 2 4 900 38% 437 60.5 1 2.5 18 10 4 0 2 2 0 950 39% 438 57
0.5 2.5 18 10 4 0 2 4 2 900 39% 439 59.5 0 2.5 18 10 4 0 0 2 4 900
39% 440 55 1 2 18 10 4 0 2 4 4 900 39% 441 57 0 3 18 10 4 0 2 4 2
900 39% 442 59 0.5 2.5 18 10 4 0 0 4 2 900 39% 443 57 0 3 18 10 4 0
4 0 4 900 39% 444 54.5 0.5 3 18 10 4 0 6 2 2 850 39% 445 64.5 0.5 3
18 10 4 0 0 0 0 950 39% 446 58.5 0.5 3 18 10 4 0 0 6 0 900 39% 447
58.5 1 2.5 18 10 4 0 0 6 0 900 39% 448 56.5 0.5 3 18 10 4 0 2 6 0
900 39% 449 59 1 2 18 10 4 0 2 0 4 900 39% 450 57 1 2 18 10 4 0 2 2
4 900 39% 451 53 0 3 18 10 4 0 2 6 4 850 40% 452 61.5 0 2.5 18 10 4
0 0 0 4 950 40% 453 56.5 0.5 3 18 10 4 0 6 0 2 900 40% 454 64.5 1
2.5 18 10 4 0 0 0 0 950 40% 455 58.5 1 2.5 18 10 4 0 4 2 0 900 40%
456 57 0.5 2.5 18 10 4 0 0 6 2 900 40% 457 56.5 1 2.5 18 10 4 0 2 6
0 900 40% 458 59 0.5 2.5 18 10 4 0 2 2 2 900 40% 459 55 1 2 18 10 4
0 0 6 4 900 40% 460 52.5 0.5 3 18 10 4 0 4 6 2 900 40% 461 61 1 2
18 10 4 0 0 2 2 950 40% 462 61 0.5 2.5 18 10 4 0 2 0 2 950 40% 463
56.5 0.5 3 18 10 4 0 4 4 0 900 40% 464 62.5 0.5 3 18 10 4 0 0 2 0
950 40% 465 55 0.5 2.5 18 10 4 0 2 4 4 900 40% 466 59 1 2 18 10 4 0
0 4 2 900 40% 467 52.5 0.5 3 18 10 4 0 6 2 4 850 40% 468 60.5 1 2.5
18 10 4 0 4 0 0 900 40% 469 60.5 0.5 3 18 10 4 0 0 4 0 950 40% 470
60.5 1 2.5 18 10 4 0 0 4 0 950 41% 471 63 0.5 2.5 18 10 4 0 0 0 2
950 41% 472 62.5 1 2.5 18 10 4 0 0 2 0 950 41% 473 54.5 0.5 3 18 10
4 0 6 0 4 900 41% 474 61 0 3 18 10 4 0 2 0 2 950 41% 475 56.5 1 2.5
18 10 4 0 4 2 2 900 41% 476 57 0.5 2.5 18 10 4 0 2 2 4 900 41% 477
57 0 3 18 10 4 0 0 4 4 900 41% 478 55 0.5 2.5 18 10 4 0 0 6 4 900
41% 479 59 0.5 2.5 18 10 4 0 2 0 4 950 41% 480 55 0 3 18 10 4 0 2 4
4 900 41% 481 59 0 3 18 10 4 0 0 2 4 950 41% 482 50.5 0.5 3 18 10 4
0 4 6 4 850 42% 483 54.5 0.5 3 18 10 4 0 4 4 2 900 42% 484 54.5 1
2.5 18 10 4 0 2 6 2 900 42% 485 58.5 1 2.5 18 10 4 0 4 0 2 900 42%
486 60.5 0.5 3 18 10 4 0 0 2 2 950 42% 487 58.5 0.5 3 18 10 4 0 0 4
2 950 42% 488 57 1 2 18 10 4 0 0 4 4 900 42% 489 58.5 0.5 3 18 10 4
0 2 2 2 950 42% 490 63 1 2 18 10 4 0 0 0 2 950 42% 491 55 0 3 18 10
4 0 0 6 4 900 42% 492 56.5 0.5 3 18 10 4 0 0 6 2 900 43% 493 57 0 3
18 10 4 0 2 2 4 900 43% 494 56.5 0.5 3 18 10 4 0 2 4 2 900 43% 495
56.5 0.5 3 18 10 4 0 4 2 2 900 43% 496 62.5 0.5 3 18 10 4 0 0 0 2
950 43% 497 52.5 0.5 3 18 10 4 0 4 4 4 850 43% 498 56.5 1 2.5 18 10
4 0 4 0 4 900 43% 499 54.5 0.5 3 18 10 4 0 2 6 2 900 43% 500 59 0.5
2.5 18 10 4 0 0 2 4 950 43% 501 60.5 1 2.5 18 10 4 0 0 2 2 950 43%
502 57 0.5 2.5 18 10 4 0 0 4 4 900 43% 503 52.5 1 2.5 18 10 4 0 2 6
4 850 43% 504 59 0 3 18 10 4 0 2 0 4 950 43% 505 58.5 1 2.5 18 10 4
0 0 4 2 950 43% 506 58.5 0.5 3 18 10 4 0 4 0 2 950 44% 507 56.5 1
2.5 18 10 4 0 2 4 2 900 44% 508 61 1 2 18 10 4 0 0 0 4 950 44% 509
59 1 2 18 10 4 0 0 2 4 900 44% 510 58.5 1 2.5 18 10 4 0 2 2 2 900
44% 511 54.5 0.5 3 18 10 4 0 4 2 4 900 44% 512 60.5 0.5 3 18 10 4 0
2 0 2 950 44% 513 52.5 0.5 3 18 10 4 0 2 6 4 900 45% 514 56.5 1 2.5
18 10 4 0 0 6 2 900 45% 515 62.5 1 2.5 18 10 4 0 0 0 2 950 45% 516
56.5 0.5 3 18 10 4 0 4 0 4 900 45% 517 54.5 1 2.5 18 10 4 0 2 4 4
900 45% 518 61 0 3 18 10 4 0 0 0 4 950 46% 519 60.5 1 2.5 18 10 4 0
2 0 2 950 46% 520 61 0.5 2.5 18 10 4 0 0 0 4 950 46% 521 56.5 0.5 3
18 10 4 0 0 4 4 950 46% 522 54.5 1 2.5 18 10 4 0 0 6 4 900 46% 523
58.5 0.5 3 18 10 4 0 0 2 4 950 46% 524 54.5 0.5 3 18 10 4 0 2 4 4
900 47% 525 56.5 1 2.5 18 10 4 0 2 2 4 900 47% 526 56.5 0.5 3 18 10
4 0 2 2 4 950 47% 527 54.5 0.5 3 18 10 4 0 0 6 4 900 47% 528 58.5 1
2.5 18 10 4 0 2 0 4 950 47% 529 58.5 1 2.5 18 10 4 0 0 2 4 950
48%
530 56.5 1 2.5 18 10 4 0 0 4 4 900 48% 531 58.5 0.5 3 18 10 4 0 2 0
4 950 50% 532 60.5 0.5 3 18 10 4 0 0 0 4 950 51% 533 60.5 1 2.5 18
10 4 0 0 0 4 950 52% 534 75.8 1 1.5 6 4 0 6 0.2 0.5 5 950 22% 535
73.8 1 1.5 6 4 2 6 0.2 0.5 5 950 22% 536 73.8 1 1.5 6 4 0 8 0.2 0.5
5 900 22% 537 71.8 1 1.5 6 4 2 8 0.2 0.5 5 950 23% 538 71.8 1 1.5 6
4 4 6 0.2 0.5 5 950 23% 539 69.8 1 1.5 6 4 4 8 0.2 0.5 5 950 23%
540 71.8 1 1.5 6 4 0 10 0.2 0.5 5 900 23% 541 69.8 1 1.5 6 4 2 10
0.2 0.5 5 900 23% 542 67.8 1 1.5 6 4 4 10 0.2 0.5 5 900 23% 543
75.8 1 1.5 6 4 2 4 0.2 0.5 5 950 23% 544 68.8 1 1.5 6 4 2 6 0.2 0.5
10 950 24% 545 68.8 1 1.5 6 4 0 8 0.2 0.5 10 900 25% 546 66.8 1 1.5
6 4 2 8 0.2 0.5 10 950 25% 547 66.8 1 1.5 6 4 0 10 0.2 0.5 10 900
25% 548 64.8 1 1.5 6 4 4 8 0.2 0.5 10 950 25% 549 64.8 1 1.5 6 4 2
10 0.2 0.5 10 900 25% 550 62.8 1 1.5 6 4 4 10 0.2 0.5 10 900 25%
551 70.8 1 1.5 6 4 0 6 0.2 0.5 10 950 25% 552 77.8 1 1.5 6 4 0 4
0.2 0.5 5 950 26% 553 68.8 1 1.5 6 4 4 4 0.2 0.5 10 950 26% 554
66.8 1 1.5 6 4 4 6 0.2 0.5 10 950 26% 555 63.8 1 1.5 6 4 0 8 0.2
0.5 15 950 27% 556 61.8 1 1.5 6 4 2 8 0.2 0.5 15 950 27% 557 71.3 1
2 6 4 2 8 0.2 0.5 5 900 27% 558 61.8 1 1.5 6 4 0 10 0.2 0.5 15 900
27% 559 70.8 1 1.5 6 4 2 4 0.2 0.5 10 950 27% 560 69.3 1 2 6 4 4 8
0.2 0.5 5 900 27% 561 69.3 1 2 6 4 2 10 0.2 0.5 5 900 27% 562 59.8
1 1.5 6 4 2 10 0.2 0.5 15 900 27% 563 67.3 1 2 6 4 4 10 0.2 0.5 5
900 27% 564 73.3 1 2 6 4 2 6 0.2 0.5 5 950 28% 565 71.3 1 2 6 4 4 6
0.2 0.5 5 950 28% 566 68.3 1 2 6 4 0 8 0.2 0.5 10 900 28% 567 57.8
1 1.5 6 4 4 10 0.2 0.5 15 900 28% 568 66.3 1 2 6 4 0 10 0.2 0.5 10
900 29% 569 72.8 1 1.5 6 4 0 4 0.2 0.5 10 950 29% 570 68.3 1 2 6 4
2 6 0.2 0.5 10 950 29% 571 70.3 1 2 6 4 0 6 0.2 0.5 10 950 29% 572
66.3 1 2 6 4 2 8 0.2 0.5 10 900 29% 573 63.8 1 1.5 6 4 4 4 0.2 0.5
15 950 29% 574 64.3 1 2 6 4 2 10 0.2 0.5 10 900 29% 575 61.8 1 1.5
6 4 4 6 0.2 0.5 15 950 29% 576 64.3 1 2 6 4 4 8 0.2 0.5 10 900 29%
577 63.8 1 1.5 6 4 2 6 0.2 0.5 15 950 30% 578 59.8 1 1.5 6 4 4 8
0.2 0.5 15 900 30% 579 62.3 1 2 6 4 4 10 0.2 0.5 10 900 30% 580
65.3 1 2 6 4 0 6 0.2 0.5 15 950 30% 581 73.3 1 2 6 4 4 4 0.2 0.5 5
950 30% 582 63.3 1 2 6 4 0 8 0.2 0.5 15 900 30% 583 65.8 1 1.5 6 4
2 4 0.2 0.5 15 950 30% 584 61.3 1 2 6 4 0 10 0.2 0.5 15 900 30% 585
65.8 1 1.5 6 4 0 6 0.2 0.5 15 950 30% 586 63.3 1 2 6 4 2 6 0.2 0.5
15 950 31% 587 73.3 1 2 6 4 0 8 0.2 0.5 5 900 31% 588 71.3 1 2 6 4
0 10 0.2 0.5 5 900 31% 589 61.3 1 2 6 4 2 8 0.2 0.5 15 900 31% 590
66.3 1 2 6 4 4 6 0.2 0.5 10 950 31% 591 59.3 1 2 6 4 2 10 0.2 0.5
15 900 31% 592 59.3 1 2 6 4 4 8 0.2 0.5 15 900 32% 593 67.8 1 1.5 6
4 0 4 0.2 0.5 15 950 32% 594 57.3 1 2 6 4 4 10 0.2 0.5 15 900 32%
595 75.3 1 2 6 4 2 4 0.2 0.5 5 950 32% 596 75.3 1 2 6 4 0 6 0.2 0.5
5 950 32% 597 65.8 1 2.5 6 4 4 6 0.2 0.5 10 950 33% 598 63.8 1 2.5
6 4 4 8 0.2 0.5 10 900 33% 599 61.8 1 2.5 6 4 4 10 0.2 0.5 10 900
33% 600 68.3 1 2 6 4 4 4 0.2 0.5 10 950 33% 601 77.3 1 2 6 4 0 4
0.2 0.5 5 950 34% 602 62.8 1 2.5 6 4 2 6 0.2 0.5 15 950 34% 603
60.8 1 2.5 6 4 2 8 0.2 0.5 15 900 35% 604 60.8 1 2.5 6 4 4 6 0.2
0.5 15 950 35% 605 58.8 1 2.5 6 4 4 8 0.2 0.5 15 900 35% 606 58.8 1
2.5 6 4 2 10 0.2 0.5 15 900 35% 607 56.8 1 2.5 6 4 4 10 0.2 0.5 15
900 35% 608 68.8 1 2.5 6 4 4 8 0.2 0.5 5 900 35% 609 66.8 1 2.5 6 4
4 10 0.2 0.5 5 900 35% 610 70.3 1 2 6 4 2 4 0.2 0.5 10 950 35% 611
65.8 1 2.5 6 4 2 8 0.2 0.5 10 900 36% 612 63.8 1 2.5 6 4 2 10 0.2
0.5 10 900 36% 613 67.8 1 2.5 6 4 2 6 0.2 0.5 10 950 36% 614 61.3 1
2 6 4 4 6 0.2 0.5 15 950 36% 615 70.8 1 2.5 6 4 4 6 0.2 0.5 5 950
36% 616 64.8 1 2.5 6 4 0 6 0.2 0.5 15 900 36% 617 62.8 1 2.5 6 4 0
8 0.2 0.5 15 900 36% 618 63.3 1 2 6 4 4 4 0.2 0.5 15 950 37% 619
60.8 1 2.5 6 4 0 10 0.2 0.5 15 900 37% 620 72.3 1 2 6 4 0 4 0.2 0.5
10 950 37% 621 67.3 1 2 6 4 0 4 0.2 0.5 15 950 38% 622 65.3 1 2 6 4
2 4 0.2 0.5 15 950 38% 623 72.8 1 2.5 6 4 4 4 0.2 0.5 5 950 38% 624
70.8 1 2.5 6 4 2 8 0.2 0.5 5 900 39% 625 68.8 1 2.5 6 4 2 10 0.2
0.5 5 900 39% 626 74.8 1 2.5 6 4 2 4 0.2 0.5 5 950 39% 627 72.8 1
2.5 6 4 2 6 0.2 0.5 5 950 39% 628 69.8 1 2.5 6 4 0 6 0.2 0.5 10 950
40% 629 67.8 1 2.5 6 4 0 8 0.2 0.5 10 900 40% 630 65.8 1 2.5 6 4 0
10 0.2 0.5 10 900 40% 631 67.8 1 2.5 6 4 4 4 0.2 0.5 10 950 40% 632
58.3 1 3 6 4 4 8 0.2 0.5 15 900 41% 633 60.3 1 3 6 4 4 6 0.2 0.5 15
900 41% 634 56.3 1 3 6 4 4 10 0.2 0.5 15 900 41% 635 69.8 1 2.5 6 4
2 4 0.2 0.5 10 950 41% 636 64.8 1 2.5 6 4 2 4 0.2 0.5 15 950 41%
637 62.8 1 2.5 6 4 4 4 0.2 0.5 15 950 41% 638 70.8 1 2.5 6 4 0 10
0.2 0.5 5 900 42% 639 72.8 1 2.5 6 4 0 8 0.2 0.5 5 900 42% 640 76.8
1 2.5 6 4 0 4 0.2 0.5 5 950 42% 641 71.8 1 2.5 6 4 0 4 0.2 0.5 10
950 42% 642 66.8 1 2.5 6 4 0 4 0.2 0.5 15 950 42% 643 74.8 1 2.5 6
4 0 6 0.2 0.5 5 950 42% 644 65.3 1 3 6 4 4 6 0.2 0.5 10 950 44% 645
61.3 1 3 6 4 4 10 0.2 0.5 10 900 44% 646 63.3 1 3 6 4 4 8 0.2 0.5
10 900 44% 647 58.3 1 3 6 4 2 10 0.2 0.5 15 900 45% 648 60.3 1 3 6
4 2 8 0.2 0.5 15 900 45% 649 62.3 1 3 6 4 2 6 0.2 0.5 15 900 45%
650 67.3 1 3 6 4 4 4 0.2 0.5 10 950 45% 651 68.3 1 3 6 4 4 8 0.2
0.5 5 900 45% 652 62.3 1 3 6 4 4 4 0.2 0.5 15 950 46% 653 66.3 1 3
6 4 4 10 0.2 0.5 5 900 46% 654 70.3 1 3 6 4 4 6 0.2 0.5 5 950 46%
655 72.3 1 3 6 4 4 4 0.2 0.5 5 950 46% 656 64.3 1 3 6 4 2 4 0.2 0.5
15 950 46% 657 65.3 1 3 6 4 2 8 0.2 0.5 10 900 47% 658 67.3 1 3 6 4
2 6 0.2 0.5 10 950 47% 659 63.3 1 3 6 4 2 10 0.2 0.5 10 900 47% 660
64.3 1 3 6 4 0 6 0.2 0.5 15 900 48% 661 69.3 1 3 6 4 2 4 0.2 0.5 10
950 48% 662 62.3 1 3 6 4 0 8 0.2 0.5 15 900 49% 663 60.3 1 3 6 4 0
10 0.2 0.5 15 900 49% 664 68.3 1 3 6 4 2 10 0.2 0.5 5 900 49% 665
70.3 1 3 6 4 2 8 0.2 0.5 5 900 49% 666 66.3 1 3 6 4 0 4 0.2 0.5 15
950 49% 667 74.3 1 3 6 4 2 4 0.2 0.5 5 950 49% 668 72.3 1 3 6 4 2 6
0.2 0.5 5 950 49% 669 67.3 1 3 6 4 0 8 0.2 0.5 10 900 50% 670 65.3
1 3 6 4 0 10 0.2 0.5 10 900 50% 671 69.3 1 3 6 4 0 6 0.2 0.5 10 950
50% 672 70.3 1 3 6 4 0 10 0.2 0.5 5 900 51% 673 71.3 1 3 6 4 0 4
0.2 0.5 10 950 51% 674 76.3 1 3 6 4 0 4 0.2 0.5 5 950 51% 675 72.3
1 3 6 4 0 8 0.2 0.5 5 900 52% 676 74.3 1 3 6 4 0 6 0.2 0.5 5 950
52%
Thermodynamic Criteria
[0189] In some embodiments, alloys can be defined by thermodynamic
criteria that result in a specified performance of an alloy. For
example, a thermodynamic criteria can be for alloys which possess
an equilibrium FCC-BCC transition temperature equal to or below
900-950K (or about 900 to about 950K), and simultaneously possess
an equilibrium total concentration of combined hard precipitates
(carbides, borides, or borocarbides) in excess of 20-30 mole
percent (or about 20 to about 30 mole percent) at a temperature of
1300K (or about 1300K). This thermodynamic criteria than can be
used to predict performance of embodiments of alloys having the
specified FCC-BCC transition temperature and the hard phase
fraction.
[0190] Thermodynamic criteria can be calculated using the CALPHAD
method. A potential result of such calculations is an equilibrium
phase diagram such as that shown in FIG. 6. The FCC-BCC transition
temperature can be defined as the temperature where the mole
fraction of the FCC phase (austenite) begins to drop with
decreasing temperature, and the BCC phase (ferrite) now exists.
Additionally, the hard phase fraction can be defined as the mole
fraction sum of all the carbides, borides, or boro-carbides at
1300K (or about 1300K). The specific carbides can change depending
on the alloy composition and the elements present in the alloy. The
hard phase fraction criterion may not be dependent on the type of
carbide, borides, or boro-carbides, rather the sum of all carbide,
borides, or boro-carbides regardless of their specific chemistry,
morphology, or atomic structure. Therefore, in some embodiments,
the alloy can be defined as an alloy which possesses a FCC-BCC
transition temperature below 900-950K (or about 900 to about 950K)
and a hard phase fraction at least above 20% (or at least above
20%).
[0191] In some embodiments, the FCC-BCC transition temperature can
be an indicator of the final phase of a hardfacing weld. As shown
in FIG. 6, the predicted final structure of the alloy shown is BCC
Fe (ferrite), which is a magnetic phase of iron or steel. Thus, it
is not obvious to suggest that a hardfacing weld overlay deposit of
this alloy will form the non-magnetic phase of iron or steel: the
FCC structure or austenite. However, as the welding process
possesses a certain cooling rate, the actual alloy microstructure
may not reach equilibrium, and thus be metastable. As such, in some
embodiments, equilibrium thermodynamic calculations can be used to
predict non-equilibrium conditions. This may not apply to
equilibrium processes and can correspond to industrial processes
with specific cooling rates which are characterized by some level
of metastability. For example, a FCC-BCC transition temperature of
900-950K (or about 900 to about 950) or below, as described above,
can be a positive indicator for forming austenitic matrix
microstructure and achieving the specified magnetic performance.
Out of the 33 alloys evaluated in Table III, 30 possessed a
calculated FCC-BCC transition temperature, and 27 were also
measured (90%) experimentally to be non-magnetic (relative
permeability <1.02).
[0192] In some embodiments, a thermodynamic criteria can be a
FCC-BCC transition temperature at or below 950K (or about 950K). In
some embodiments, a thermodynamic criteria can be a FCC-BCC
transition temperature at or below 900K (or about 900K). 92% of the
alloys evaluated in Table III that met this criteria were
determined to be non-magnetic (relative permeability <1.02). In
some embodiments, a thermodynamic criteria can be a FCC-BCC
transition temperature at or below 850K (or about 850K). 100% of
the alloys evaluated in Table III that met this criteria were
determined to be non-magnetic (relative permeability <1.02).
[0193] Additionally, in some embodiments, the hard phase fraction
can be an indicator of the hardness and/or wear resistance of the
hardfacing alloy. Due to issues with predicting metastable
processes with equilibrium calculations, the hard phase fraction
can be calculated from at a temperature of 1300K (or about 1300K).
Thus, the hard phases fraction of the weld can be considered
`frozen in` at this temperature due to the cooling rate of the
hardfacing process, and not allowed to further change. This has
been supported with experimental measurements. A hard phase
fraction at or above 0.2-0.30 mole fraction (or about 0.2 to about
0.30 mole fraction) can be a positive indicator for reaching the
wear and hardness performance criteria described in this
disclosure. Out of the 33 alloys evaluated in Table III, 75% of
those with a hard phase fraction of 20% or greater possessed
greater than 40 HRC.
[0194] In some embodiments, a thermodynamic criteria can be a mole
fraction of no less than 0.20 (or about 0.20) hard particles. In
some embodiments, a thermodynamic criteria can be a mole fraction
of no less than 0.25 (or about 0.25) hard particles. Out of the 33
alloys evaluated in Table III, 90% of those with a hard phase
fraction of 25% or greater possessed greater than 40 HRC. In some
embodiments, thermodynamic criteria can be a mole fraction of no
less than 0.30 (or about 0.30) hard particles. Out of the 33 alloys
evaluated as shown in Table III, 100% of those with a hard phase
fraction of 30% or greater possessed greater than 40 HRC.
[0195] In the specific example of Alloy 1, shown in FIG. 6, the
hard precipitates include cementite, NbC,
(Cr,Mn).sub.23(C,B).sub.6, Cr.sub.3C.sub.2, Mn.sub.7C.sub.3, and
WC. The sum of these hard precipitates is 32% mole fraction.
[0196] In some embodiments, the thermodynamic criteria can be
useful for defining alloy performance used in processes with
cooling rates from 1K/s to 10,000 K/s (or about 1K/s to about
10,000 K/s). In some embodiments, the thermodynamic criteria can be
useful for defining alloy performance used in processes with
cooling rates from 10K/s to 100K/s (or about 10K/s to about
100K/s), 1K/s to 500 K/s (or about 1K/s to about 500K/s), or 50 K/s
to about 500 K/s (or about 50 K/s to about 500 K/s).
Microstructural Criteria
[0197] In some embodiments, an alloy can be defined by the
microstructural criteria which result in a specified performance of
the alloy. The microstructural criteria of this disclosure can be
divided into two categories, the matrix phase and the hard
precipitates. In some embodiments, the disclosure can be defined by
a set of microstructural features such as, for example, alloys
which possess an 90-95% (or about 90 to about 95%) or greater
volume fraction of austenite in the matrix phase, and possess a
hard precipitate fraction (carbides, borides, or borocarbides) in
excess of 20-30 (or about 20 to about 30) volume percent when
deposited as a hardfacing layer.
[0198] In some embodiments, the matrix phase can be austenitic
iron, which is the non-magnetic form of iron or steel. In some
embodiments, the matrix can be predominantly austenitic in order
for specified performance criteria to be met. In some embodiments
of this disclosure, the matrix can be at least 90%, 95%, or 99%
austenite (or about 90%, about 95%, or about 99% austenite).
Ferrite and martensite are the two most common and likely forms of
the matrix phase in this alloy space, however both are highly
magnetic and may prevent the hardfacing alloy from meeting the
magnetic performance requirements if present in sufficient
quantities. Therefore, ferrite and martensite can be minimized in
embodiments of the alloys.
[0199] Further, hard precipitates can precipitate into embodiments
of alloys. Hard precipitates can be defined as carbide, boride, or
borocarbide phases which can be present in a range of morphologies.
In some embodiments, the hard precipitate volume fraction can
exceed 20 volume % (or about 20 volume %). This can ensure that the
hardfacing alloy meets the hardness and wear resistance performance
criteria discussed in this disclosure.
[0200] FIG. 7 and FIG. 8 show scanning electron micrographs (SEM)
of Alloy 17 and Alloy 18, respectively, described in Table III,
which meet the above described microstructural criteria. The
micrographs show an austenitic matrix (darker grey phase) embedded
with hard particles (white and lighter grey phases). The phase
fractions of each alloy were evaluated using image analysis
software. Alloy 17 possesses 22.5% volume fraction carbides (or
about 22.5% volume fraction carbides) and Alloy 18 possesses 24.9%
volume fraction carbides (or about 24.9% volume fraction carbides).
This corresponds closely to the calculated mole fractions of hard
particles for each alloy as shown in Table III. Both alloys
contained three different types of hard particles:
(Mn,Cr).sub.23(C).sub.6, (Nb,Ti)C, and W.sub.6C.
[0201] In some embodiments, such as those having some level of
impact resistance or mechanical toughness, there may be an upper
limit on the hard phase fraction. For example, embodiments could
have a hard phase fraction greater than 20% (or greater than about
20%), but lower than 30% (or lower than about 30%).
[0202] Furthermore, in some embodiments, manufacturing processes
can be controlled. For example, by varying welding parameters, a
high rate of dilution with the base material can be achieved, which
can result in an artificially low hard phase volume fraction using
alloys of this disclosure. In some embodiments, the disclosed
alloys can be used as either feedstock chemistry for a specific
coating process or as the final chemistry of the coating after
process related effects, such as dilution with the base material,
have occurred. Thus, embodiments of the disclosed alloy composition
embodiments may possess a microstructure or performance
characteristic outside of the specified bounds when used in certain
coating deposition processes.
Performance Criteria
[0203] In some embodiments, alloys can be defined by their
performance. In some embodiments, two performance criteria can be
1) the relative magnetic permeability and 2) the wear resistance of
the hardfacing layer.
[0204] For example, in some embodiments, alloys can have a relative
magnetic permeability of 1.02 or less, or 1.01 or less (or about
1.02 or less, or about 1.01 or less), when deposited as a
hardfacing layer. Further, in some embodiments, the durability of
embodiments of the alloys can be defined by the ASTM G65 procedure
A test, hereby incorporated by reference in its entirety, and the
hardfacing layer can exhibit 1.5 grams or less mass loss when
subjected to this test, below 1.0 grams or less, or below 0.5 grams
or less (or below about 1.5 grams or less, below about 1.0 grams or
less, or below about 0.5 grams or less). In some embodiments, the
durability of embodiments of the alloys can be defined by mass loss
measured in ASTM G105 testing can be below 0.5 grams, below 0.2
grams, or below 0.05 grams (or below about 0.5 grams, below about
0.2 grams, or below about 0.05 grams). In some embodiments, the
durability of the alloy can be defined by the Rockwell C hardness,
which, for example, can be 40, 45, or 50 HRC (or about 40, about
45, or about 50 HRC) or greater. Testing results of certain
embodiments of alloys are shown in Table V.
TABLE-US-00005 TABLE V Wear Performance Results of Selected Alloy
Compositions Alloy ASTM G65 ASTM G105 1 0.24 N/M 8 0.48 N/M 14 0.43
0.15 15 1.32 0.046 All measurements in grams lost (N/M = not
measured)
[0205] In some embodiments, the hardfacing layer can have a minimum
level of corrosion resistance. Certain embodiments of this
disclosure have shown a desirable corrosion resistance to salt
water, an environment relevant to many industries, such as oil and
gas, mining, marine, construction, automotive, aerospace, and
others. Embodiments which have demonstrated this resistance by
exhibiting a corrosion rate of 2 mils per year or less (or about 2
mils per year or less) in the produced water (100,000 ppm NaCl, 500
ppm acetic acid, 500 ppm sodium acetate in tap water) include but
are not limited to Alloy 14 and Alloy 15. The corrosion rate of
Alloy 14 and 15 were measured at 2 mpy or less when tested under
ASTM G31 in produced water.
[0206] In some embodiments, the hardfacing layer can have a minimum
layer of impact resistance. It is expected that due to the
austenitic matrix present in the embodiments of this disclosure,
that such embodiments will inherently have high impact resistance,
exceeding those of ferritic or martensitic hardfacing
materials.
Applications
[0207] In some embodiments, the alloys described above can be
suitable for use as hardbanding/hardfacing in hard bodies wear
applications. In these applications, the material loss in coatings
is typically caused by abrasive wear of the harder abrading
particles, such as sand, rock, or earth. To reduce the material
loss in this process, the hardness of the coating can be increased
and/or the amount of comparably hard particles (comparable as
related to the abradable particles) or phases within the coating
can be increased. In some embodiments, the alloys can contain a
sufficient amount of hard particles and display a sufficient
hardness property for the protected equipment under these
conditions.
[0208] In some embodiments, the metal alloys can be applied onto a
surface using techniques including, but not limited to, thermal
spray coating, laser welding, weld-overlay, laser cladding, vacuum
arc spraying, plasma spraying, and combinations thereof. In some
embodiments, the alloys can be deposited as wire feedstock
employing hardfacing known in the art, e.g., weld overlay. The
alloys can be applied with mobile or fixed, semi or automatic
welding equipment. In some embodiments, the alloys are applied
using any of laser welding, shielded metal arc welding (SMAW),
stick welding, plasma transfer arc welding (PTAW), gas metal
arc-welding (GMAW), metal inert gas welding (MIG), submerged arc
welding (SAW), or open arc welding (OAW), although the type of
application is not limiting.
[0209] In some embodiments, the alloy can be deposited onto a
machined surface. In some embodiments, the surface can be surface
blast cleaned to white metal (e.g., ISO 8501-1, hereby incorporated
by reference in its entirety). The depth of the machined surface
can be grooved for flush type application depends on the welding
applicator. In some embodiments for application on a used pipe, the
existing hardbanding can be first completely removed by gouging,
grinding, or using other suitable techniques.
[0210] The coating can be applied as raised ("proud") or flush
("recessed") coating. The coating can be applied on used equipment,
e.g., pipe with no previous hardbanding, or to be hardbanded on new
work pieces. The coating can be deposited over pre-existing weld
deposits and many other previous hard-facing and hard-banding
deposits. In some embodiments, the old hardbanding on the equipment
is first removed before the application of the alloy
[0211] The disclosed alloys can be particularly useful for oil
& gas applications, such as for prolonging service life. For
example, the alloys can be used for work pieces employed in
directional drilling operations as coating for drill stem
assemblies, exposed outer surface of a bottom hole assembly,
coatings for tubing coupled to a bottom hole assembly, coatings for
casings, hardbanding on at least a portion of the exposed outer
surface of the body, and as coatings for oil and gas well
production devices, such as disclosed in U.S. Patent Publication
No. 2011/0042069A1, hereby incorporated by reference in its
entirety. Examples further include devices for use in drilling rig
equipment, marine riser systems, tubular goods, wellhead, formation
and sandface completions, lift equipment, etc. Specific examples
include drillpipe tool joints, drill collars, casings, risers, and
drill strings. The coating can be on a least a portion of the inner
surface of the work piece, at least a portion of the outer surface,
or combinations thereof, preventing wear on the drill collar. The
coatings can provide protection in operations with wear from
vibration (stick-slip and torsional) and abrasion during straight
hole or directional drilling, allowing for improved rates of
penetration and enable ultra-extended reach drilling with existing
equipment.
[0212] Besides the use as protective coatings, embodiments of the
above disclosed alloys can be used in the fabrication of articles
of manufacture, including drill collars and housings for containing
measurement-while-drilling equipment used in the directional
drilling of oil and gas wells. A drill collar can be made from a
bar, which can be trepanned to form an internal bore to desired
dimensions. Following trepanning, at least the interior surface can
be treated so as to place it into compression, for example as by
burnishing or peening.
[0213] Outside the oil & gas industry, the alloys can also be
used as coatings or forming work pieces in many other applications,
including but not limited to, coatings for fuel cell components,
cryogenic applications, and the like, for equipment operating in
corrosive environments with non-magnetic requirements.
[0214] In some embodiments, combinations of powders of the above
described alloys may be contained in conventional steel sheaths,
which when melted may provide the targeted alloy composition. The
steel sheaths may include plain carbon steel, low, medium, or high
carbon steel, low alloy steel, or stainless steel sheaths.
[0215] The ingots may then be melted and atomized or otherwise
formed into an intermediate or final product. The forming process
may occur in a relatively inert environment, including an inert
gas. Inert gasses may include, for example, argon or helium. If
atomized, the alloy may be atomized by centrifugal, gas, or water
atomization to produce powders of various sizes, which may be
applied to a surface to provide a hard surface.
[0216] The alloys may be provided in the form of stick, wire,
powder, cored wire, billet, bar, rod, plate, sheet, and strip. In
some embodiments, the alloys are formed into a stick electrode,
e.g., a wire, of various diameters, e.g., 1-5 mm (or about 1 to
about 5 mm). In some embodiments, the cored wire may contain flux,
which may allow for welding without a cover gas and without
porosity-forming in the weld deposit.
[0217] In some embodiments, the surfaces for deposition can be
first preheated at a temperature of 200.degree. C. (or about
200.degree. C.). or greater, e.g., 275-500.degree. C. (or about
275.degree. C. to about 500.degree. C.), for 0.01 hours to 100
hours (or about 0.01 to about 100 hours). In some embodiments, the
preheat may reduce or prevent cracking of the deposited welds.
[0218] The alloy may be applied to a surface in one or more layers
as an overlay. In some embodiments, each layer can have an
individual thickness of 1 mm to 10 mm. In some embodiments, the
overlay has a total thickness of 1 to 30 mm. In some embodiments,
the width of the individual hard-band ranges from 5 mm to 40 mm. In
another embodiment, the width of the total weld overlay ranges from
5 mm to 20 feet.
[0219] After deposition on a substrate, the alloy can be allowed to
cool to form a protective coating. In some embodiments, the cooling
rate can range from 100 to 5000 K/s (or about 100 to about 5000
K/s), a rate sufficient for the alloy to produce iron rich phases
containing embedded hard particles (e.g., carbides, borides, and/or
borocarbides). Embodiments of alloys that have been tested as welds
(e.g. 1, 2, 3, 8, 14, and 15) have shown that ferrite formation can
be prevented when the cooling rate is above 50 K/s (or above about
50 K/s). Embodiments of alloys that have been tested as ingots
(e.g. all alloys in Table 2) have shown that ferrite formation is
prevented when the cooling rate is above 1000 K/S (or above about
1000 K/s). After weld deposition, cooling in open air can cause a
cooling rate which is too rapid, leading to cracking of the weld.
Wrapping of the welded part with a thermally insulating blanket can
be sufficient to reduce the cooling rate to an acceptable
level.
[0220] Features, materials, characteristics, or groups described in
conjunction with a particular aspect, embodiment, or example are to
be understood to be applicable to any other aspect, embodiment or
example described herein unless incompatible therewith. All of the
features disclosed in this specification (including any
accompanying claims, abstract and drawings), and/or all of the
steps of any method or process so disclosed, may be combined in any
combination, except combinations where at least some of such
features and/or steps are mutually exclusive. The protection is not
restricted to the details of any foregoing embodiments. The
protection extends to any novel one, or any novel combination, of
the features disclosed in this specification (including any
accompanying claims, abstract and drawings), or to any novel one,
or any novel combination, of the steps of any method or process so
disclosed.
[0221] While certain embodiments have been described, these
embodiments have been presented by way of example only, and are not
intended to limit the scope of protection. Indeed, the novel
methods and systems described herein may be embodied in a variety
of other forms. Furthermore, various omissions, substitutions and
changes in the form of the methods and systems described herein may
be made. Those skilled in the art will appreciate that in some
embodiments, the actual steps taken in the processes illustrated
and/or disclosed may differ from those shown in the figures.
Depending on the embodiment, certain of the steps described above
may be removed, others may be added. Furthermore, the features and
attributes of the specific embodiments disclosed above may be
combined in different ways to form additional embodiments, all of
which fall within the scope of the present disclosure.
[0222] Although the present disclosure includes certain
embodiments, examples and applications, it will be understood by
those skilled in the art that the present disclosure extends beyond
the specifically disclosed embodiments to other alternative
embodiments and/or uses and obvious modifications and equivalents
thereof, including embodiments which do not provide all of the
features and advantages set forth herein. Accordingly, the scope of
the present disclosure is not intended to be limited by the
specific disclosures of preferred embodiments herein, and may be
defined by claims as presented herein or as presented in the
future.
* * * * *