LOW RHENIUM SINGLE CRYSTAL SUPERALLOY FOR TURBINE BLADES AND VANE APPLICATIONS

Abstract

A low rhenium nickel-base superalloy for single crystal casting that exhibits excellent high temperature creep resistance, while also exhibiting other desirable properties for such alloys, comprises 5.60% to 5.80% aluminum by weight, 9.4% to 9.9% cobalt by weight, 4.9% to 5.5% chromium by weight, 0.08% to 0.35% hafnium by weight, 0.50% to 0.70% molybdenum by weight, 1.4% to 1.6% rhenium by weight, 8.1% to 8.5% tantalum by weight, 0.60% to 0.80 titanium by weight, 7.6 to 8.0% tungsten by weight the balance comprising nickel and minor amounts of incidental impurity elements.

Claims

1. A nickel-base superalloy for single crystal casting, comprising: 5.60% to 5.80% aluminum by weight; 9.4% to 9.9% cobalt by weight; 4.9% to 5.5% chromium by weight; 0.08% to 0.35% hafnium by weight; 0.50% to 0.70% molybdenum by weight; 1.4% to 1.6% rhenium by weight; 8.1% to 8.5% tantalum by weight; 0.60% to 0.80 titanium by weight; 7.6 to 8.0% tungsten by weight; the balance comprising nickel and minor amounts of incidental elements, the total amount of incidental elements being about 1% or less; and wherein the casting exhibits a rupture life of at least about 200.2 hours at a temperature of 1800 F. under a load of 36.0 ksi.

2. The casting of claim 1 comprising: about 5.72% aluminum by weight; about 9.7% cobalt by weight; about 5.4% chromium by weight; about 0.30% hafnium by weight; about 0.59% molybdenum by weight; about 1.5% rhenium by weight; about 8.3% tantalum by weight; about 0.71% titanium by weight; and about 7.8% tungsten by weight.

3. The casting of claim 1, exhibiting a rupture life of at least about 983.5 hours at a temperature of 1600 F. under a load of 65 ksi, and a rupture life of at least 199.6 hours at a temperature of 1900 F. under a load of 25 ksi.

4. The casting of claim 1, wherein the time to 1% creep at a temperature of 1800 F. under a load of 36 ksi is at least 109.7 hours.

5. The casting of claim 4, wherein the time to 1% creep at a temperature of 1600 F. under a load of 65 ksi is at least 407.8 hours, and the time to 1% creep at a temperature of 1900 F. at a load of 25 ksi is at least 65.3 hours.

6. The casting of claim 1 that is homogenized and heat treated.

7. The casting of claim 6, wherein the homogenization is for a period of from 16 hours to 24 hours at temperatures from 2340 F. to 2408 F.

8. The casting of claim 6, wherein the heat treatment is for a period of 24 hours at temperatures from 2050 F. to 1600 F.

9. The casting of claim 8, wherein the homogenization is for a period of from 16 hours to 24 hours at temperatures from 2340 F. to 2408 F. and wherein the heat treatment is for a period of 24 hours at temperatures from 2050 F. to 1600 F.

10. A nickel-base superalloy single crystal casting comprising: about 5.72% aluminum by weight; about 9.7% cobalt by weight; about 5.4% chromium by weight; about 0.30% hafnium by weight; about 0.59% molybdenum by weight; about 1.5% rhenium by weight; about 8.3% tantalum by weight; about 0.71% titanium by weight; and about 7.8% tungsten by weight; the balance comprising nickel and minor amounts of indicated elements being about 1% or less; wherein the casting exhibits a rupture life of at least about 200.2 hours at a temperature of 1800 F. under a load of 36.0 ksi, a rupture life of at least about 983.5 hours at a temperature of 1600 F. under a load of 65 ksi, and a rupture life of at least 199.6 hours at a temperature of 1900 F. under a load of 25 ksi.

11. The casting of claim 6, wherein the time to 1% creep at a temperature of 1800 F. under a load of 36 ksi is at least 109.7 hours, the time to 1% creep at a temperature of 1900 F. at a load of 25 ksi is at least 65.3 hours.

12. The casting of claim 10 that is homogenized and heat treated.

13. The casting of claim 12, wherein the homogenization is for a period of from 16 hours to 24 hours at temperatures from 2340 F. to 2408 F.

14. The casting of claim 12, wherein the heat treatment is for a period of 24 hours at temperatures from 2050 F. to 1600 F.

15. The casting of claim 12, wherein the homogenization is for a period of from 16 hours to 24 hours at temperatures from 2340 F. to 2408 F. and wherein the heat treatment is for a period of 24 hours at temperatures from 2050 F. to 1600 F.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0015] FIGS. 1A, 1B and 1C are optical micrographs of castings made from the disclosed alloys (LA-11825, CMSX-8, test bar #N926, solutioned+2050 F./4 hours, gage area).

[0016] FIGS. 2A, 2B and 2C are scanning electron micrographs of castings made using the disclosed alloys (LA-11825, CMSX-8, test bar #N926, solutioned+2050 F./4 hours, gage area).

[0017] FIGS. 3 and 4 are Larson-Miller stress-rupture and stress-1.0% creep diagrams showing that the alloys disclosed herein have properties similar to advanced CMSX-4 single crystal nickel-base superalloy having a substantially higher rhenium content, up to 1900 F. (1040 C.).

[0018] FIGS. 5A, 5B and 5C are optical micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #A925, 1562 F./94.4 ksi/211.9 hours, fracture area).

[0019] FIGS. 6A, 6B and 6C are scanning electron micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #A925, 1562 F./94.4 ksi/211.9 hours, fracture area).

[0020] FIGS. 7A, 7B and 7C are optical micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #A925, 1562 F./94.4 ksi/211.9 hours, gage area).

[0021] FIGS. 8A, 8B and 8C are scanning electron micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #A925, 1562 F./94.4 ksi/211.9 hours, gage area).

[0022] FIGS. 9A, 9B and 9C are optical micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #E926, 1800 F./36 ksi/246.7 hours, fracture area).

[0023] FIGS. 10A, 10B and 10C are scanning electron micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #E926, 1800 F./36 ksi/246.7 hours, fracture area).

[0024] FIGS. 11A, 11B and 11C are optical micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #E926, 1800 F./36 ksi/246.7 hours, gage area).

[0025] FIGS. 12A, 12B and 12C are scanning electron micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #E926, 1800 F./36 ksi/246.7 hours, gage area).

[0026] FIGS. 13A, 13B and 13C are optical micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #L926, 2050 F./15 ksi/285.4 hours, fracture area).

[0027] FIGS. 14A, 14B and 14C are scanning electron micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #L926, 2050 F./15 ksi/285.4 hours, fracture area).

[0028] FIGS. 15A, 15B and 15C are optical micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #L926, 2050 F./15 ksi/285.4 hours, gage area).

[0029] FIGS. 16A, 16B and 16C are scanning electron micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11848, CMSX-8, test bar #L926, 2050 F./15 ksi/285.4 hours, gage area).

[0030] FIGS. 17A, 17B and 17C are optical micrographs showing adequate solutioning and/or homogenizing of an alloy casting using a shortened heat treatment cycle (LA-11862, CMSX-8, test bar #A926, solutioned to 2408 F./8 hours, longitudinal).

[0031] FIG. 18 is a Larson-Miller stress-rupture graphs showing the surprisingly good stress-rupture life properties of single crystal test bars and turbine blade castings made from the disclosed alloys.

[0032] FIGS. 19A, 19B and 19C are optical micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11890, CMSX-8, test bar #A926, 2050 F./15 ksi (1121 C./103 MPa)/271.8 hours, gage area).

[0033] FIGS. 20A, 20B and 20C are scanning electron micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are no detectable TCP phases (LA-11890, CMSX-8, test bar #A926, 2050 F./15 ksi (1121 C./103 MPa)/271.8 hours, gage area).

[0034] FIG. 21 is a drawing in cross section of a single crystal solid turbine blade cast from an alloy as disclosed herein which has the facility to machine both mini-bar and mini-flat specimens for machined-from-blade (MFB) stress-rupture testing.

[0035] FIGS. 22A, 22B and 22C are optical micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are negligible detectable TCP phases (needles) (LA-11895, CMSX-8, test bar #R926, 2000 F. (1093 C./83 MPa)/12 ksi/1979.9 hours, gage area).

[0036] FIGS. 23A, 23B and 23C are scanning electron micrographs demonstrating that the post-test phase stability of single crystal test bar castings made using the disclosed alloys is surprisingly good, and that there are negligible detectable TCP phases (needles) (LA-11895, CMSX-8, test bar #R926, 2000 F. (1093 C./83 MPa)/12 ksi/1979.9 hours, gage area).

DETAILED DESCRIPTION

[0037] The low-rhenium nickel-base superalloys for single crystal casting disclosed herein will be designated CMSX-8 alloys, and will be referred to as such herein. The term CMSX is a trademark registered to Cannon-Muskegon Corporation for use in connection with the sale of a family of single crystal (SX) nickel-base superalloys.

[0038] Unless otherwise indicated herein, all amounts of elements are given as a percentage by weight or in parts per million (ppm) by weight based on the entire weight of the alloy composition.

[0039] Single crystal superalloys and castings have been developed to exhibit an array of outstanding properties including high temperature creep resistance, long fatigue life, oxidation and corrosion resistance, and solid solution strengthening, with desired casting properties with low rejection rates, and phase stability, among others. While it is possible to optimize a single additive for a particular property, the effects on other properties are often extremely unpredictable. Generally, the relationships among the various properties and various elemental components are extremely complex and unpredictable such that it is surprising when a substantial change can be made to the composition without deleteriously affecting at least certain essential properties.

[0040] With the embodiments disclosed herein, refractory metal elements (tantalum, tungsten, rhenium and molybdenum) (Table 1) were maintained at a total amount of from about 18% to about 19% by weight, while balancing the amounts of the refractory elements to achieve good creep-rupture mechanical properties along with acceptable alloy phase stability (freedom from excessive deleterious topological close-packed (TCP) phasesnormally tungsten, rhenium and chromium rich in this type of alloy). Chromium and cobalt amounts are targeted accordingly to ensure this required phase stability. The high tantalum at approximately 8% is designed to give good single crystal castability and freedom from freckling defects, and, along with the 5.7% aluminum and the 0.7% titanium, appropriate volume fraction at approximately 70% and low negative / mismatch for high temperature creep strength, and acceptable room temperature density of about 8.85 gms/cc (kg/dm.sup.3). The density of CMSX-4 is 8.70 gms/cc (kg/dm.sup.3) and PWA 1484 is 8.95 gms/cc (kg/dm.sup.3). Aluminum, tantalum and titanium are targeted at volume fraction (Vf) attainment, along with low molybdenum for good high temperature oxidation properties. The small hafnium addition is required for coating life attainment at high temperatures.

[0041] Typical chemistry for the alloys disclosed and claimed herein are listed in Table 1. However, there are certain minor variations. First, in order to achieve enhanced oxidation resistance and/or enhanced thermal barrier coating life, it is desirable to add lanthanum and/or yttrium in amounts such that the total of lanthanum and yttrium is targeted to provide from about 5 to 80 ppm in the single crystal castings made from the alloys. As another variation, in the case of large industrial gas turbine (IGT) single crystal applications where low angle boundary (LAB) strengthening is provided up to 12 degrees, carbon and boron additions are targeted in the range from about 0.02% to 0.05% and 40-100 ppm, respectively.

TABLE-US-00001 TABLE 1 CHEMISTRY (WT %/ppm) SPECIFICATIONS CMSX-8 ALLOY Aero engine Applications C 100 ppm Ta 8.1-8.5 Si .04% Max Ti .60-.80 Mn .01% Max W 7.6-8.0 S 3 ppm Max Zr 150 ppm Max Al 5.60-5.85 Cu .01% Max B 30 ppm Max Fe .15% Max Cb (Nb) .10% Max V .10% Max Co 9.4-9.9 Ru .10% Max Cr 4.9-5.5 Pt .15% Max Hf .08-.35 Pd .15% Max Mo .50-.70 Mg 200 ppm Max Ni Balance [N] 5 ppm Max Re 1.4-1.6 [O] 5 ppm Max Enhanced oxidation resistance/coating and thermal barrier coating (TBC) life S 0.5 ppm max La + Y 5-80 ppm (In the SX castings). Industrial Gas Turbine (IGT) SX Applications Low angle boundary (LAB) Strengthened up to 12. C 0.05% Max B 100 ppm Max TRACE ELEMENT CONTROLS - ALL APPLICATIONS Ag 2 ppm Max Hg 2 ppm Max Bi .2 ppm Max Cd 2 ppm Max Ga 10 ppm Max Ge 2 ppm Max Ca 25 ppm Max Au 2 ppm Max Pb 1 ppm Max In 2 ppm Max Se .5 ppm Max Na 20 ppm Max Te .2 ppm Max K 10 ppm Max Tl .2 ppm Max Ba 10 ppm Max Sn 10 ppm Max P 30 ppm Max Sb 2 ppm Max U 2 ppm Max As 2 ppm Max Th 2 ppm Max Zn 5 ppm Max Density: 8.85 gms/cc (kg/dm.sup.3).

[0042] The invention will be described below with respect to certain illustrative, non-limiting embodiments that will facilitate a better understanding.

[0043] A 470 lb 100% virgin initial heat of CMSX-8 alloy was melted in May 2011 in the CM V-5 Consarc VIM furnace using aim chemistry to CM KH 04/20/11 (CM CRMP #81-1708 Issue 1). The heat (5V0460) chemistry is shown in Table 2.

[0044] Two molds (#s 925 and 926) of SX NNS DL-10 test bars were cast to CMSX-4 casting parameters by Rolls-Royce Corporation (SCFO). DL-10 test bar yield at 23 fully acceptable out of a total 24 cast was excellent.

[0045] These DL-10 test bars were solutioned/homogenized and double aged heat treated at Cannon-Muskegon Corporation as followsbased on prior work with a precursor similar family alloy designated CMSX-7.

[0046] Solutioning and Homogenization

[0047] 2 hrs/2340 F. (1282 C.)+2 hrs/2360 F. (1293 C.)

[0048] +4 hrs/2380 F. (1304 C.)+4 hrs/2390 F. (1310 C.)

[0049] +12 hrs/2400 F. (1316 C.) AC (air cool)ramping up at 1 F./min. between steps

[0050] Double Aged Heat Treatment

[0051] 4 hrs/2050 F. (1121 C.) AC+20 hrs/1600 F. (871 C.) AC

[0052] Good microstructure attainment is evident in FIGS. 1-2complete solutioning, little remnant / eutectic, no incipient melting and approximately 0.45 m average cubic, aligned , indicating appropriate / mismatch and / inter-facial chemistry, following the 4 hr/2050 F. (1121 C.) high temperature age.

[0053] Creepand stress-rupture specimens were low stress ground and tested by Joliet Metallurgical Labs, with the results to date shown in Table 3. Larson-Miller stress-rupture and stress1.0% creep (FIGS. 3 & 4) show CMSX-8 has similar and surprisingly good creep strength/stress-rupture life properties to CMSX-4 alloy (3% Re) up to approximate 1850 F.-1900 F. (1010-1038 C.), with fall-off at 2050 F. (1121 C.) due to its cost saving lower Re (1.5%) content. All these properties are significantly higher than Rene N-5 (3% Re) and Rene N-515 (low Re) alloys (JOM, Volume 62, Issue 1, pp. 55-57).

TABLE-US-00002 TABLE 2 HEAT #5V0460 CMSX-8 - 100% VIRGIN CHEMISTRY (WT ppm/%) C 9 ppm Si <.02 Mn <.001 S 1 ppm Al 5.72 B <20 ppm Cb (Nb) <.05 Co 9.7 Cr 5.4 Hf .30 Mo .59 Ni Balance Re 1.5 Ta 8.3 Ti .71 W 7.8 Zr <10 ppm Cu <.001 Fe .010 V <.005 Ru <.01 Pt <.001 Pd <.001 Mg <100 ppm [N] 2 ppm [O] 2 ppm Y <.001 La <.001 Ce <.002 Ag <.4 ppm Bi <.2 ppm Ga <10 ppm Ca <25 ppm Pb <.5 ppm Se <.5 ppm Te <.2 ppm Tl <.2 ppm Sn <2 ppm Sb <1 ppm As <1 ppm Zn <1 ppm Hg <2 ppm Cd <.2 ppm Ge <1 ppm Au <.5 ppm In <.2 ppm Na <10 ppm K <5 ppm Ba <10 ppm P 6 ppm U <.5 ppm Th <1 ppm

TABLE-US-00003 TABLE 3 CMSX-8 Heat - 5V0460 Molds 925/926 - RR SCFO [Indy] - LA 11832 (Joliet/CM 366) Fully Heat Treated - Solution + Double Age [DL-10 s] Creep-Rupture Rupture Life, % % 1% 2% Test Condition ID hrs Elong RA Creep Creep 1562 F./94.4 ksi A925 211.9 17.5 21.5 7.3 39.1 [850 C./651 Mpa] B926 157.1 16.4 22.8 2.3 23.2 1600 F./65.0 ksi B925 1072.0 27.4 33.5 482.8 631.5 [871 C./448 Mpa] C926 983.5 26.8 33.0 407.8 536.4 1800 F./36.0 ksi C925 200.2 35.0 43.3 109.7 125.1 [982 C./248 Mpa] E926 246.7 44.6 46.0 120.0 140.1 1850 F./38.0 ksi E925 86.0 37.2 38.6 39.7 46.6 [1010 C./262 Mpa] H926 65.9 41.4 44.0 28.6 35.6 1900 F./25.0 ksi H925 214.7 38.6 39.4 82.0 105.0 1038 C./172 Mpa] J926 199.6 33.2 39.5 65.3 93.7 1904 F./21.0 ksi J925 362.4 30.0 37.5 141.3 182.6 [1040 C./145 Mpa] K926 359.1 33.1 34.8 164.2 194.6 1950 F./18.0 ksi L925 481.1 31.4 34.9 194.1 246.1 [1066 C./124 Mpa] M926 449.6 40.0 38.9 166.1 211.5 Stress-Rupture Test Condition ID Rupture Life, hrs (4 D) % Elong % RA 2000 F./12.0 ksi N925 1983.2 13.0 37.9 [1093/83 Mpa] R926 1979.9 24.8 33.0 2050 F./15.0 ksi R925 275.5 24.5 38.3 [1121/103 Mpa] L926 285.4 22.9 40.4 Alternate Heat Treatment (Tmax 2408 F.) 1800 F./36.0 ksi D925 249.0 43.1 44.0 114.5 134.8 [982 C./248 Mpa] 2050 F./15.0 ksi A926 271.8 13.6 38.1 [1121/103 Mpa]

[0054] Phase stability is surprisingly good with absolutely negligible TCP phases apparent in the post-test creep/stress rupture bars examined to date (FIGS. 5-16 inclusive and 22-23 inclusive).

[0055] Recent work has shown it is possible to adequately solution/homogenize heat treat a single crystal test bar in the alloy (FIG. 17), using a shortened cycle2 hrs/2365 F. (1296 C.)+2 hrs/2385 F. (1307 C.)+2 hrs/2395 F. (1313 C.)+2 hrs/2403 F. (1317 C.)+8 hrs/2408 F. (1320 C.) AC (8 hrs shorter). Limited creep/stress-rupture properties at critical conditions using this shorter solution/homogenization heat treatment show very similar results to the original solution heat treatment condition (Table 3 and 4) and good phase stability [no TCP phases] (FIGS. 19 & 20).

[0056] Burner rig dynamic, cyclic oxidation and hot corrosion (sulfidation) testing is currently scheduled at a major turbine engine company.

[0057] Creep/stress-rupture data for fully heat treated solution/homogenized and double aged (DL-10s) test specimens for the disclosed alloys are presented in Table 4.

TABLE-US-00004 TABLE 4 CMSX-8 Heat 5V0460 Heat 5V0460 - Mold 54275 - HP2 Solid Turbine Blades RR SCFO [Indy] - LA11865 (Joliet 9220/CM-373) Fully Heat Treated - Solution + double age - 2050 F. Primary age Stress-Rupture MFB Mini Bars [0.070 gage] (LLE) Rupture Life, % (4 D) % Test Condition ID hrs Elong RA 1562 F./94.4 ksi 54275A-B 449.0 16.3 18.7 [850 C./651 MPa] 54275B-B 359.8 18.7 19.9 1800 F./36.0 ksi 54275E-B 223.4 43.1 45.6 [982 C./248 MPa] 54275H-B 219.1 45.1 46.9 1850 F./38.0 ksi 54275I-B 74.2 46.2 47.8 [1010 C./262 MPa] 54275J-B 76.7 39.2 43.8 1900 F./25.0 ksi 54275K-B 181.8 41.2 48.5 [1038 C./172 MPa] 54275L-B 190.8 41.8 38.9 1904 F./21.0 ksi 54275R-B 354.0 43.9 40.2 [1040 C./45 MPa] 54275O-B 599.3 39.2 45.7 1950 F./18.0 ksi 54275T-B 410.1 27.9 48.8 [1066 C./124 MPa] 54275U-B 420.6 39.1 41.1 2050 F./15.0 ksi 54275X-B 287.5 26.3 32.7 [1121 C./103 MPa] 54275Y-B 205.8 22.7 25.1 MFB Mini Flats [0.020 Thick Gage] (LTE) Test Condition ID Rupture Life, hrs % Elong 1800 F./30.0 ksi 54275A-F 490.7 41.1 [982 C./207 MPa] 54275B-F 446.0 28.8 54275E-F 437.5 24.2 54275H-F 381.9 31.6 1904 F./21.0 ksi 54275I-F 404.0 36.4 [1040 C./145 MPa] 54275J-F 325.1 28.6 54275K-F 312.1 24.5 54275L-F 341.1 26.6

[0058] Mini-flat bar stress-rupture testing was performed on single crystal solid turbine blades 10 (FIG. 21) cast from alloys as disclosed herein that have facility to machine mini-bar specimens 15 and mini-flat specimens 20.

[0059] A Larson-Miller stress-rupture graph (FIG. 18) shows CMSX-8 alloy has surprisingly good stress-rupture life properties, from machined-from-blade (MFB) mini-flat (0.020 (0.508 mm) gage thickness) specimens, that are close to those of a CMSX-4 alloy.

[0060] The embodiments disclosed herein are non-limiting examples that are provided to illustrate and facilitate a better understanding, the scope of the invention being defined by the appending claims as properly construed under the patent laws, including the doctrine of equivalents.

[0061] The above description is intended to be illustrative, not restrictive. The scope of the invention should be determined with reference to the appended claims along with the full scope of equivalents. It is anticipated and intended that future developments will occur in the art, and that the disclosed devices, kits and methods will be incorporated into such future embodiments. Thus, the invention is capable of modification and variation and is limited only by the following claims.