WO1999061195A1

WO1999061195A1 - Cobalt-chromium-palladium-based brazing alloys

Info

Publication number: WO1999061195A1
Application number: PCT/US1999/011867
Authority: WO
Inventors: Anatol Rabinkin
Original assignee: Alliedsignal Inc.
Priority date: 1998-05-29
Filing date: 1999-05-28
Publication date: 1999-12-02
Also published as: IL139994A0; CN1311725A; JP2002516183A; IL139994A; EP1082190B1; EP1082190A1; CN1113725C; HK1040066B; WO1999061195A9; CA2333630A1; DE69902383T2; AU4318999A; HK1040066A1; US6165290A; DE69902383D1

Abstract

This invention relates to brazing metals composed of cobalt-chromium-palladium-based alloys containing transition metals such as cobalt, nickel, tungsten, molybdenum and certain metalloids; and more particularly to multicomponent alloys containing cobalt, chromium, palladium, nickel, tungsten, molybdenum, boron, and silicon, which are especially useful for brazing metals at high temperatures to produce high strength, high oxidation and high temperature and corrosion-resistant brazements. Alloys of the present invention have a composition represented by the formula: CraNibWcPddSieBfCobal (plus incidental impurities), where the subscripts 'a', 'b', 'c', 'd', 'e', and 'f' are in atomic percent and 'a' is in the range of about 15 and about 22, 'b' is between about 0 and about 20, 'c' is in the range of about 1 to about 5, 'd' is between about 1 and about 10, 'e' is in the range of about 5 and about 12, and 'f' is between about 5 to about 12 and 'bal' is the balance amount to total 100 percent.

Description

COBALT-CHROMIUM-PALLADIUM-BASED BRAZING ALLOYS

BACKGROUND OF THE INVENTION

1. Field Of The Invention:

This invention relates to brazing metals composed of cobalt-chromium-

palladium-based alloys containing transition metals such as cobalt, nickel, tungsten,

molybdenum and certain metalloids; and more particularly to multicomponent alloys containing cobalt, chromium, palladium, nickel, tungsten, molybdenum,

boron, and silicon, which are especially useful for brazing metals at high temperatures to produce high strength, high oxidation and high temperature and

corrosion-resistant brazements. Alloys of the present invention have a

composition represented by the formula:

Cr.NibW.Pdd SieBfO

(plus incidental impurities), where the subscripts "a", "b", "c", "d ", "e", and "f '

are in atomic percent and "a" is in the range of about 15 and about 22, "b" is

between about 0 and about 20, "c" is in the range of about 1 to

about 5, "d" is between about 1 and about 10, "e" is in the range of about 5 and

about 12, and "f ' is between about 5 to about 12 and "bal" is the balance amount

to total 100 percent. 2. Description of the Prior Art:

Brazing is a process for joining metal parts, often of dissimilar composition,

to each other. Typically, brazing is accomplished by interposing a filler metal that

has a melting point lower than that of the parts to be joined to form an assembly.

The assembly is then heated to a temperature sufficient to melt the brazing filler metal. Upon cooling, a strong, preferably high oxidation and high temperature and

high corrosion resistant joint is formed.

A few classes of products produced by brazing processes are used as

critical parts of power turbines which are operated, for example as jet engines in the aerospace industry and in stationary power plants to generate electrical energy.

Particular power turbine parts, such as turbine seals, first-stage turbine nozzle guide vanes, and turbine blades, are subjected to high temperature highly oxidized environments in operation. Thus, the brazed parts used in these applications must

be able to withstand such harsh operating conditions in order to achieve high

energy efficiency that directly relates with operating temperature.

An another important application of brazing technology is the manufacture

of light-weight high temperature resistant honeycomb structures for leading edges

of wings and other body parts of supersonic jets and reusable shuttles. In these applications, the base metals to be joined are mostly nickel- and cobalt-based

superalloys and high chromium containing iron-based alloys. Such superalloys and

iron-chromium-based alloys have complex compositions comprised of some or all

of a group of transition elements such as cobalt, nickel, chromium, iron, and some refractory elements. Additionally, all these alloys also typically contain aluminum,

titanium and, sometimes, yttria additions to improve their high temperature and high oxidation resistance. The latter is achieved due to intrinsic formation of oxide

alumina/titania surface protecting film on such base metal parts. Of particular importance for all parts subjected to high temperature service

environment is their resistance to oxidation while maintaining the part's mechanical integrity. The oxidation resistance of these base metals is due to existence of the above mentioned dense alumina/titania protecting film on the part surface.

Unfortunately, brazing by using filler metals containing active metalloid elements such as boron and silicon, causes a partial or even complete dissolution of these

protecting oxide films in the brazed areas. As a result, the brazed interfaces act as

conduits for oxygen penetration which can cause catastrophic part oxidation.

Therefore, during the brazing of materials it is of paramount importance to preserve the integrity of the braze interfaces even if these oxide films cannot be

preserved in the initial state.

Previously, some amorphous brazing filler metals consisting of

cobalt/nickel-chromium-based alloys have been developed which exhibit a

sufficient strength and good corrosion resistance at elevated temperatures. Such

alloys have been disclosed, for example, in U.S. Pat. Nos. 4,260,666, 4,515,868,

4,515,869, 4,515,870, and 4,801,072. The alloys disclosed in these patents,

however, each exhibit drawbacks, which make them unsuitable for brazing

products that require prolonged service life at high temperature and in highly oxidizing and corrosive environments. For example, the alloys disclosed in U.S Pat. No. 4,260,666, 4,515,868 and 4,801,072 contain the transition and refractory

elements and boron and silicon Unfortunately, boron due to its very small atomic

radius diffuses extensively out of the joint area into alloys, particularly in those containing chromium, because of tendency to form strong chromium borides.

These borides are formed preferentially at grain boundaries resulting in alloy brittleness and excessive oxidation or even complete failure. At the same time, these alloys contain no elements which protect the base metal from boron diffusion

Regarding the multicomponent alloys disclosed in U.S. Pat. Nos. 4,515,869 and 4,515,870, they also contain the similar transition and refractory elements and

boron and silicon but are based on nickel. Therefore these multicomponent alloys, contain only a moderate (less than 30 atom per cent) amount of cobalt and as a

result are is insufficient to protect brazed parts from high temperature and highly oxidizing environment. For the above reasons, the alloys previously known are not effective for

use in brazed products to be employed in high temperature, high oxidizing and high

stress environments existing in turbine engines and supersonic airspace structural

applications.

Accordingly, there remains a need in the art for improved brazing filler

materials suitable for brazing superalloys and iron-chromium-based alloys at high

temperatures that can withstand a service in high temperature and highly oxidizing environments under high stresses for a long time. Specifically, there has been a need in the art for a brazing filler metal that

would form naturally a protecting layer of high temperature resistant phases at the

braze interface, protecting base metal parts from excessive boron penetration on completing of brazing. Moreover, it would be even more beneficial if this layer

could keep boron inside the joint preventing it from excessive diffusion into the base metal. Thus, it is an object of the present invention to provide such a brazing metal.

It is a further object of the present invention to provide brazing filler metals

that first, contain major metallic elements that are compatible with high

temperature resistant base metals; second, can wet oxide covered surface during

brazing operation; and third, contain an element or elements that predominantly

migrate to and form a protecting phase layer at the joint interface.

SUMMARY OF THE INVENTION

The present invention provides an improved brazing filler metal which possesses

high temperature melting characteristics and forms brazements that have high

strength and high oxidation resistance at very high service temperatures. Brazing

alloys particularly suited for use as the filler metal contain cobalt, chromium,

palladium, nickel, tungsten, molybdenum, boron, and silicon, which are especially

useful for brazing metals at high temperatures to produce high strength, high oxidation and high temperature and corrosion-resistant brazements. Alloys have a

composition represented by the formula:

Cr_aNi_bW_cPd_d Si_eBfCθbai.

plus incidental impurities, where the subscripts "a", "b", "c", "d ", "e", and "f" are in atomic percent and "a" is in the range of about 15 and about 22, "b" is between about 0 and about 20, "c" is in the range of about 1 to about 5, "d" is between about 1 and about 10, "e" is in the range of about 5 and

about 12, and "f" is between about 5 to about 12 and "bal" represents the balance

of to total 100 percent.

The alloys of the present invention exhibit a number of advantageous

properties not recognized nor disclosed heretofore. These alloys exhibit a high

melting temperature in the range of about 1050 and about 1180°C . These alloys

exhibit virtually negligible diffusion problems associated with boron containing alloys because they contain only low amount of boron and, most importantly,

contain palladium. Palladium forms a predominant layer of high melting high

oxidation resistant aluminum-palladium AlPd intermetallic phase at joint interfaces

thus preventing boron penetration, changing, refining favorably the joint

microstructure and protecting joints from oxidation. Further, in spite of the

presence of palladium, minimization of boron concentration coupled with

maintaining silicon concentration at relatively low levels the alloys of the present

invention can be manufactured as a ductile product. More further, increasing the palladium concentration at the expense of the cobalt concentration preserves the

ability of the alloy to be formed in the amorphous state and to remain ductile in the foil form.

The brazed base metal parts are protected from oxidation and their high temperature strength is at a high level because the alloys of the present invention

exhibit excellent protection from excessive detrimental boron diffusion into the

base metal due to formation of a beneficial layer of AlPd phase at joint interfaces.

Likewise, because the high temperature solid AlPd phase forms first at the solid base metal/liquid filler metal interface, the erosion of thin base metal stock is substantially restrained due to curtained interaction between liquid filler and solid

base metals.

Brazements produced using such filler metal have substantially uniform microstructure and possess high strength at elevated temperatures. In addition, the

invention provides brazing filler metals in the form of homogeneous ductile foils

which are composed of metastable materials preferably having at least 80%

amorphous structure.

Further, in accordance with the present invention, an improved process is

provided for joining superalloys and/or iron-chromium-based honeycomb

structures, which process comprising the steps of: interposing a filler metal of the

above described composition between base metal parts to form an assembly,

heating the assembly to a temperature about 25 to 50°C above the liquidus temperature of the brazing filler metal and holding at this temperature for a time

sufficient to form a strong and oxidation resistant joint.

BRIEF DESCRIPTION OF THE DRAWING

This invention will be more fully understood and further advantages will

become apparent when reference is made to the following detailed description of the preferred embodiments of the invention and the accompanying drawing, in

which: FIG. 1 is an SEM micrograph of a iron-chromium-aluminum-based joint made using a filler metal manufactured according to previous art as depicted in US

Patent No. 4,260,666, the micrograph depicting presence of a substantial amount

of chromium borides (at black arrows) precipitated in the body of base metal part.

These borides segregate predominantly at planes which are parallel to the direction

of rolling of the base metal alloy.

FIG. 2 is an SEM micrograph of an iron-chromium-aluminum-based joint

made using a filler metal which contains 3 wt.% palladium and was manufactured according to the present invention, the micrograph depicting a dense layer of AlPd

intermetallic phase formed at the joint interface (at empty arrows) and protecting

base metal from boron penetration and formation of detrimental chromium borides.

The base metal has a substantially uniform, single phase microstructure with a very

limited amount of precipitated chromium borides. FIG. 3 is an SEM micrograph of an iron-chromium-aluminum-based joint

made using a filler metal which contains 5 wt.% palladium and was manufactured

according to the present invention, the micrograph depicting the same beneficial

basic features of the joint microstructure as that shown in FIG. 2 but containing a

substantially larger amount of the AlPd phase (at empty arrows). This

demonstrates that formation of AlPd phase is indeed related to the amount of palladium in the filler metal alloy of the present invention.

Fig. 4 is an x-ray diffraction patent taken from foil Sample No. 4 which

shows a diffused hallo characteristics of amorphous state.

DETAILED DESCRIPTION OF THE INVENTION

In any brazing process, the brazing material must have a melting point that

will be sufficiently high to provide strength to meet service requirements of the

metal parts to be brazed together. Further, the material must be compatible, both

chemically and metallurgically, with the base metal parts being brazed. Ideally, the

brazing material should be in 100% metal containing foil form so that complex

shapes may be stamped therefrom and so that brazing of complex structures can be

readily accomplished. Moreover, brazing foils should be homogeneous and ductile;

that is, contain no binders or other materials that would otherwise form voids or

contaminating residues during brazing, and exhibit sufficient flexibility such that the foil can be bent to a round radius as small as about 10 times the foil thickness without fracture.

In accordance with the present invention, multicomponent cobalt/nickel-

chromium-based alloys are provided which exhibit a liquidus of at least about 1090 degree(s) C, and are particularly suitable for brazing superalloys and iron-

chromium-aluminum-based alloys . The brazing filler metals have a composition

represented by the formula:

Cr_aNibW_cPdd SieB_fCo_bai.

plus incidental impurities, where the subscripts "a", "b", "c", "d ", "e", and "f ' are

in atomic percent and "a" is in the range of about 15 and about 22, "b" is between about 0 and about 20, "c" is in the range of about 1 to about 5, "d" is between about 1 and about 10, "e" is in the range of about 5 and

about 12, and "f ' is between about 5 to about 12 and "bal" represents the balance

amount to total 100 percent.

Boron and silicon are added to enhance the ability of the alloys to exist in

the amorphous form and to lower the melting point of the alloys. The additions of

boron and silicon also provide wettability and ensure metallurgical bonding

between the filler metal and the base. Individually, boron is present in the amount

of about 5 to about 12, and more preferably about 6.5 to about 8.0 atom percent,

to improve amorphability and interaction between base and filler metals. The

silicon content ranges from about 5 to about 12, and more preferably from about 5.0 to about 10.5 atom percent. In these amounts, it is believed that silicon

operates to induce formation of the amorphous structure and contributes to

brazeability of the filler metal. The total boron and silicon content cannot be so great as to cause excessive erosion of the base metal during brazing or to cause the excessive formation of separate brittle intermetallic compound phases in the

brazement. Preferably, the total boron and silicon content of the filler metal ranges from about 14.5 to about 20 atom percent, and more preferably ranges from 14.5

to about 17 atom percent.

Of critical importance is palladium in an amount 1 atom percent to about 10

atom percent and more preferable 1.5 to 7 atom percent to form a protecting layer of high temperature intermetallic aluminum-palladium phase at the interface between the braze and the base metal. According to binary aluminum-palladium

constitutional phase diagrams, both these elements form a very high melting (T _meu.

=1645°C) strong and oxidation resistant AlPd intermetallic component which exist

in a narrow compositional range. See "Binary Alloy Phases Diagnosis" Ed. T. Misoalski, ASM 1990, p. 139-191. This compound, according to the standard

thermodynamics data, has a very high value of entalphy of formation compared

with that of any other potential intermetallic and other phases which cobalt,

chromium, tungsten, iron, and silicon may form with aluminum. The high value of

entalphy of formation is a basic measure of the intensity of a chemical reaction

between elements involved and an indicative of the chemical stability and the

mechanical strength of its resulting product substance(s), i.e., AlPd in this particular case. (See Table 1) It was discovered in this invention that during

brazing operation the AlPd binary intermetallic phase segregates first at the joint

interface between multicomponent base and filler metals. It is believed that as a

result, formation of a protective phase layer occurs. In addition, preferably, tungsten is also present in an amount between about

1 and about 5 atom percent, and more preferably in an amount ranging from about 3.0 to about 3.5 atom percent. The role of tungsten in the alloys of the present

invention is to preserve the high melting temperature of the alloy while increasing

the overall strength of the passive film forming on brazes. Cobalt and chromium, major elemental components, constitute the compositional base of the alloys of the present invention and they are particularly suited to provide a high temperature oxidation resistance of brazes formed. The

presence of nickel in alloys of the present invention greatly improves their

resistance to certain non-oxygenating corrosive media. Nickel also imparts other

desired properties, such as amorphability, ductility and the like.

The alloys of the present invention can be produced in various forms, such

as powders, foils, ribbons and wires by application of various well known

techniques. The alloys of the present invention may also be produced in the form

of metastable powders, homogeneous, ductile foils or wires by casting alloys

of the above described composition using rapid solidification techniques.

Methods commonly used to fabricate alloys in powder form include gas or water

atomization or mechanical pulverization. The most preferred method used to fabricate alloys of the present invention into foils, ribbons or wire is rapid

solidification.

The alloys of the present invention exhibit a number of advantageous properties neither recognized nor disclosed heretofore. These alloys exhibit a high

melting temperature and no significant diffusion problems, generally associated with high boron-containing alloys, because boron concentration is kept at a

minimum whereas the presence of palladium keeps boron predominantly inside of the braze. At the same time, boron concentration, coupled with sufficient silicon

concentration, enables the production of a ductile and thick ribbon product by

rapid solidification technology. Moreover, containing combined boron and silicon concentration at sufficient levels and keeping chromium concentration at about 21 atom % threshold preserves the ability of the alloy to be formed in the amorphous

state and to remain ductile in the ribbon shape. Finally, the alloys of the present

invention do not substantially erode the base metal, thereby preserving the integrity

of thin fin parts used in honeycomb and plate-type structures.

The alloys of the present invention may be produced in the form of

homogeneous, ductile foils or wires by casting alloys of the above described

composition using rapid solidification techniques. More specifically, the

homogeneous brazing filler metals of the present invention may be fabricated by a

rapid solidification process which comprises forming a melt of the composition,

and quenching the melt on a rotating quenching wheel at a rate of at least about 10⁵ degree(s) C per second. Such a process is disclosed in U.S. Pat. No. 4,142,571.

Under these quenching conditions, a metastable, homogeneous ductile

product is obtained. The metastable material may be amorphous, in which case

there is no long range order as evidenced by X-ray diffraction patterns which show

a diffuse halo, similar to that observed for inorganic oxide glasses (Fig. 4).

Preferably, the microstructure of alloys of the present invention contained at least 50% of amorphous phase to achieve superior ductility, and most preferably it is at

least about 90% amorphous. Metastable products may also be a solution of constituent elements. In the case of the alloys of the present invention, such metastable, solid solution phases

are not ordinarily produced under conventional processing techniques employed in

the art of fabricating crystalline alloys. Accordingly, the above-described casting

processes are employed. These metastable products may be rapidly solidified powders or foils which are also ductile.

Foils produced by the rapid solidification process described herein are

between about 13 and about 100 micrometers thick, ordinarily between about 13

and about 76 micrometers thick and up to 200 mm wide and more. Because these

products are homogeneous (i.e., of substantially uniform composition in all

directions), brazements produced therefrom are quite uniform and substantially free

of voids. Within the broad range of the compositions of the present invention, a preferred embodiment has been discovered having a composition of about 18 atom

percent to about 22 atom percent chromium, 12 to about 17 atom percent nickel, about 1.5 to about 7 atom percent palladium, about 3.0 to about 3.5 atom percent

tungsten, about 5 to about 10.5 atom percent silicon, and about 6.5 to about 8.0

atom percent boron, the balance being essentially cobalt and incidental impurities. The alloys within this most preferred embodiment exhibit a melting temperature

range of between about 1010 degree(s) C and about 1180 degree(s) C and, most preferably, range from about 1015 degree(s) C to about 1160 degree(s) C. The specific advantages of these alloys include the ability to braze at high temperatures

and to provide a brazement which can be employed at elevated temperature under high oxidation and corrosive environment without any significant degradation of

mechanical properties.

Alloys produced in accordance with the invention are particularly suited for

the brazing of turbine parts and air and space craft structures used in aircraft

industries and power plant.

The following examples are presented to provide a more complete

understanding of the invention. The specific techniques, conditions, materials,

proportions and reported data set forth to illustrate the principles and practice of

the invention are exemplary and should not be construed as limiting the scope of the invention. Example 1

Ribbons about 2.54 to about 200 mm (about 0.1 to about 8 inches) wide

and about 13 to about 76 micrometers (about 0.0005 to about 0.003 inch) thick are

formed by continually depositing a melt of each of the compositions set forth in Table 2 below, by overpressure of argon onto a rapidly rotating copper chill wheel

(surface speed about 3000 to about 6000 ft/min). Metastable homogeneous ribbons having substantially glassy structure are produced. The liquidus and solidus temperatures of the ribbons described in Table 2 are determined by the

Differential Thermal Analysis (DTA) technique. The individual samples are heated

side by side with an inert reference material at a uniform rate, and the temperature difference between them is measured as a function of temperature. A thermogram

is produced (a plot of heat-energy change vs. temperature) from which the beginning of melting and the end of melting, known respectively as solidus and

liquidus temperatures, is determined. The values are reported in Table 2 below.

EXAMPLE 2

Specimens for metallographic tests are dimensioned and fabricated as

"sandwich-like" lap type specimens. Each specimen is comprised of two 125 μm

thick strips of alloy PM2000, having a composition 20 wt.% Cr, 5.5 % Al, 0.5 %

Ti, 0.45% Y₂O₃, and the balance being iron, and a single 25 μm thick foil of one of

the samples presented in Table 2. The foils include Sample No.1 manufactured

according to previous art and samples of nominal composition of Nos. 4 and 5

manufactured according to the present invention. The single brazing foil is

preplaced between two PM2000 strips. The width of the PM2000 strips and all

brazing filler metal alloys is about 10 mm. In the case of these brazing alloys, the

ribbons act as spacers. Brazing is done in a vacuum furnace which is evacuated to

a pressure of equal or lower than 1.33X10^"2 Pa (10^"4 Torr). The brazing is carried

out at 1195°C for 15 min. Upon cooling in the furnace, segments are cut from brazed specimens, mounted in plastic form, and polished on standard equipment to

accomplish preparation of metallographic specimens for scanning electron microscopy metallographic observations. Joint microstructure is observed using SEM/EDAX and Auger analytical methods. The typical microstructure of a joint

prepared using alloy with nominal composition of Sample 1 which is manufactured

using previous art shown in Fig. 1. The micrograph depicts presence of a substantial amount of chromium borides precipitated in the body of base metal

part. These borides (at black arrows) segregate predominantly at planes, which are

parallel to the direction of rolling of the base metal alloy. FIG. 2 is an SEM micrograph of a specimen prepared using a filler metal foil with a nominal composition Sample No. 4 which contains 3 wt.% palladium and is

manufactured according to the present invention, the micrograph depicting a dense layer of AlPd intermetallic phase (at empty arrows) formed at the joint interface and protecting base metal, from boron penetration and formation of detrimental

chromium borides. The base metal has a substantially uniform, single-phase

microstructure with a very limited amount of precipitated chromium borides. FIG.

3 is a micrograph of joint made using a filler metal foil with a nominal composition

Sample 6 No. 5 which contains 5 wt.% palladium and is manufactured according to

the present invention, the micrograph depicting the same beneficial basic features

of the joint microstructure as that shown in FIG. 2 but containing a substantially

larger amount of the AlPd phase (at empty arrows). This demonstrates that formation of AlPd phase is indeed related to the amount of palladium in the filler

metal alloy of the present invention.

Having thus described the invention in rather full detail, it will be

understood that such detail need not be strictly adhered to but that various changes and modifications may suggest themselves to one skilled in the art, all falling within

the scope of the present invention as defined by the subjoined claims.

Claims

What is claimed is:

1. A brazing material comprising a composition defined by the formula:

Cr. Nib WcPdd SU BfCobai.

plus incidental impurities, where the subscripts "a", "b", "c", "d ", "e", and "f ' are in atomic percent and "a" is in the range of about 15 and about 22, "b" is between about 0 and about 20, "c" is in the range of about 1 to

about 5, "d" is between about 1 and about 10, "e" is in the range of about 5 and about 12, "f ' is between about 5 to about 12 and "bal" is the balance amount to

total 100 percent.

2. The brazing material as recited in claim 1 wherein the material is a powder.

3. The brazing material as recited in claim 1 wherein the material is an alloy.

4. The alloy as recited in claim 3 wherein the alloy is at least about

50% glassy.

5. The alloy as recited in claim 3 wherein the alloy is at least about 80% glassy.

6. A brazing material , as recited by claim 1, having a solidus of at least about

1010 degree(s) C and a liquidus ranging from at least about 1130 degree(s) C to

about 1180 degree(s) C.

7. The brazing material as recited in claim 1 wherein the material is a foil..

8. A brazing foil formed from the alloy of claim 3

9. A brazing foil formed from the alloy of claim 4.

10. A brazing foil formed from the allow of claim 5

11 A brazing foil, as recited by claim 6 having a thickness ranging from about

lO ╬╝m tolOO ╬╝m

12 A brazing foil, as recited by claim 6 wherein "a" ranges from about 18 to

about 22 atom percent

13 A brazing foil, as recited by claim 6. wherein "b" ranges from about 12 to

about 17 atom percent

14 A brazing foil as recited by claim 6, wherein "c" ranges from about 3 0 to

about 3 5 atom percent

15 A brazing foil, as recited by claim 6, wherein "d" ranges from about 1 5 to

about 7 atom percent

16 A brazing foil as recited by claim 6, wherein "e" ranges from about 5 to

about 10.5 atom percent

17 A brazing foil, as recited by claim 6, wherein "f ' ranges from about 6.5 to

about 8.0 atom percent

18. A process for fabricating a brazed article, comprising the steps of

(a) interposing a brazing material as recited in claim 1 between base

metal parts to form an assembly,

(b) heating the assembly to a temperature of about 25-50┬░C above the

liquidus temperature of said brazing material and holding at said

temperature for a time sufficient to form a joint.

19. A process for fabricating a brazed article, comprising the steps of:

(a) interposing a brazing material as recited in claim 1 between base

metal parts to form an assembly;

(b) heating the assembly to a temperature of about 25-50┬░C

above the liquidus temperature of said brazing filler metal and holding at

said temperature for a time sufficient to form during brazing and

afterwards cooling to about 1000┬░C and holding at said temperature for a

time sufficient for postbrazing annealing of said structure;

(c) cooling the assembly to provide a brazed structure.

20. A brazed article produced by a process comprising the steps of:

(a) interposing a brazing material as recited in claim 1 between base

metal parts to form an assembly; (b) heating the assembly to a temperature of about 25-50┬░ C above the

liquidus temperature of said brazing material,

(c) cooling the assembly to provide a brazed structure.

21. A brazed article, said article having a brazement substantially free

from brittle intermetallic chromium borides phases in the base metal parts.

22. A brazing material comprising a composition defined by the formula:

Cr.NibW_cPdd Si_eBfC╬╕b.1.

plus incidental impurities, where the subscripts "a", "b", "c", "d ", "e", and "f ' are in atomic percent and "a" is in the range of about 18 and about 22, "b" is between

about 12 and about 17, "c" is in the range of about 3.0 to

about 3.5, "d" is between about 1.5 and about 7, "e" is in the range of about 5 and

about 10.5, "f ' is between about 6.5 to about 8 and "bal" is the balance amount to

total 100 percent.

23. The brazing material as recited in claim 22 wherein the material is a powder.

24. The brazing material as recited in claim 22 wherein the material is an alloy.

25. The alloy as recited in claim 23 wherein the alloy is at least about

50% glassy.

26. The alloy as recited in claim 24 wherein the alloy is at least about 80%) glassy.

27. A brazing material , as recited by claim 22, having a solidus of at least about

1010 degree(s) C and a liquidus ranging from at least about 1130 degree(s) C to

about 1160 degree(s) C.

28. The brazing material as recited in claim 22 wherein the material is a foil.

29. A brazing foil formed from the alloy of claim 24

30. A brazing foil formed from the alloy of claim 25.

31. A brazing foil formed from the alloy of claim 26

32. A brazing foil, as recited by claim 26 having a thickness ranging from about

14 ╬╝m tolOO ╬╝m.

33. A process for fabricating a brazed article, comprising the steps of:

(a) interposing a brazing material as recited in claim 22 between base

metal parts to form an assembly;

(b) heating the assembly to a temperature of about 25-50┬░C above the

liquidus temperature of said brazing material and holding at said

temperature for a time sufficient to form a joint.

34. A process for fabricating a brazed article, comprising the steps of:

(a) interposing a brazing material as recited in claim 22 between

base metal parts to form an assembly;

(b) heating the assembly to a temperature of about 25-50┬░C

above the liquidus temperature of said brazing filler metal and holding at

said temperature for a time sufficient to form during brazing and

afterwards cooling to about 1000┬░C and holding at said temperature for a

time sufficient for postbrazing annealing of said structure;

(c) cooling the assembly to provide a brazed structure.

35. A brazed article produced by a process comprising the steps of:

(a) interposing a brazing material as recited in claim 22 metal between

base metal parts to form an assembly; (b) heating the assembly to a temperature of about 25-50┬░ C above the

liquidus temperature of said brazing material,

(c) cooling the assembly to provide a brazed structure.

36. The brazing material of claim 1 having a melting temperature range from

about 10100 degrees C to about 1190 degrees C.

37. The brazing material of claim 22 having a melting temperature range from

about 1080 degrees C to about 1150 degrees C.