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1. WO1995006758 - ALLIAGES DE RECHARGEMENT DUR CONTENANT DES CARBURES OU BORURES METALLIQUES PRECIPITES ET LEUR PROCEDE DE FABRICATION

Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

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HARD SURFACING ALLOY WITH PRECIPITATED
METAL CARBIDES OR BORIDES AND PROCESS

Related Applications
This application is a continuation-in-part of U.S. Serial No. 07/934,555, filed August 24, 1992.

Background
The present invention relates to high temperature corrosion resistant hard surfacing alloys which are of extremely high hardness. More particularly, the present invention relates to hard surfacing alloys which contain tungsten carbide, chromium carbide and bi-metallic tungsten chromium carbide precipitates or metallic borides which are precipitated in the alloy and are thus bound in the hard surfacing alloy. Alloys of the present invention produce superior surfaces for improved wear in high temperature, high corrosive, high abrasion environments such as glass mould plungers and the like.
Plungers used in glass moulding are exposed to some of the most extreme and corrosive environments which are found in modern industry. These plungers are subjected to hundreds of thousands of high impact high temperature plunging operations in the glass moulding industry. In the past, these plungers have been a source of down time in that they are subject to rapid wear. Also, plungers used in the glass mould industry must have surfaces of very low porosity to provide the proper surface in the final finished glass piece. Thus, improper wearing of plunger surfaces mandates repair or replacement. Prior alloys used for surfacing of glass mould plungers have demonstrated "hot wiping" of the alloys from the glass plunger surface. This condition reduced longevity in that the surface alloy was worn away creating out of specification conditions requiring replacement and/or repair.
It has been known that if hard surfacing alloys could be achieved which have high Rockwell C hardnesses of greater than 50, such an alloy would greatly increase longevity of these plungers. However, such alloys have not been readily available in the prior art. Additionally, improvements in abrasion resistance would add life to such plungers.
Because of such high Rockwell C hardness requirements it has been generally recognized that materials containing carbides such as tungsten carbides and the like would be advantageous in such alloys.
In other applications, high hardness alloys have been successfully utilized using sintered cobalt structures employing tungsten carbide particles which are encapsulated therein. These cobalt sintered structures rely on the encapsulation of tungsten carbide particles in the alloy to produce high hardness type alloys in the ranges necessary for glass mould plungers. Such alloys are known and have been used in other applications, however, when these alloys are used in glass plunger applications it was found that the final plunger produced by such an alloy was not suitable for a glass plunger application due to the porosity of the alloy produced. Such porosity is undesirable as stated above. Additionally, because of the extreme working conditions in glass plunger applications extraordinary quantities of tungsten carbides would need to be utilized. The sintered type structures have not been found to readily accommodate such high quantities of tungsten carbides.
Sintered structures also are prone to loss of the critical tungsten carbide particles under use, apparently due to the relatively "loose" encapsulation of tungsten carbides in the structure. Thus, as these structures wear the tungsten carbide particles tend to dislodge from the structure reducing the hardness of the structure.
Thus, it has been a goal in the art to provide a high hardness surfacing alloy which contains high quantities of tungsten carbide particles or other high hardness particles and the like and which has low porosity characteristics and improved abrasion resistance.
Summary of the Invention
In accordance with these goals there is provided in the present invention a hard surfacing alloy which has a Rockwell C hardness of greater than about 50 and which includes tungsten carbide, chromium carbide and bi-metallic chromium and tungsten carbide crystals which are precipitated in the alloy. Alloys of the present invention in their nominal composition comprise from about 12% to about 20% tungsten; from about 13% to about 30% chromium; an effective amount of carbon for forming carbides with the tungsten and chromium and effective amounts of fluxes and melting point depressants and the like. The balance of the composition is nickel. Alloys of the present invention include precipitated carbide crystals of chromium, tungsten and bi-metallic mixtures thereof which are interspersed through the hard surfacing alloy and are metallurgically bonded in the metal matrix of the alloy. In accordance with improved abrasion resistance alloys the carbon content is reduced to less than .06% and the boron concentration increase .5% to produce a large number of metal boride precipitated crystals which improve abrasion resistance. Alloys in accordance with the present invention have extremely low porosities and therefore are suitable for glass plunger and other applications where low porosity is essential. Also, because these alloys have precipitated metal carbides or metal borides which are bound in the structure there is less occurrence of the carbide crystals coming loose in the hard surfacing alloys of the present invention.

Brief Description of the Drawings
Fig. 1 is a photomicrograph taken at a magnification of X 1880, of an alloy made in accordance with the teachings of the present invention, showing the bi-metallic crystalline particle and the distribution of tungsten carbides and chromium carbides in the alloy; and
Fig. 2 is a photomicrograph taken at magnification of X 2520 which shows a typical sintered tungsten structure illustrating the undesirable porosity of prior art structures.
Fig. 3 is a photomicrograph taken at a magnification of X 1000 which shows the large number of precipitated metal borides found in the alternate embodiment of the present invention.

Description of the Preferred Embodiments
Hard surfacing alloys in accordance with the present invention typically have a Rockwell C hardness in a range of from about 50 to about 70 and preferably from about 58 to 65. In nominal composition these alloys include from about 12% to about 20% tungsten and preferably 15% to about 18% tungsten; from about 13% to about 30% chromium and preferably from about 14% to 18% chromium; and an effective amount of carbon with the balance being nickel. Also incorporated in the present invention are suitable fluxes and melting point depressants to provide an effective hard surfacing alloy. For instance, preferred compositions of the present invention include boron, silicon and iron in ranges of from about 2% to about 5%. Preferably, iron is used in ranges of from about 3 to about 4 and the silicon from about 3.5 to about 5.0. Effective amounts of carbon in the present invention include carbon in ranges of from about .5% to about 1%.
Referring now to Fig. 1, critical in the present invention are the existence of precipitated tungsten carbide crystals, chromium carbide crystals, and bi-metallic tungsten chromium carbide crystals. Referring now to Fig. 1, these crystals may be best identified by size and shapes therein. For instance, the larger rectangular shaped crystal 12 is the bi-metallic chromium and tungsten carbide crystal. The bi-metallic tungsten and chromium carbide crystal 12 is typical of the present invention and also includes a number of chromium carbide precipitate crystals 14 therein which are of a smaller magnitude than the larger particles 12 and have a characteristic hexagonal shape. Tungsten carbide precipitate crystals 16 which are interspersed throughout the remainder of the metal are the smallest of the crystalline constituents.
The larger bi-metallic particles 12 typically are from about 25 to 100 microns across with preferable sizes being in the 40 to 50 micron range. These bi-metallic particles have hardnesses of about 2050 on the vickers hardness scale.
The smaller chromium carbide particles 14 and tungsten carbide crystals 16 range in size from about 1 to about 10 microns with the chromium carbide crystals being at the larger end of that range and the tungsten carbide crystals at the smaller end of that range. The tungsten carbides have hardnesses of about 2400 and the chromium carbides of about 1600 on the vickers hardness scale. In preferred compositions of the present invention the chemistry and temperature of the melt time may be controlled for precipitation of these crystals such that from about 10% to about 15% of the surface area of the alloy is populated with the larger bimetallic tungsten and chromium carbide crystals 12 and approximately from about 35% to 50% of the total composition is tungsten carbide and chromium carbide type precipitates.
It is critical in the present invention that these carbide crystals are precipitated in the alloy such that they are metallurgically bonded in the alloy and provide a much smoother low porosity surface than the prior art shown in Fig. 2. Thus, the present invention has low porosity ranges such that no porosity is visible at a magnification of at least times 10. As shown in Fig. 2, the porosity of the prior art sintered tungsten carbide structure is readily notable. In this structure blackened areas 18 indicate the existence of unacceptable porosity and also the tungsten carbide containing areas 20 are very coarse in nature. In contrast, Fig. 1, which depicts the alloy of the present invention, has no visible porosity, even at the X 1880 magnification. Thus, hard surfacing alloy compositions of the present invention are extremely well suited for low porosity type applications.
When alloys of the present invention are applied to glass plunger parts it has been found that substantially no "hot wiping" occurs on plungers up to the useful life of prior art type plungers (approximately 635,000 bottles) and beyond. Glass plungers utilizing alloys in accordance with the present invention have found to stay hard up to and above 1850°F. Alloys of the present invention are substantially free from softening or corrosion at these temperatures and have very good abrasion resistance even under the extreme conditions of glass moulding operations.
In accordance with the process aspects of the constituents in the ranges set forth above must be alloyed together in a melt and heated at a temperature of greater than about 2250°F and preferably of from about 2800°F to 3200°F to provide the necessary conditions for carbide formation. Alloys of the present invention are viscous even at these melt temperatures having the consistency of honey. In a preferred embodiment the melt is processed through a rapid solidification nozzle with the resulting powder including the precipitated tungsten chromium and bi-metallic carbide particles.
Typically, powders of the present invention have sizes of from about 140 to about 400 mesh and preferably 170 to about 325 mesh. These powders are formed by heating the constituents of the present invention at high temperatures of from about 2,500°F to 3,000°F and using a Krupp 4a or other type rapid solidification nozzle to rapidly solidify these particles from this temperature which produces the precipitation carbide products. Such conditions with the presence of high concentrations of the chromium, carbon and tungsten constituents facilitates the formation of the bi-metallic tungsten and chromium carbide crystals of the present invention.
In a preferred embodiment of the process of the present invention, the nickel constituent is utilized in the form of a pure pelletized nickel and can be obtained from INCO International Co. of Saddle Brook, New Jersey. The nickel is initially melted in a furnace utilizing about 1/3 of the amount of weighed nickel boron. Thus, a portion of the nickel concentration comes from the addition of nickel boron which can be obtained through Shield Alloy of South Holland, Illinois or SKW Metals & Alloys of Niagara Falls, New York. The boron constituent of the present invention acts as a melting point depressant, hardening agent and a flux in the alloys of the present invention. After melting this initial charge completely the entire amount of tungsten is added to the melt and completely dissolved. Thereafter, the remaining elements are added and dissolved with the silicon constituent being added immediately prior to atomization.
Iron is provided for improving ductility of the final alloy. Thus, improving the impact resistance of the alloy. Whereas the silicon acts to depress the melting point of the present alloy and adds oxidation resistance to the alloy. Pure silicon such as that obtained from Elkem Metals Co. of Marietta Ohio may be utilized in the present invention. For processing into a powder form the silicon constituent is added immediately prior to atomization.
In an alternate embodiment of the present invention by abrasion resistance of the surfacing alloy is improved by substantially reducing the carbon content to trace i.e. less than about .06% and slightly increasing the boron concentration by about .5% to from about 2.5% to about 5.5%. It has been discovered that with this combination precipitated bimetallic borides are formed in the alloy pursuant to the process steps of the present invention.
Referring to Fig. 3 the bimetallic boride crystals 22 exist in populations of from about 14% to about 22% of the surface area of the alloy, with the crystalline particle sizes ranging from about 15 to about 25 microns. It is believed that these crystals are chromium-tungsten borides which are extremely hard i.e. about 2600 KNOOP. It has been found that because the particles are extremely hard and the great numbers of particles the surfacing alloys of the present invention have extremely high abrasion resistance on the order of greater than about 1703-1870 volume loss in cubic millimeters using the G-65 ASTM test. Utilizing the "pin on disk" test these alloys have a relatively high abrasion resistance of about 16.8 mg weight loss which indicates that these alloys would provide improvements in high abrasion applications.

Thus, alloys of this embodiment of the present invention generally include from about

12% to about 20% tungsten, from about 13% to about 30% chromium, from about 2% to about

5% silicon, from about 2% to about 5% iron, with from about 2.5% to about 5.5% boron and with total carbon content of less than about .06%. Preferably, tungsten is utilized in amounts of from about 15% to about 18%, chromium is utilized in amounts of from about 14% to about 18%, silicon is utilized in amounts of from about 3% to about 4%, iron is utilized in amounts of from about 3.5% to about 5% with boron in preferred amounts of from about 2.5% to about 4.5% and less than .06% carbon.
The process parameters of this embodiment of the present invention are the same as set forth in the bi-metallic carbide embodiment with the exception that no carbon is added and higher quantities of boron are utilized.

Further understanding of the present invention will be had from the following examples which are given herein for purposes of illustration but not limitation.
Example I
In the present example the weights of constituents and aimed for percentages are set forth below in Table I.
Table I
Aim Percent Weight (lbs.. & (gms.
Boron1 2.50 % 1.430 lbs. 649 gms.

Carbon2 0.65 % 0.065 lbs. 30 gms.

Chromium3 14.00 % 1.400 lbs. 636 gms.

Iron4 3.00 % 0.300 lbs. 136 gms.

Silicon5 3.50 % 0.350 lbs. 159 gms.

Tungsten6 16.00 % 1.600 lbs. 726 gms.

Nickel7 60.35 % 4.855 lbs. 2294 gms.
1 Source of boron is nickel boron usually containing approximately 17.50% boron obtained from Shieldalloy Corporation of South Holland, Illinois.
2 Carbon (graphite flake) obtained from Cummingsmoore Graphite, Co. of Detroit,

Michigan.
3 Aluminothermic grade chromium Shieldalloy Corporation of South Holland, Illinois.

4 Pure Iron obtained from Armco Steel Corporation of Middletown, Ohio.
5 Pure silicon obtained from Elkem Metals Company of Marietta, Ohio.
6 Pure tungsten obtained from Kaichen's Metal Mart of Paramount, California.
7 The nickel contained in nickel boron is already subtracted from the amount of pure nickel obtained from INCO International Co. of Saddle Brook, New Jersey.

A 10 pound melt of the alloy was prepared in accordance with the following procedure.

The entire amount of nickel and 1/3 of the amount of nickel boron was placed in a zirconium

oxide crucible in an INDUCTOTHERM induction melt furnace and heated to a temperature

of about 2500°F. The temperature was maintained until complete melting of the nickel and nickel boron occurs. Thereafter, the entire quantity of tungsten was added and allowed to dissolve into the melt for about 20 minutes, until completely dissolved in the melt. Thereafter, the remainder of the constituents were added, with the exception of silicon, and allowed to melt completely. The silicon was then added to the melt. With the temperature increased to about 2800°F to prepare for atomization, a Krupp type 4a nozzle with a gap of .015" was used at a - 8/ 1 -nozzle pressure of about 500 psi to produce a 325 mesh powder. The resulting alloy was found

- 9 -to contain bi-metallic carbide, tungsten carbide and chromium carbide crystals throughout. A
TM
Wall Colmonoy SPRAYWELDER type thermal spray applicator is used to hard surface a

glass mold plunger. The resulting hard surface coating is found to be very low in porosity and is resistant to hot wiping in a glass moulding manufacturing operation.

Example II
In the present example the weights of constituents and aimed for percentages are set forth below in Table II.
Table II
Aim Percent Weight (lbs.) & (gms.)
Boron1 3.50 % 2.040 lbs. 925 gms.
Carbon2 0.95 % 0.095 lbs. 43 gms.
Chromium3 18.00 % 1.800 lbs. 817 gms.
Iron4 4.00 % 0.400 lbs. 182 gms.
Silicon5 5.00 % 0.500 lbs. 227 gms.
Tungsten6 18.00 % 1.800 lbs. 817 gms.
Nickel7 50.55 % 3.365 lbs. 1528 gms.

1 Source of boron is nickel boron usually containing approximately 17.50% boron obtained from Shieldalloy Corporation of South Holland, Illinois.
2 Carbon (graphite flake) obtained from Cummingsmoore Graphite, Company of Detroit, Michigan.
3 Aluminothermic grade chromium Shieldalloy of South Holland, Illinois.
4 Pure Iron obtained from Armco Steel Corporation of Middletown, Ohio.
5 Pure silicon obtained from Elkem Metals Company, Marietta, Ohio.
6 Pure tungsten obtained from Kaichen's Metal Mart of Paramount, California.
7 The nickel contained in nickel boron is already subtracted from the amount of pure nickel obtained from INCO International Company of Saddle Brook, New Jersey.

A 10 pound melt of the alloy was prepared in accordance with the following procedure. The entire amount of nickel and 1/3 of the amount of nickel boron was placed in a zirconium oxide crucible in an INDUCTOTHERM induction melt furnace and heated to a temperature of about 2500°F The temperature was maintained until complete melting of the nickel and nickel boron occurs. Thereafter, the entire quantity of tungsten was added and allowed to dissolve into the melt for about 20 minutes, until completely dissolved in the melt. Thereafter, the remainder of the constituents were added, with the exception of silicon, and allowed to melt - 9/1 -completely. The silicon was then added to the melt. With the temperature increased to about 2800°F to prepare for atomization, a Krupp type 4a nozzle with a gap of .015" was used at a nozzle pressure of about 500 psi to produce a 325 mesh powder. The resulting alloy was found

- 10 -to contain bi-metallic carbide, tungsten carbide and chromium carbide crystals throughout. A

Wall Colmonoy SPRAYWELDER type thermal spray applicator is used to hard surface a glass mold plunger. The resulting hard surface coating was found to be very low in porosity and is resistant to hot wiping in a glass moulding manufacturing operation.
Example III
In the present example the weights of constituents and aimed for percentages are set forth below.
Table HI
Aim Percent Weight (lbs.) & (gms.)
Boron1 3.00 % 1.750 lbs. 793 gms

Carbon2 0.80 % 0.080 lbs. 36 gms.
Chromium3 15.00 % 1.500 lbs. 681 gms.
Iron 4 3.50 % 0.350 lbs. 159 gms.
Silicon5 4.00 % 0.400 lbs. 182 gms

Tungsten6 17.25 % 1.725 lbs. 783 gms.
Nickel7 56.45% 4.195 lbs. 1.905 gms
' Source of boron is nickel boron usually containing approximately 17.50% boron obtained from Shieldalloy Corporation of South Holland, Illinois.
2 Carbon (graphite flake) obtained from Cummingsmoore Graphite, Company of Detroit, Michigan.
3 Aluminothermic grade chromium Shieldalloy Corporation of South Holland, Illinois. 4 Pure Iron obtained from Armco Steel Corporation of Middletown, Ohio.
5 Pure silicon obtained from Elkem Metals Company of Marietta, Ohio.
6 Pure tungsten obtained from Kaichen's Metal Mart of Paramount, California.
7 The nickel contained in nickel boron is already subtracted from the amount of pure nickel obtained from INCO International of Saddle Brook, New Jersey.

A 10 pound melt of the alloy was prepared in accordance with the following procedure. The entire amount of nickel and 1/3 of the amount of nickel boron was placed in a zirconium

oxide crucible in an INDUCTOTHERM induction melt furnace and heated to a temperature

of about 2500°F. The temperature was maintained until complete melting of the nickel and nickel boron occurs. Thereafter, the entire quantity of tungsten was added and allowed to dissolve into the melt for about 20 minutes, until completely dissolved in the melt. Thereafter, the remainder of the constituents were added, with the exception of silicon, and allowed to melt - 10/1 - completely. The silicon was then added to the melt. With the temperature increased to about 2800°F to prepare for atomization, a Krupp type 4a nozzle with a gap of .015" was used at a nozzle pressure of about 500 psi to produce a 325 mesh powder. The resulting alloy was found

- 11 -to contain bi-metallic carbide, tungsten carbide and chromium carbide crystals throughout. A

Wall Colmonoy SPRAYWELDER™ type thermal spray applicator is used to hard surface a glass mold plunger. The resulting hard surface coating was found to be very low in porosity and is resistant to hot wiping in a glass moulding manufacturing operation. The alloy was found to have a hardness of about 64 on the Rockwell C scale.

Example IV
Hard surfacing alloys are prepared in accordance with the procedure of Example III utilizing: in a first alloy 12% tungsten, 30% chromium, 2% boron, 2% iron, 2% silicon and .5% carbon, balance nickel; and in a second alloy 20% tungsten, 13% chromium, 5% boron, 5% iron, 5% silicon, 1% carbon and the balance nickel. The resulting powders include tungsten carbide, chromium carbide and bi-metallic tungsten and chromium carbide crystals metallurgically bound therein.
A first glass mould plunger is hard surfaced with the first alloy. .A second glass mould plunger is hard surfaced with the second alloy. The resulting surface of both glass mould plungers is found to have a hardness of greater than 50 and are low in porosity.

Example V
A hard surfacing alloy is prepared in accordance with the melt steps set forth in the procedure of Example III with the exception that no carbon was added to the melt. The aim point and amount of each constituent added is set forth below in Table IV.

- 12 - Table IV
Aim Percent Weight (lbs.)
Boron1 3.6% 2.042 lbs.
Carbon2 06% 0.000 lbs.
Chromium3 15.0% 1.500 lbs.
Iron 4 3.0% 0.300 lbs.
Silicon5 4.2% 0.420 lbs.
Tungsten6 17.7% 1.770 lbs.
Nickel7 56.50% 4.200 lbs.

1 Source of boron is nickel boron usually containing approximately 17.50% boron obtained from Shieldalloy Corporation of South Holland, Illinois.
2 Carbon is found in trace quantities in other additions.
3 Aluminothermic grade chromium Shieldalloy of South Holland, Illinois.
4 Pure Iron obtained from Armco Steel Corporation of Middletown, Ohio.
5 Pure silicon obtained from Elkem Metals Company, Marietta, Ohio.
6 Pure tungsten obtained from Kaichen's Metal Mart of Paramount, California.
7 Pure nickel obtained from INCO International of Saddle Brook, New Jersey.

The resulting powders include a large population of bimetallic chromium-tungsten boride crystals throughout its structure and metallurgically bound therein.
A glass mold plunger is then hard surfaced with the resulting alloy. The resulting surface has a hardness of about 58 on the Rockwell C scale. An abrasion resistance test, utilizing the ASTM G-65 and the "pin on disk" method revealed that the abrasion resistance of this alloy was in the range of about 16.8 mg. weight loss. Abrasion resistance was found to be about three times higher than the alloys of the other embodiment illustrated in Examples I through IV. The alloy of this example was also found to have higher impact strength than the previous embodiment.
Example VI
Hard surfacing alloys are prepared in accordance with the procedure of Example V utilizing: in a first alloy 12% tungsten, 30% chromium, 2.5% boron, 2% iron, 2% silicon and < .06% carbon, balance nickel; and in a second alloy 20% tungsten, 13% chromium, 5.5% boron, 5% iron, 5% silicon, < .06% carbon and the balance nickel. The resulting powders include bimetallic boride crystals metallurgically bound therein.

- 13 - A first glass mould plunger is hard surfaced with the first alloy. A second glass mould plunger is hard surfaced with the second alloy. The resulting surface of both glass mould plungers is found to have a hardness of greater than 50; is low in porosity; and is high abrasion resistance.
While the above description constitutes the preferred embodiments of the present invention it is to be appreciated that the invention is susceptible to modification, variation and change without departing from the proper scope and fair meaning of the accompanying claims.