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Publication numberUS3779728 A
Publication typeGrant
Publication dateDec 18, 1973
Filing dateMar 13, 1973
Priority dateDec 12, 1969
Publication numberUS 3779728 A, US 3779728A, US-A-3779728, US3779728 A, US3779728A
InventorsGetz R, Hansen J
Original AssigneeGetz R, Hansen J
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
High temperature - high strength alloy glass fiber forming bushing
US 3779728 A
Abstract
A high temperature-high strength alloy comprising platinum, rhodium and one or more metals consisting of molybdenum, tungsten, iridium, and rhenium is fabricated into apparatus adapted to receive and controllably emit molten material for attenuation into glass fibers.
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United States Patent [1 1 Hansen et al.

[ Dec. 18, 1973 HIGH TEMPERATURE HIGH STRENGTH ALLOY GLASS FIBER FORMING BUSHING Inventors: James H. Hansen, Rt. 3; Ralph W.

Getz, 421 Alford Dr., both of Newark, Ohio 43055 Filed: Mar. 13, 1973 Appl. No.: 340,861

Related US. Application Data Continuation-impart of Ser. No. 884,689, Dec. 12, 1969, Pat. Nov 3,622,289, Continuation of Ser. No. 192,293, Oct. 26, 1971.

U.S. Cl 65/1, 65/374, 75/172 Int. Cl C03b 37/02 Field of Search 75/172, 134 U; 65/1,

Primary ExaminerRobert L. Lindsay, Jr. Att0rney-Robert E. Witt [57] ABSTRACT A high temperature-high strength alloy comprising platinum, rhodium and one or more metals consisting of molybdenum, tungsten, iridium, and rhenium is fabricated into apparatus adapted to receive and controllably emit molten material for attenuation into glass fibers.

18 Claims, No Drawings HIGH TEMPERATURE HIGH STRENGTH ALLOY GLASS FIBER FORMING BUSHING This is a Continuation-in-Part of our co-pending ap- I plication, Ser. No. 884,689, filed on Dec. 12, 1969 now U.S. Pat. No. 3622289, granted Nov. 23, 1971. This is a continuation of application Ser. No. 192,293, filed Oct. 26, 1971.

BACKGROUND OF THE INVENTION This invention relates to platinum-rhodium alloys and more sepcifically to a platinum-rhodium alloy having a third metal addition wherein its high temperaturehigh strength properties are greatly increased. A high rhodium alloy is very desirable because of its high melting properties thereby being capable of exposure to high operating temperatures during service operations.

High rhodium content alloys in the past have been demonstrated to be capable of being produced without difficulty by a normal vacuum melting process. Platinum-rhodium alloys comprising from 20-40 percent rhodium are capable of being fabricated by a process of hot working followed by normal cold working. For example, in the case of sheet material, hot rolling is followed by cold rolling. Rhodium contents of more than 40 percent have been fabricated but they require more sophistication, e.g. powder techniques.

However, by increasing the rhodium content of these alloys their affinity for oxygen also increases, i.e. the oxygen solubility of the alloy increases thereby reducing the ductility of the alloy. Extreme care must be taken when using current production welding techniques (tungsten arc-inert gas shield) to prevent brittle welds. The chance of embrittlement due to oxygen 'absorption by these alloys is greatest during welding when the alloy is in the molten state.

During service operation at elevated temperatures, the ductility of a high rhodium alloy is reduced by increased oxygen solubility thereby creating a potential for premature failure of the alloy due to stress cracking. Weld failures have been noted on fabricated parts of a high rhodium alloy when exposed to high temperature.

To improve the high temperature ductility of a high rhodium content alloy and also assure weld integrity, the following high rhodium alloy system has been developed; platinum 14 to 79 percent, rhodium 20 to 85 percent and a third metal addition of from 0.01 to 1.0 percent, wherein good homogenization of the third metal addition is required.

The third metal additions are selected from the refractory or platinum group metals, such as for example, iridium, tungsten, rhenium and molybdenum and combinations thereof. Originally selected for use as solid solution strengtheners to yield a stronger alloy, these metals have been found to increase the high temperature ductility of high rhodium content alloys.

SUMMARY This high temperature-high strength alloy finds immediate use in the glass fiber industry in bushings and other standard high-temperature applications. The development of such an alloy has been prompted'by the increased emphasis on higher melting glasses wherein high strength requirements for bushings are necessi-' tated because of the higher operating temperatures,

characteristics of these glasses. 1

Among the problems encountered when a bushing is in service are the volatilization losses of the alloy from the bushing and creep deformation of the bushing structure which decreases the efficiency and life of the bushing and which lends to lower quality glass fibers.

The advantage of using an alloy of the inventive concept includes a reduction in the precious metal volatilization losses from the bushing during service and improved strength characteristics of the alloy to reduce high temperature creep rates.

Molybdenum is the preferred third metal addition in the platinum-high rhodium content alloys of this invention because of their intended use in high-temperature resistant glass handling apparatus, although the other named third metal additions function in the same manner. Molybdenum is not known in the art to improve the ductility of the platinum-rhodium alloy, so that the use herein of small percentages of molybdenum to improve the ductility of a platinum-rhodium alloy is totally unexpected and unobvious. Very small additions of molybdenum to a platinum-rhodium alloy make it possible to use rhodium in proportions as high as 20 to 85 percent whereas in prior platinum-rhodium alloys, without molybdenum, the maximum practical rhodium content was limited to approximately 20 to 40 percent.

The percentage of the third metal addition that is added to the platinum-rhodium alloy is based upon the rhodium content, i.e. as the latter is increased so is the former. However, the amount of the third metal addition in the alloy should not exceed 1.0 percent by weight because of the potential of undesirable internal void formations developing during service applications which embrittles the alloy.

Some of the general characteristics of the alloy of this invention include improved tensile properties, slightly reduced oxidation losses of precious metal due to preferential oxidation of the third metal addition, improved high temperature ductility, improved creep rupture life, and improved weld integrity.

The ranges of proportions of the metals making up the alloys of this invention, expressed in weight percent, are:

PLATINUM 14-79 RHODIUM 20-85 THIRD METAL ADDlTlON 0.01-1.0

The preferred ranges expressed in weight percent are:

platinum 29 59 rhodium 40 third metal addition 005 0.75

The preferred composition of the inventive alloy, expressed in weight percent comprises:

platinum 40.0 rhodium 59.5 third metal addition 0.5

Molybdenum is the preferred third metal addition in the above compositions although the other named third metals and combinations thereof function in the same manner.

Examples of the alloys of this invention, expressed in weight percent, include the following:

EXAMPLE 1 platinum 14.0 rhodium 85.0 molybdenum 1.0

tungsten 0.5 EXAMPLE ll EXAMPLE XVlll platinum 79.00 rhodium 20.99 platinum 40.0 molybdenum 0.01 h dium 59.5 5 iridium 0.5 EXAMPLE Ill EXAMPLE XIX platinum l4.0 "mdium platinum 40.0 tungsten L0 rhodium 59.5 l0 rhenium 0.5 EXAMPLE IV platinum 7900 Examples of alloys of this invention which employ at $22; 8-3? least two of the third metal additions, expressed in g weight percent, include the following:

EXAMPLE v EXAMPLE XX platinum l4.0 $113.? :33 h d' irigi i molybdenum 0.5 tungsten 0.5

EXAMPLE EXAMPLE XXI platinum 79.00 I.f"" -99 fliilllfi Z23 Indium t molybdenum 0.5 EXAMPLE vII 2 platinum 14.0 rhodium 85.0 r platinum t4.0 rhen'um rhodium 85.0 I bd 0.9 EXAMPLE VIII 3.150,? d.

platinum 79.00 medium 2099 EXAMPLE XXIII rhcmum 0,0] Platinum 590 rhodium 40.0 V V 7' EXAMPLE IX I tungsten 0.3 platinum 5900 iridium 7 rhodium 40.25 molybdenum 075 EXAMPLE XXIV XA X platinum 29.00 rhodium 70.00 platinum 29.95 tungsten 0.0l rhodium 70.00 rhcnium 0.99 molybdenum 0.05 4() EXAMPLE XXV EXAMPLE X] lutinum 40.00 platinum 59.00 p rhodium 40.25 33 tungsten rhcnium 0 05 EXAMPLE EXAMPLE XXVI platinum 29.95 rhodium 70.00 platinum l4.0 tunstcn 0.05 rhodium 85.0 molybdenum 0.5 EXAMPLE XI" tungsten 0.3 iridium 0.2 platinum 59.00 F".f" EXAMPLE XxvII indium 0.75

l t' 30.0 EXAMPLE XIv ihiiiriii' platinum 2995 molybdenum rhodium 70.00 iridium 0.05

EXAMPLE XV EXAMPLE XXVllI latinum 4 5900 platinum 59 Ehodium 40.25 60 tungsten 0.4 EXAMPLE XVI rhenium 0.3

platinum 29.95 rhodium 70.00 EXAMPLE XXIX rhenium 0.05 platinum 78 5 EXAMPLE XvII 'ggff 3f platinum 40.0 rhenium 0.1 0.5

rhodium 59.5 molybdenum EXAMPLE XXX platinum rhodium molybdenum tunstcn iridium rhenium Alloys containing platinum and a high proportion of rhodium typically exhibit very brittle characteristics unless their purity is very high and their gas content very low. Even the highest purity alloys, however, exhibit some brittleness especially after exposure to operating temperatures of 1,800F. to 2,750F. Due to lattice changes with increasing rhodium content, highrhodium alloys have a great affinity for gas, particularly oxygen. The addition of a third element, which forms a volatile oxide more readily than platinum or rhodium tends to minimize the effects of impurities or dissolved gas on high rhodium content alloys. The effect of the third metal addition on high content rhodium alloys may be theorized by one of the following phenomena: (1) the third metal element ties up and carries away oxygen thereby preventing formation of a thin film of oxide on grain boundaries or (2) the third metal element ties up and carries away oxygen much faster than the diffusion of oxygen in the lattice network, thus preventing embrittlement or (3) the third metal element tends to further refine and degas the alloy during melting which results in improved properties, or (4) the third metal additions acts as an absorbing media for adsorbed and dissolved oxygen in the alloy. It is theorized that the third metal addition is converted to a volatile oxide which inhibits oxygen absorbtion into the alloy. Thus the ductility of the alloy is maintained and the high rhodium alloy may be welded and used in high temperature service applications.

It is therefore an object of this invention to provide a platinum-high rhodium content 'alloy capable of being fabricated into desired articles and capable of withstanding high operating temperatures.

It is another object to provide an alloy which is highly resistant to attack by molten glass and air, which has good creep (Creep is defined as deformation or elongation as a function of time at a uniform stress, usually at high temperatures.) resistance, good creep-rupture life Creep-rupture life is defined as the time until fracture at a given temperature and stress), and which has high load carrying ability at elevated temperatures.

These and other objects will be readily apparent from the following detailed description which it intended only to illustrate and disclose the invention.

In a platinum-high rhodium content alloy, it is desirable to have a minimum creep rate, good creep-rupture life and high strength at high operating temperatures.

Alloys comprising a very high rhodium content (at least 20 percent) find application where service temperatures are very high (2700 2800F.) or in high stress applications at moderate temperatures (220 2600F.) to prevent excessive deformation thereof.

It is known that rhodium is a good hardener for a platinum containing alloy, i.e. it is a good solid solution strengthener and forms a continuous solid solution. Rhodiums oxidation resistance approximates that of platinum and is therefore the basis for selecting a platinum-rhodium system.

The third metal addition to the platinum-rhodium system adds stability to the system in that it extends the operating life of articles fabricated therefrom. The third metal addition forms an oxide more readily than platinum or rhodium and it volatilizes during welding operations thereby maintaining the ductility of the alloy. Without the third metal addition, the alloy would readily absorb oxygen and become brittle and thereby be impossible to fabricate and would have a shorter operating life.

Alloys comprising up to about 40 percent rhodium are commercially available but in order to increase alloy strength, the rhodium content must be increased. However, by increasing the rhodium content, the ductility of the alloy is adversely affected because of the oxygen absorption, hence the third metal addition is employed in the inventive concept to remedy the situation.

The criteria for the third metal addition(s) include (1) a capability of forming a volatile oxide above 1,800F. that volatilizes faster than platinum or rhodium, (2) a modulus higher than that of platinum or rhodium, (3) a suitable lattice structure (4) a high valence state (7,8,9,), i.e. its free electrons are available for bonding purposes, to increase the alloys resistance to creep, and (5) a high melting point to withstand high service temperatures.

A desired article or apparatus is usually made from our platinum-rhodium alloy for forging and rolling it into sheet form, followed by fabrication and welding. However, the alloy of this invention is capable of being cast into shapes i.e. slinger cups, spinnerettes, etc.

A double vacuum melting process is preferred when making articles for use in high temperature applications to help insure a homogeneous mix and uniform properties throughout the alloy, and especially to help distribute losses of the third metal addition by volatilization.

When a bushing structure is fabricated for use at high service temperatures, it is sometimes desirable to make a composite structure comprising different alloys having the same constituents but different proportions. For example, the body, tip sections, and tips of a bushing structure may be fabricated from platinum-high rhodium content alloys whose compositions vary in order to meet specific operating temperatures. More specifically a lower content of rhodium (2025 percent) in a platinum-rhodium-X ternary system may be used in a bushing body to help maintain proper bushing current distribution and to maintain ductility whereas a higher content of rhodium (up to 60 percent) in a platinumrhodium-X ternary system may be used in the tip section to reduce the creep deformation of the composite structure.

Electrical resistivity plays an important role in the selection of alloys for fabrication into bushings and other apparatus where electrical current is passed therethrough. As the rhodium content is altered in a platinum-rhodium system to obtain specific properties, the resistivity of the latter is altered. In order for these alloys having varying rhodium contents to be fabricated into composite bushings, varying amounts of the third metal are added in order to obtain a certain resistivity. That is, the composite structure requires the resistivities thereof to approximately be of the same magnitude. Therefore the resistivity of these alloys have been made to be a function of the amount of the third metal therein. The importance of the resistivities being of the same magnitude is because temperature differentials would arise as the resistivity varied, thereby decreasing the efficiency of the fabricated article, such as a bush- It has been observed that the addition of small amounts of a third metal to a platinum-rhodium alloy increases the contact angle of the alloy. This characteristic is critical in the manufacture of glass fibers to prevent a condition known as flooding from occurring. Contact angle is defined as 2 tan (h/X) wherein h is the height of a molten bubble of glass on a particular substrate and x is the radius of the base of the bubble. Flodding is defined as the covering or wetting of a substrate, such as the tip plate or sidewall of a feeder, housing hollow projections or tips, with molten glass which disrupts the formation of glass fibers. As the contact angle increases the tendency toward flooding decreases, thereby leading to a more efficientoperation.

Composite bushing structures were fabricated from the platinum-rhodium-x ternary alloy systems of this invention, wherein the compositions for the sidewalls, tip plate, and tips were as follows, expressed in weight Platinum Rhodium Sidewalls 75 -85 -25 trace Tip plate 60-40 40-60 up to 1.0 Tips 70-80 -30 trace The amount of the third metal added to each alloy was based upon the rhodium content of the alloys so that the composite structure possessed substantially uniform electrical resistivity. Molybdenum is the preferred third metal addition in the above composition ranges for alloys employed in a composite bushing structure. However, the other named third metal additions and combinations thereof function in the same manner.

We claim:

1. A glass feeder, comprising sidewalls, and a plurality of hollow projections extending outwardly from a particular sidewall, adapted for containing and controllably emitting a plurality of streams of molten glass for formation into glass filaments, fabricated from an alloy consisting essentially of platinum, rhodium and a third metal selected from the group consisting of tungsten, iridium and rhenium and combinations thereof, said third metal being present in an amount sufficient to increase the ductility of the alloy.

2. The glass feeder, as claimed in claim 1, wherein the feeder is fabricated from an alloy comprising, by weight percent, platinum 14-79, rhodium 20-85 and a third metal 001-10.

3. The glass feeder, as claimed in claim 2, wherein the third metal is tungsten.

4. The glass feeder, as claimed in claim 2, wherein the third metal is iridium.

5. The glass feeder, as claimed in claim 2, wherein the third metal is rhenium.

6. The glass feeder, as claimed in claim 1, wherein the feeder is fabricated from an alloy comprising, by weight percent, platinum 29-59, rhodium 40-70, and

a third metal 0.05-0.75.

7. The glass feeder as claimed in claim 6, wherein the third metal is tungsten.

8. The glass feeder, as claimed in claim 6, wherein the third metal is iridium.

9. The glass feeder, as claimed in claim 6, wherein the third metal is rhenium.

10. The glass feeder, as claimed in claim 1, wherein the feeder is fabricated from an alloy comprising, by weight percent, platinum 40.0, rhodium 59.5 and a third metal 0.5.

11. The glass feeder, as claimed in claim 10, wherein the third metal is molybdenum.

12. The glass feeder, as claimed in claim 10, wherein the third metal is tungsten.

13. The glass feeder, as claimed in claim 10, wherein the third metal is iridium.

14. The glass feeder, as claimed in claim 10, wherein the third metal is rhenium.

15. The glass feeder, as claimed in claim 1, wherein the feeder is fabricated from an alloy comprising, by weight percent, platinum 14-79, rhodium 20-85 and at least two of the third metals 001-10 16. A composite glass feeder having a substantially uniform electrical resistivity, comprising sidewalls, and hollow projections located on a particular sidewall fabricated from different alloys having the same constituents, but in different proportions, consisting of:

1. a high temperature alloy for the sidewalls comprising platinum 75-85 percent by weight, rhodium 15-25 percent by weight, and a trace of a third metal selected from the group consisting of tungsten, iridium, rhenium and combinations thereof;

2. a high temperature alloy for the particular sidewall comprising platinum 40-60 percent by weight rhodium 40-60 percent by weight, and up to 1.0 percent by weight of a third metal selected from the group consisting of tungsten, iridium, rhenium and combinations thereof, said third metal being present in an amount sufficient to increase the ductility of the alloy; and

3. a high temperature alloy for the follow projections comprising platinum -80 percent by weight, rhodium 20-30 percent by weight, and a trace of a third metal selected from the group consisting of tungsten, iridium, rhenium and combinations thereof; wherein the third metal in said alloys is present in an amount sufficient to maintain the resistivities of the alloys at the same magnitude when the feeder is in use at high temperatures.

17. The glass feeder as claimed in claim 15 wherein molybdenum is used in combination with the third metals.

18. The composite glass feeder as claimed in claim 16 wherein molybdenum is used in combination with the third metals.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2239561 *Jan 17, 1940Apr 22, 1941Baker & Co IncSpark plug
US2460547 *Oct 7, 1946Feb 1, 1949Glass Fibers IncDrawing crucible
US3362799 *May 10, 1965Jan 9, 1968Int Nickel CoDuctile ruthenium alloy and process for producing the same
US3622289 *Dec 12, 1969Nov 23, 1971Owens Corning Fiberglass CorpGlass feeder made of pt-rh-mo high temperature-high strength alloy
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4123263 *Nov 2, 1977Oct 31, 1978Owens-Corning Fiberglas CorporationPlatinum-rhodium alloys
US5140732 *Jun 13, 1991Aug 25, 1992Manville CorporationMethod of forming bushing plate for glass filaments
US5853904 *Apr 17, 1997Dec 29, 1998Johnson Matthey Public Limited CompanyHigh temperature articles
US6250111 *Dec 1, 1998Jun 26, 2001Nh Technoglass Co.Lining material for glass melting furnaces, glass melting furnaces, process for producing glass products, and process for purifying the lining material
US6401493 *Sep 7, 1999Jun 11, 2002Nh TechnologiesLining material for glass melting furnaces, glass melting furnaces, process for producing glass products, and process for purifying the lining material
US6589475Mar 20, 2002Jul 8, 2003Nh Technoglass Co.Lining material for glass melting furnaces, glass melting furnaces, process for producing glass products, and process for purifying the lining material
US6982059 *Oct 1, 2001Jan 3, 2006General Electric CompanyRhodium, platinum, palladium alloy
US7980099Mar 15, 2007Jul 19, 2011Ocv Intellectual Capital, LlcMultiple alloy bushing assembly
US8001807Mar 15, 2007Aug 23, 2011Ocv Intellectual Capital, LlcPalladium screens for bushing assembly and method of using
US20050265888 *Oct 1, 2001Dec 1, 2005Jiang LiangRhodium, platinum, palladium alloy
US20070227195 *Apr 7, 2005Oct 4, 2007Saint-Gobain Vetrotex France S.A.Die For Producing Filaments, In Particular Glass Filaments And The Fibre Drawing System Thereof
US20080141726 *Mar 15, 2007Jun 19, 2008Purvis David FPalladium screens for bushing assembly
US20080141727 *Dec 14, 2006Jun 19, 2008Sullivan Timothy ARefractory system for bushing assembly
US20080223082 *Mar 15, 2007Sep 18, 2008Harms Todd MMultiple alloy bushing assembly
EP0702093A1 *Sep 1, 1995Mar 20, 1996Johnson Matthey Public Limited CompanyHigh temperature articles
EP2420583A3 *Jul 12, 2011Jul 4, 2012C. Hafner GmbH + Co. KGPerfectly white, tarnish-proof noble metal jewellery alloy
Classifications
U.S. Classification65/493, 65/374.12, 420/462, 420/467
International ClassificationC22C5/00, C22C5/04, C03B37/00, C03B37/095
Cooperative ClassificationC22C5/04, C03B37/095
European ClassificationC22C5/04, C03B37/095
Legal Events
DateCodeEventDescription
Jul 31, 1987ASAssignment
Owner name: OWENS-CORNING FIBERGLAS CORPORATION, FIBERGLAS TOW
Free format text: TERMINATION OF SECURITY AGREEMENT RECORDED NOV. 13, 1986. REEL 4652 FRAMES 351-420;ASSIGNORS:WILMINGTON TRUST COMPANY, A DE. BANKING CORPORATION;WADE, WILLIAM J. (TRUSTEES);REEL/FRAME:004903/0501
Effective date: 19870730
Free format text: TERMINATION OF SECURITY AGREEMENT RECORDED NOV. 13, 1986. REEL 4652 FRAMES 351-420;ASSIGNORS:WILMINGTON TRUST COMPANY, A DE. BANKING CORPORATION;WADE, WILLIAM J. (TRUSTEES);REEL/FRAME:4903/501
Owner name: OWENS-CORNING FIBERGLAS CORPORATION, A CORP. OF DE
Nov 13, 1986ASAssignment
Owner name: WADE, WILLIAM, J., ONE RODNEY SQUARE NORTH, WILMIN
Free format text: SECURITY INTEREST;ASSIGNOR:OWENS-CORNING FIBERGLAS CORPORATION;REEL/FRAME:004652/0351
Effective date: 19861103
Owner name: WILMINGTON TRUST COMPANY, ONE RODNEY SQUARE NORTH,
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Owner name: WADE, WILLIAM, J.,DELAWARE
Owner name: WILMINGTON TRUST COMPANY,DELAWARE
Owner name: WILMINGTON TRUST COMPANY, DELAWARE
Owner name: WADE, WILLIAM, J., DELAWARE