Hot isostatic pressing using a vitreous container

Jan. 14, 1975 c. J. havel Re· 28,301

HOT ISOSTATIC PRESSING USING A VITREOUS CONTAINER

Original Filed Feb. 28, 1968

Sheets-Sheet 1

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Jan. 14, 1975 C. J. HAVEL &amp;^e- 28,301

HOT ISOSTATIC PRESSING USING A VITREOUS CONTAINER ._ 3 Sheets-Sheet

Original Filed Feb. 28, 1968

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FIG.4.

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Jan. 14, 1975

C. J. HAVEL

Re. 28,301

HOT ISOSTATIC PRESSING USING A VITREOUS CONTAINER

Original Filed Feb. 28, 196S

Sheets-Sheet ?

FIGS.

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LOG. VISCOSITY-POISES

Re. 28,301

Reissued Jan. 14, 1975

United States Patent Office

28,301

HOT ISOSTATIC PRESSING USING A VITREOUS CONTAINER Charles J. Havel, 162 Proctor Blvd., Utica, N.Y. 13501

Original No. 3,622,313, dated Nov. 23, 1971, Ser. No. 734,822, Feb. 28, 1968, which is a continuation-in-part of abandoned application Ser. No. 636,700, May 8, 1967. Application for reissue Nov. 19, 1973, Ser. No. 416,967

Int. Cl. B22f 3/14

U.S. CI. 75—223 28 Claims .Matter enclosed in heavy brackets [] appears in the original patent but forms no part of this reissue specification; matter printed in italics indicates the additions made by reissue.

ABSTRACT OF THE DISCLOSURE

Hot compacting of metallic powders in a vitreous evacuated container of a predetermined shape corresponding to the shape of the densified object desired by subjecting the container to a temperature sufficient to render the container plastic and the contents densifiable, by the application of external pressure upon the container walls.

This application is a continuation in part of my application Ser. No. 636,700, filed May 8, 1967, now abandoned.

This invention relates to a process of hot compacting metallic powders into ingots or objects of predetermined shape.

The invention is directed to the formation of objects of various shapes from powdered metal or metal oxides such as beryllium oxide and the like and combinations of metallic and inorganic nonmetallic particulate material, by what may be called hot isostatic pressing. The pressing comprises the placing of such powders in containers, or capsules of glass or other vitreous substances, the container or capsule having an internal shape corresponding essentially to the shape of the finished articles to be produced by the metallic powder. The container or capsule is of a vitreous substance capable of maintaining its shape under the temperatures necessary to cause densification of the powdered metal contained therewithin, allowance being made to compensate for size change when the capsule is under pressure and subjected to the heat required for densification of the powdered contents.

More particularly the invention contemplates the densification of powdered metal while contained in a glass or equivalent container, the characteristics of which in relation to the characteristics of the powdered metal is such that the glass of the container will hold its shape without deforming except to plastically shrink until the powdered metal core develops enough mechanical strength so as to be capable of supporting the glass shape through further shrinkage and compaction. The glass may be conveniently blow molded, slip cast, or pressed to any desired shape before filling the same with the powder.

The above and other novel features of the invention will appear more fully hereinafter from the following detailed description when taken in conjunction with the accompanying drawings. It is expressly understood that the drawings are employed for purposes of illustration only and are not designed as a definition of the limits of the invention, reference being had for this purpose to the appended claims.

In the drawings, wherein like reference characters indicate like parts:

FIG. 1 shows a vessel containing a pot within which resistance heating in a salt bath may be employed;

FIG. 2 shows the vessel provided with a muffle having a resistance heating element;

FIG. 3 shows the vessel provided with a susceptor heated by an induction coil;

FIG. 4 shows the vessel provided with a coil for high frequency induction heating; and

FIG. 5 shows temperature viscosity curves for several types of glass and the useful temperature ranges for each.

Referring to FIGS. 1-4 of the drawings there is shown 10 a capsule or container 18 or 18' having metallic powder 20 therewithin. The container may be of any shape desired so as to produce an article of predetermined shape upon densification of the metallic powder therewithin.

It may be a blow molded, slip cast or pressed glass con15 tainer, and given its shape by the shape of the mold.

In FIG. 1 the container 18 is shown placed on a support 24, surrounded by salt 22 contained within the ceramic or brick pot 25. The salt is heated electrically by electrodes 26 connected by leads 30 to a high amperage low ²⁰ voltage source of alternating current which may be supplied through a recorder and controller 44.

In FIG. 2 the insulation 32 is shown as extending to a ceramic or metallic muffle 60 heated by a resistance heating element 62 connected to a suitable source of power as 25 desired, the muffle surrounding the container 18' of glass or the like having the powdered metal within, which may rest on a ceramic plate 17.

In FIG. 3 there is shown a tubular graphite susceptor 74 of carbon or other suitable material with a ceramic ³⁰ surrounding layer and support 72 for a water cooled induction coil 70, and in FIG. 4 there is shown a water cooled high frequency induction coil 80. In each of FIGS. 2, 3 and 4 the glass container may rest on a ceramic base 17 in the manner shown, and may be surrounded by air or gas introduced into the vessel 30.

The pot 25 or heating coils of FIGS. 2, 3 and 4 are surrounded by heat insulation 32, within a pressure vessel 30, having a lid or closure 36 secured to the vessel by a 4θ threaded ring 38, the lid being seated and sealed to the vessel by suitable gaskets. The vessel is provided with a conduit 46 adapted for connection to a source of compressed air or gas, and an indicator 50 is provided to observe the pressure. The lid 36 is provided with a sight port 45 40 for an optical pyrometer 42, which may be connected to the controller to provide regulation. The vessel and lid may be provided wih water cooling coils.

The filled and sealed container may be preheated to the strain point to reduce shock and in the apparatus as shown 50 in FIG. 1, the container is placed in the hot molten salt bath 22. Thereafter the vessel is closed and subjected to high pressure air or gas if desired. The glass container and powdered metal may thereby be subjected to differential pressure due to both vacuum within the container as 55 well as gas pressure applied to the vessel. Equal pressure from all directions is exerted upon the container, and due to the plasticity of the glass, at the pressing temperature, the powder will be subjected to compacting forces allowing it to be densified into a shape corresponding to the internal 60 wall of the container.

After the elapse of an appropriate time, at the selected temperature and pressure, the vessel 30 is bled to atmospheric pressure, the end closure removed, and the densified compacted object is extracted from the molten salt. 65 Due to the wide difference in thermal shrinkage of the compacted metal and the surrounding glass, the glass will flake off, leaving a glass-free densified metal form.

In practice, the glass container having the internal shape to be produced, with appropriate allowances for size change during densification, is filled with metallic powder, and evacuated, as by a suitable vacuum pump, and is then hermetically sealed. The selection of glass or other vitreous

28,301 ubstance should be determined by the desired temperaure of pressing. It is believed to be critical that the glass imployed has a viscosity at the pressing temperature of no nore than 10¹¹ poises.

Following are a number of representative types of glass ₅vhich may be employed for the purpose, with their repective operating ranges in degrees Centigrade.

type of glass Operating range, ⁰ C.

(1) Lead Alkali Silicate_______________410-630 (2) Borosilicate (Pyrex)______________ 550-900 ¹⁰ (3) Aluminosilicate __________________ 700-980 (4) 96% Silica (Vycor)__ 890-greater than 1600 (5) Fused Silica_________1130-greater than 1600

Other sections were flat forged perpendicular to the longitudinal axis on a mechanical press at 2025° F. Successive reductions of 20 percent, 20 percent and 40 percent were taken in one blow each, with no cracking. The forged coupons or flat sections were then heat treated as above and tested.

In addition compacts were formed having a diameter of 2½ inches and a length of 3 inches, approximately, as above, and thereafter extruded to a diameter of % inch (6.6 to 1 extrusion ratio) at a temperature of 1975° F. Such extrusions were then heat treated as above and tested. The results of the tests are as follows:

TABLE OF PROPERTIES DETERMINED ON UDIMET 700 COMPACTS

Stress rupture at 1,300°F., tensile l,800°F./18₍000 p.s.i.

<td> Condition</td><td> Hours</td><td> Percent El.</td><td> Percent RA</td><td> UTS (Ks.l.)</td><td> .2 ΥΘ</td><td> Percent El.</td><td> Percent RA</td><td> Grain size (ASTM)</td><td> Hardness (Rc)</td>

<td> Compacted, and heat treated......................</td><td> .......... 65.8</td><td> 6.6</td><td> 5.6</td><td> 170.3</td><td> 125.0</td><td> 12.0</td><td> 13.1</td><td> 2</td><td> 40</td>

<td> Compacted, heat treated and forged--.-...........</td><td> .......... &lt;&gt;)</td><td> (*)</td><td> ()</td><td> 177.2</td><td> 136.4</td><td> 22.3</td><td> 22.7</td><td> 6</td><td> 40</td>

<td> Compacted, extended and heat treated............</td><td> .......... 69.1</td><td> 7.3</td><td> 8.1</td><td> 175.0</td><td> 139.5</td><td> 38.0</td><td> 35.1</td><td> 7</td><td> 41</td>

&gt; Not determined.

The viscosity characteristics in the temperature range ippropriate to the procedure herein are indicated by curves L, 2, 3, 4 and 5 respectively in FIG. 5, curve 1 being that or lead Alkali Silicate glass referred to above, for ex- ₃θ unple. It will be noted that the temperature range for this ^ύ’lass between the anneal point and a lower limit of approximately IO⁶·⁵ poises, as indicated by the anneal point par 6 and the lower limit bar 7 on FIG. 5 approximates 110-630° C. Below the lower limit, the glass adheres to ₃pther objects and will also penetrate into the surface of he powder mass, causing a contaminated layer. If the glass s heated in the vicinity of 10⁴ poises or less there is danger :hat it will flow to an extent to expose the metal core directly to the compacting gas and thereby destroy the dif- 40 ierential pressure necessary for successful compaction.

A glass the type having a temperature range of 410°530° C. would be suitable for pressing brasses, aluminum ind aluminum alloys, and magnesium and its alloys.

A glass of the type whose viscosity-temperature charac- 45 teristics are illustrated by curve 4 for 96 percent Silica, which contains about 3 percent of Boric Oxide and the palance of other oxides isused for the compaction of a super alloy identified as Udimet 700, (Astrology). This powder includes Aluminum, Titanium, Molybdenum, 50 Chromium, Cobalt and Nickel in the following nominal proportions:

Al Ti Mo Cr Co Ni P.p.m. Mesh

A...... 4.5 3.5 5 15 18 Balance490... 0 -100 ⁵⁵

Such powder when loaded into standard Vycor tubing of 30 mm. outside diameter and of a desired length such as 6 inches, is evacuated to 1 micron vacuum and sealed off. A plurality of such tubes when placed in an auto- 60 clave are heated to 1288° C. (2350° F.), stabilized, and then subjected to a gas pressure of 15,000 pounds per square inch for an hour or less.

Upon removal from the autoclave, the density of the pieces so formed was determined to be 8.02 g./cc. or 100 65 percent of theoretical density. This was then confirmed by fluorescent penetrant inspection and metallographic examination. Sections were cut and heat treated:

2150° F.-4 hours-air cooled

1975° F.-4 hours-air cooled

1550° F.-24 hours-air cooled and

1400° F.-16 hours-air cooled

A feature of the technique is that compacting may be done at a temperature betwen the liquidus and solidus temperatures so that incipient melting occurs while the mass is subjected to exterior pressure. The 2350° F. compacting temperature in the previous example is between the liquidus-solidus for the Udimet 700 alloy used. Under these conditions the liquid phase formed at the elevated temperature containing an M₃B₃ boride, is believed to flux the oxide film on the surface of each powder particle, allowing base metal to metal contact of the particles, resulting in a true metallurgical bond. It is believed that the surface oxide on each particle dissolves in the liquid phase.

Upon cooling, the vitreous container collapses, compensating for shrinkage of the incipient melt phase as it freezes, thereby eliminating microporosity prevalent in compacts which are liquid phase sintered.

Previous attempts to hot press superalloy powders have been done below the solidus temperature. The resulting compacts have shown remnant surface oxide from the original powder particles which is detrimental to their properties, since a strong metallurgical bond cannot be made due to the oxide film interference. Furthermore hot working, rolling, extrusion, forging, etc., will not mechanically break down the film and the particles never lose their original identity in the compacted mass.

Hot working will deform the particles, but not destroy the oxide film. Upon solution treatment after hot working recrystallization takes place within each film, powder particle, but not across the particle -boundary oxide film.

The unique result of hot pressing in the incipient melt area, that is, above the solidus, below the liquidus, is that the original powder particles lose their identity, while at the same time, grain growth is retarded due to the fact that the solid portion of the powder particles that remain, act as nuclei for the grains of the final compact. In essence, the technique will produce extremely fine grain large and small castings which will have improved properties and hot workability over conventionally cast material.

The incipient melting compacting technique is applicable to all alloys and not only to superalloys. In those alloys where the incipient melting phase does not flux particle surface oxide, innocuous additions of boron may be made to cause a boride phase to melt.

In the conventional isopress with a steel or other metal can, the powder is precompacted at room temperature to about 80 percent density in the shape of the piece to be produced and the steel can is built around it. The precompacting is necessary since the steel can cannot and the properties determined.

28.301 shrink to the extent required when going from a loose powder density to a full density without severe ripping (approximately 50 percent loose powder density to 100 percent compact density). The ripping referred to results in a wrinkled surface on the compact. The precom- 5 pacting process is therefore employed to reduce the shrinkage required of the can.

All of the above is due to the fact that the steel or other metal can cannot easily plastically shear. The vitreous container, on the other hand, accomplishes plastic 10 shear quite readily, and pieces can be produced without precompacting and without wrinkles on the compact surface.

In the pressing example previously described with Udimet 700 no wrinkles were observed even though the 15 powder was loaded into the glass container at a bulk density of 55 percent and was compacted to 100 percent density.

It would appear that the process would not work, since beyond the annealing point of a glass, the container and 20 its contents would deform of their own weight. It might be expected therefore that in the attempt to produce a given shape that the glass container would deform under gravitational forces and therefore produce a misshapen piece. 25

The factor which prevents the above situation from occurring is the result of the metal core developing enough mechanical strength after the powder filled container passes the annealing point, to cause the core to support the glass shape rather than the glass shape 30 support the metal core.

The development of core strength can be achieved by applying pressure, over and above atmospheric, once the temperature has passed the strain point of the glass employed. The amount of pressure applied is governed by 35 the compacting characteristics of the powder metal core as well as the pressure limitations of the autoclave used.

Some glass-metal powder combinations such as Pyrex and pure iron powder, will retain shape without the aid of pressure superimposed beyond atmospheric.

The method is applicable to such metals as powdered beryllium, superalloys, titanium, etc., and inorganic nonmetallic such as tungsten carbide, beryllium oxide, and also combinations of metallic and nonmetallic composites as well as others. From the foregoing it can be seen that the process is capable of producing hollow parts such as tube blanks, hollow hemispheres, shaped solid articles such as turbine disc blanks, turbine blades, and any other shape for which a container can be formed of glass, or other vitreous substance which on exposure to heat behaves in a glass-like manner.

The shapes so formed may be of the precise shape desired, or so near as to require a minimum of machining or other surface treatment. _r

While a single form of apparatus has been illustrated ⁰⁵and described for use in the process, it is to be understood that the invention is not limited thereto. As various changes in the construction and arrangement and procedures may be made without departing from the spirit θθ of the invention, as will be apparent to those skilled in the art, reference will be had to the appended claims for a definition of the limits of the invention.