US3762026A

US3762026A - Method of making a high temperature body of uniform porosity

Info

Publication number: US3762026A
Application number: US00751680A
Authority: US
Inventors: Z Shapiro
Original assignee: NUCLEAR MATERIALS AND EQUIP CO
Current assignee: NUCLEAR MATERIALS AND EQUIP CO; NUCLEAR MATERIALS AND EQUIP CORP US
Priority date: 1963-01-08
Filing date: 1968-07-29
Publication date: 1973-10-02
Anticipated expiration: 1990-10-02

Abstract

A method of making a high temperature and stress resistant body of desired porosity in whose practice a green porous body (FIGS. 4, 5, 9, 10) of higher than the desired porosity is formed by compacting different size fractions of spherical particles (A, 23, 27 FIGS. 4, 5) or by winding fine cold-drawn wire (53 FIG. 9) or mesh of fine cold-drawn wire (73 FIG. 10) on a mandrel (51 FIG. 7; 71 FIG. 10). The green body is cemented into a rigid body and at the same time its porosity is decreased to the desired magnitude by depositing cementing material (H5 FIG. 11, 61 FIG. 9, 77 FIG. 10) in the pores (25 FIGS. 5 and 6; 55 FIG. 9) from a gas. Typically a body of tungsten is formed by reducing a tungsten halide in the pores with hydrogen.

Description

1 1 Oct. 2, 1973 METHOD OF MAKING A HIGH TEMPERATURE BODY OF UNIFORM POROSITY [75] Inventor: Zalmarl M. Shapiro, Pittsburgh, Pa.

[73] Assignee: Nuclear Materials and Equipment Corporation, Apollo, Pa.

[22] Filed: July 29, I968 [21] Appl. No.: 751,680

Related'U.S. Application Data [6 Continuation of ser. No. 250,112, Jan. 8, 1963,

abandoned.

[52] US. Cl 29/420, 29/419, 29/530 [51] Int. Cl. B22f [58] Field of Search 29/419, 420, 527.1, 29/5272, 527.4, 423, 424

[56] References Cited UNITED STATES PATENTS 2,475,601 7/1949 Fink 117/107.2 3,049,799 8/1962 Breining et al. 29/420 3,135,044 6/1964 Mote et a1. 29/423 3,139,658 7/1964 Brenner et a1. 22/200 3,153,279 10/1964 Chessin 29/420 Primary Examiner-John F. Campbell Assistant ExaminerD. C. Reiley AttrneyI-Iymen Diamond [57] ABSTRACT A method of making a high temperature and stress resistant body of desired porosity in whose practice a green porous body (FIGS. 4, 5, 9, 10) of higher than the desired porosity is formed by compacting different size fractions of spherical particles (A, 23, 27 FIGS. 4, or by winding fine cold-drawn wire (53 FIG. 9) or mesh of fine cold-drawn wire (73 FIG. on a mandrel (51 FIG. 7; 71 FIG. 10). The green body is cemented into a rigid body and at the same time its porosity is decreased to the desired magnitude by depositing cementing material (H5 FIG. 11, 61 FIG. 9, 77 FIG. 10) in the pores FIGS. 5 and 6; FIG. 9) from a gas. Typically a body of tungsten is formed by reducing a tungsten halide in the pores with hydrogenv 9 Claims, 11 Drawing Figures Pmwrmm 3.T82.028

SHEET HP 2 METHOD F MAKING A IllIGII TEMPERATURE BODY OF UNIFORM POROSITY This application is a continuation of application Ser. No. 250,] 12, filed Jan. 8, 1963, and now abandoned.

This invention relates to the art of fabricating or forming bodies of materials which do not readily lend themselves to the usual forming operations such as machining, molding, casting, forging, spinning, rolling and the like. In one of its specific, but highly important aspects, this invention is applicable to bodies of tungsten. But in its broader aspects this invention applies to such materials as tantalum, niobium, zirconium, titanium, vanadium, silicon, rhenium, chromium and molybdenum. These materials may be characterized as highly refractory, high strength materials; that is, each of these materials has a high melting temperature and is capable of manifesting high strength.

Specifically, this invention deals with producing bodies of predeterrninable shape or form which have a predeterminable porosity. This invention also relates to the art of producing hightemperature and high-stress resistant materials and of bodies of such materials having predeterminable shape and porosity. This invention has particular relationship to the production of such materials and bodies which are capable of withstanding the environmental and operating conditions to which critical components of the nuclear and aerospace apparatus are subjected. Typical of such components are the nozzles of space rockets.

The temperature and pressure of the gases blasting through the nozzle of a space rocket operating with acceptable efficiency may exceed 6,000" F and 900 pounds per square inch of area. The abruptness with which the mechanical and thermal stresses imposed on the material of the nozzle chance enhances the severity of these conditions. On ignition, the temperature of the nozzle rises sharply and non-uniformity giving rise to high thermal and mechanical stresses which may cause the nozzle to spall and crack. In addition, the high temperature and reactive nature of the propellant gases as well as the possible presence of particulate matter tend to alter the original nozzle shape and size through the loss of material by melting, corrosion and erosion. Any of these deleterious effects may deteriorate the nozzle enough to prevent the rocket from accomplishing its mission and it is indispensable that the nozzle be fabricated of such material and in such manner as to minimize these changes.

It is an object of this invention to provide a method of producing a high temperature resistant body having a selectable form and porosity It is another object of this invention to provide a method of producing a material for a rocket nozzle or the like which shall be capable of meeting the above described rigorous conditions; it also is an object of this invention to provide a body such as a rocket nozzle of such a material.

In providing rocket nozzles and like bodies, the practice has been adopted of forming the body of a highmelting point substance. Such substantces as tantalum carbide (melting point 7,0l5 F) and hafnium carbide (meIting point 7,025 F) have high melting points but do not in their present form have the necessary physical attributes to lend themselves to the fabrication of such bodies. Tungsten (melting point 6,l70 F) which has a 6 In addition, with the advent and use of more advanced propellants, even tungsten must be impregnated with evaporative coolant materials such as silver or copper to prevent the surface from melting at the higher gas temperatures generated. For this purpose the body must be porous so that it can absorb the cooling metals during fabrication and release the cooling metals during the high temperature application. It is moreover essential that the pores be in communication and that the body have a mean porosity for the communicating pores which shall be reliably predictable and shall be constant, as required by the conditions of application. The higher gas pressures generated by these propellants also require stronger, tougher bodies to withstand the thermal shock and the resulting mechanical stresses. Conversely at the same gas pressures, stronger materials would permit reduction in weight.

In the practice of this art, porosity may be measured as a direct function of the purpose which it is to serve by measuring the quantity of a liquid which a porous body can absorb. in carrying out this measurement, mercury (or other dense liquids as carbon tetrachloride or acetylene tetrabromide) is injected in the pores under pressure and the quantity of mercury injected under preset conditions is determined. This procedure measures the mean open porosity which is of essential interest. The mean total porosity may be measured by determining the density of the body. The density may be expressed in terms of percent of the density of the solid substance (tungsten for example).

It is another object of this invention to provide a tough, strong body having a constant mean porosity which shall be capable of withstanding the thermal shock and stresses to which a rocket nozzle is subjected.

In accordance with the teaching of the prior art, refractory structure such as nozzles are made from tungsten powder by the isostatic pressing at high pressures (approximately 40 tons per square inch) and sintering at high temperatures (2,0002,200 C). The process is excessively costly and requires complicated equipment. In addition, the powder used is produced by chemically reducing a compound such as ammonium paratungstate. The resulting structure has relatively poor mechanical properties and must be massive.

The powder which is compressed usually is irregularly shaped and of a size distribution suited to achieve sintered densities between and theoretical from the green billets. Because of the nature of the powder and the fabrication process, the pores obtained are irregular in shape and random in distribution and size. A good percentage of the pores are totally closed and not interconnected with other pores and are not available as regards filling with cooling metals. Not only does the quantity of silver or copper which can be absorbed in such bodies vary somewhat from nozzle to nozzle, but the effusion and evaporation of the silver or copper during operation is dependent upon the nature of the pores from area to area and the protection afforded the nozzle varies in the same manner. Other shortcomings of this prior art practice are:

1. Die design and fabrication are costly, and heavy expensive presses and heating equipment are involved.

2. The practice is adaptable to fabrication only of relatively simple shapes, thus often forcing compromising of superior performance design to minimize fabrication difficulties.

3. Even though the starting powder may have been prepared carefully as to particle shape and particle size distribution, the pressed object invariably shows considerable variation from region to region in density and extent and nature of porosity (i.e., open versus closed porosity). Further, laminations and cracks are invariably present.

4. The high temperature sintering cycle is conducive to grain and crystal growth, thus leading to lowering of the mechanical strength below the poor strength which is at best available.

It is an object of this invention in its specific aspects to overcome the above described difficulties. Another object of this invention is to provide a low-cost method or a process for making a porous body of selectable shape and porosity and also to provide such a method for making a high temperature and high-stress resistant porous body such as a rocket nozzle, the pores of which shall communicate and the porosity of which shall be constant or reproducible within narrow limits. A further object of this invention is to provide such porous bodies.

A specific object of this invention is to provide a process or method for making tungsten and other refractory metal skeletal structures of reliably controllable density and porosity, which structures shall be capable of being infiltrated and/or consolidated with other metals such as silver, copper, silicon, hafnium, vanadium, chromium, niobium, zirconium, tantalum, tungsten, molybdenum rhenium and others as well as alloys of these and others or with refractory materials including ceramics, such as hafnium carbide, zirconium carbide, tantalum carbide, alumina and other carbides, borides, silicides and nitrides.

This invention in one of its aspects arises from the realization that the closer complete uniformity in pore size and characteristic is approached, the more uniform, predictable and reliable is the performance of the infiltrated nozzle. It was also realized that ideal uniformity might be closely approached by replacement of the reduced powder by spherical particles of specific size fractions, the quantity of each fraction and the particle dimensions being selected so as to provide the final required porosity. But such spherical powder is relatively inactive due to the low specific surface (surface area per unit mass) and previous preparation history and cannot readily be sintered. In accordance with this invention in one of its aspects a method is provided for cementing the spherical particles together without significant alteration in the geometry and uniformity of the pores and without weakening the green shape.

In accordance with this invention in one of its specific aspects one or more carefully selected size fractions of spherical tungsten particles are prepared by plasma jet fusion or other methods such as fluidizedbed decomposition or reduction of the halides and packed into appropriate shapes by mechanical packing and/or compaction in the manner described in R.K. McGeary's paper Mechanical Packing of Spherical Particles, Journal of Americans Ceramic Society 44 5l3-522 (1961). This paper is included herein by reference. For packings consisting of more than one fraction, the particles of each successive fraction would have a diameter of approximately 1/10 to 1/5 of the diameter of the preceding fraction. These particles dimensions may range between +400 U.S. standard mesh and 60 U.S. standards mesh; that is, the particles are of such dimensions as to pass through a 60 mesh sieve and be retained by a 400 mesh sieve.

The mass compacted as disclosed above is then consolidated or cemented together by reacting a tungsten halide such as pure tungsten hexafluoride or tungsten hexachloride with pure hydrogen obtained for example by diffusion through a silver-palladium membrane in the pores of the mass. Tungsten hexaiodide may also be used. This compound requires less or no hydrogen to effect the deposit. The reduction may also be effected by other reducing gases such as cracked ammonia. The mass may be precleaned to remove oxide or other contaminants prior to the cementing. This reaction produces uniform deposition of tungsten on the surface of the particles throughout the interstices of the porous body. As the tungsten deposits, it bridges the particles and connects them together. To assure uniformity of penetration and deposit, fine-grain structure, the reaction is best carried out slowly at relatively low temperatures up to approximately 900 F. Deposition at temperatures of about 480 to 900 F does not significantly alter the ductile-to-brittle transition temperature or the mechanical properties of the green mass. Because of the manner in which the spherical particles arrange themselves in a nested fashion during the compacting, the pores are in communication. The ultimate porosity is determined in the initial porosity and the amount of material deposited.

For example, assume that a final porosity ranging between 17 and 25 percent is desired. An initial packing density of approximately 60 percent would then allow for the deposition of adequate tungsten from the vapor phase to yield a strong body containing the desired pore volume. Such an initial packing density is readily achievable with spheres of a single size by the technique described in the McGeary paper cited above. Should it be desirable to reduce the amount of tungsten deposited from the vapor phase, higher initial green densities can be achieved by the utilization of a binary system consisting of spherical particles of two sizes. As cited above, use of ternary or quaternary systems of spherical particles can be used to obtain a range of initial green packed densities up to approximately 93 percent.

Another aspect of this invention arises from the realization that the tensile strength of substance such as tungsten increases and the ductile-brittle transition temperature decreases with the density of the substance and the fineness of its grain. Very dense, fine grained tungsten or other like material may be obtained by cold working (cold drawing or rolling) the material. Thus, the ultimate tensile strength of cold-drawn tungsten wire of 1 mil diameter wire at room temperature may exceed 600,000 pounds per square inch while that of sintered percent dense tungsten may just exceed 50,000 pounds per square inch. ln accordance with this aspect of the invention use is made of the high strength of tungsten wire for fabrication of complex shapes, particularly where additional reliability and weight reduction is very important, as for example, in the making of rocket nozzles. Conceivably the mass so formed may be cemented or bonded by plasma-jet flame spraying with tungsten. But more satisfactory bonding is achieved by reducing tungsten compounds in situ and thus depositing tungsten in the pores of the mass and this mode of bonding constitutes one of the important contributions of this invention.

In accordance with this specific aspect of the invention fine cold-drawn tungsten wire is wound on a mandrel with many lateral holes to allow the easy passage of gas through the holes. The mandrel has the internal shape of the desired object. Depending on the tension of the wire, a body is thus wound which typically may be 60-65 percent dense with respect to theoretical density. A tungsten halide, typically tungsten hexafluoride or tungsten hexachloride is then passed through the holes in the mandrel and through pores formed by the turns of the wire and reduced there by pure hydrogen. The deposited tungsten bridges the strands of wire and cements them together. The deposition takes place at a controlled temperature which may range from 480 to about 900 F, far below the recrystallization temperature of the wire and does not alter the mechanical properties of the wire. The wire in this case typically may be of a diameter of between 0.0001 inches and 0.020 inches. The diameter is determined by the porosity and mechanical properties desired. Successive layers after the first may be wound over the regions where successive turns of the lower layers are in contact. The winding is such that the pores of the structure are in communication. The wire can also be cross wound to achieve desired porosity, geometry, and mechanical properties.

The structure produced by winding wire on a mandrel as just described is stronger in a direction perpendicular to the axis of the turns than in a direction parallel to the axis of the turns. In accordance with a further aspect of this invention high strength in all directions of the structure (e.g., in the direction of the axis of the nozzle as well as in the direction perpendicular to the axis) is achieved by winding on a mandrel fine cold-drawn tungsten wire mesh or cloth of a variety of weaves, properly tailored to give the desired density or porosity and shape. This forms a green body of uniform pore size and distribution which is then cemented by the vapor phase reduction of the tungsten hexafluoride or chloride with high purity hydrogen. As in the other embodiments, the deposition is accomplished slowly at temperatures ranging from 480 F to approximately 900 F to minimize alteration in the favorable mechanical properties of the structure.

This invention in its specific aspects contemplates tungsten structures and tungsten is peculiarly suitable for the practice of this invention. In its broader aspects, this invention is not limited to tungsten, but includes structures of powder, wire or mesh of niobium, tantalum, zirconium, titanium, silicon, vanadium, hafnium, rhenium, chromium, and molybdenum. Further, the bonding or cementing agent may also include all of the aforementioned materials, and is not limited to tungsten or the base metal used to make the green shape.

Within its broader aspects this invention also includes deposition of refractory and ceramic materials within the interstices of cemented-bonded shapes prepared from particles, wires, and mesh to form cermetlike composite materials. Several such materials can be simultaneously co-deposited or several materials can be despoited in succession. Successive deposition is particularly suitable where it is desirable to deposit a barrier material to prevent interaction with the green mass or a layer on the green mass. In certain situations the green mass may be heated so that the outer layer fuses and cements the mass on cooling.

Metals may also be deposited to cement green masses of ceramic or glass particles, filaments or fibers including carbonaceous filaments or fibers. Deposition of these metals is accomplished by vapor phase reduction or decomposition or liquid phase infiltration followed where required by chemical reaction. As indicated previously, the materials which can be inserted into the porosities of the consolidated/cemented shapes include in addition to the metals the carbides of zirconium, tantalum, thorium, hafnium, niobium and the oxides of uranium, thorium, aluminum, magnesium, and zirconium as well as nitrides, silicides and borides. These materials have attractive properties, in that they combine the high strengths of the metal matrix with the additional refractory properties of the ceramic. Such materials have special use and attractiveness in high temperature applications where both high strength and good thermal shock properties are required.

The novel features considered characteristic of this invention are disclosed generally above. For a more thorough understanding of this invention both as to its organization and as to its operation, together with additional objects and advantages thereof, reference is made to the following description taken in connection with the accompanying drawings, in which:

FIG. 1 is a generally diagrammatic fragmental view in side elevation, highly enlarged, of a mass of spherical particles as they are packed in the practice of the aspect of this invention involving the compacting of particles;

FIG. 2 is a view taken in the direction of line IIII of FIG. 1;

FIG. 3 is a view in section taken along line III-III of FIG. 2;

FIG. 4 is a view in top elevation showing one layer of the largest particles of FIG. I and the smaller particles nested in the spaces between progressively larger particles;

FIG. 5 is a view in isometric of the layer shown in FIG. 4;

FIG. 6 is a view in section further enlarged taken along line VI--VI of FIG. 4;

FIG. 7 is a view in asymmetric illustrating apparatus for practicing the aspect of this invention involving the winding of wire into a mass;

FIG. 8 is a fragmental view in side elevation of a portion of a body produced with the apparatus shown in FIG. 8;

FIG. 9 is a view in section taken along line IX-IX of FIG. 8;

FIG. 10 is a fragmental view in section enlarged showing apparatus for practicing the aspect of this invention involving the formation of a body from wire mesh; and

FIG. 11 is a reproduction of a photomicrograph of about X magnification showing a portion of a body produced in the practice of this invention.

The article shown in FIGS. 1 through 6 is a portion of a porous body made up by mechanical packing or compacting a number of sizes of generally spherical particles. The largest particles as shown in FIGS. it and 2 are disposed in layers, the particles in the center layers being labelled A, the particles in the layer below A, B, and the particles in the layer above A, C. The particles A, B, C, should be compacted under such pressure that adjacent spheres are generally tangent. The pressure should not be so high that the spheres are deformed into a mass of appreciable solidity. Pressures of the order of 1.0 to 50 pounds per square inch are satisfactory.

With the particles A, B, C compacted so that they are tangent, there are regions 2i between the particles which are bounded by the adjacent spherical surfaces. These regions are in communication. Within these regions 21 smaller particles 23 may be nested. Typically the particles 23 of next smaller size than the particles A, B and C should have a diameter of HS to 1/10 the diameter of the particles A. There are spaces 25 defined by surfaces of the larger particles A, B, C and of the smaller particles 23. Within these spaces still smaller particles 27 having diameters of about 1/5 to 1/10 of the particles 23 are deposited.

In making the mass the spherical particles can be formed by feeding powder into a plasma jet torch and collecting the particles emitted by the plasma. The spherical particles are then assembled one fraction at a time while vibrated mechanically and tumbled thoroughly so that the distribution of the particles is relatively uniform. The loading may be effected by depositing the particles in the form under a piston on which a relatively small weight, of about 20 or 30 pounds, is placed. The second and next smaller size fraction is then added and caused to nest into the appropriate voids as shown in FIG. 3 by mechanical vibration with a load applied in the same way as to the largest fraction. The particles of the second size are deposited in the voids of the particles of the first size so that the volume of the mass remains unchanged. The position of the piston under the weight is also unchanged. This process is repeated for each successive smaller sized particles. The particles are thus compacted into a porous mass. The spaces between the particles are in communication.

The green compacted mass has a predetermined porosity. To reduce the porosity to the desired magnitude or to cement the particles, tungsten deposits 31 are produced in the pores by reducing a tungsten halide with pure hydrogen at controlled temperature in the range of 480 F to about 900 F. The spherical particles A, B, C, 23, and 27 are bridged by the deposit.

A body having a desired form and a desired porosity is readily fabricated in this way. The physical properties of this body can be set by proper selection of the green material and the cement and their relative properties and is determined primarily by the particle geometry.

In FIG. l I a photomicrograph of a body of tungsten in accordance with this invention is shown. This body includes particles M and 83 of two sizes. As can be seen from FIG. M, the deposited tungsten 45 cements the particles together.

The apparatus shown in FIGS. 7, 8, 9 includes a mandrel H on which a fine, cold drawn, tungsten wire 53 is wound. The mandrel 51 is rotatable by a suitable drive (not shown) to effect the winding of the wire. Between the turns of wire 511 there are spaces 54. Because of these spaces the green wound structure is porous and the pores 55 are in communication. The mandrel S11 is hollow and has holes 59 in its surface. A tungsten halide and pure hydrogen are conducted through the pores and produces tungsten deposits 61 in the pores. The deposit at is discontinuous as can be seen from FIG. 8.

In accordance with a further specific aspect of this invention, the wire 53 may be wound on the mandrel 51 under tension and may be maintained in tension while the tungsten is deposited from the halide. After the deposit is completed, the tension may be relaxed. A body formed in this way is prestressed and its strength is increased.

The embodiment of the invention shown in FIG. 110 includes a perforated mandrel 71 on which a mesh 73 of fine, cold-drawn, tungsten wire is deposited. A tungsten halide and pure hydrogen are conducted through the holes 75 in the mandrel. The mass is maintained at a temperature which can range from 480 to 900 F. Reduced tungsten deposits 77 are produced in the body wound on the mandrel. The deposits start at the junctions of the wires and spread out from these junctions. The quantity deposited depends on the density of the gas flow and the duration of the reducing process. Usually the deposited material is so small a proportion of the body volume as not to affect the strength. The desirable tensile properties of the wire is not affected by heating to 900 F during the time required for cementation. The mesh may be pretensioned in different directions during the winding and the cementing to produce a prestressed structure.

In accordance with a further aspect of this invention a green body consisting of some one or more flat layers of mesh or filaments or wires, prestressed, may be cemented by deposition as disclosed to produce a plate.

While as a rule uniform deposition from the halide is desirable, situations may arise where the cementing substance should be concentrated in one part or another of the green mass to achieve variable porosity or other properties. Variable deposition is achieved by localizing the flow of the halide, varying its concentration or varying the temperature of the green mass.

While preferred embodiments have been disclosed herein, many modifications thereof are feasible. This invention then is not to be restricted except insofar as is necessitated by the spirit of the prior art.

I claim:

1. The method of producing a body of predetermined substantially uniform communicative porosity throughout, which comprises compacting more than one selected size fractions of generally spherical particles, assembled one size fraction at a time, to produce a porous mass having a porosity greater than said predetermined porosity, so that the distribution of the particles is relatively unifonn and the particles of smaller size fractions are effectively nested throughout in the volumes defined between the particles of larger size fractions, the particles being selected from one or more materials of the class of materials consisting of tungsten, rhenium, niobium, tantalum, silicon, zirconium, titanium, vanadium, hafnium, chromium and molybdenum, and reacting in the pores of said mass one or more of the halides of said one or more materials with hydrogen to deposit said one or more materials in the pores of said mass to cement said mass into a rigid body, the quantity of said one or more materials deposited being such that said body has said predetermined substantially uniform porosity.

2. The method of forming a porous body resistant to high temperatures typically exceeding 6,000F which comprises compacting more than one selected size fractions of generally spherical particles of tungsten, assembled one size fraction at a time, to produce a porous mass, each of said size fractions being mechanically treated so that the distribution of particles is relatively uniform and mixtures of different size fractions being mechanically treated so that the smaller size fractions nest throughout in the voids of the larger fractions whereby a porous mass of substantially uniform porosity is produced, and thereafter reacting within the pores of said mass at a temperature which does not significantly alter the mechanical properties of said mass, one or more of the class of compounds consisting of tungsten hexafluoride and tungsten hexachloride with hydrogen to deposit tungsten from said compounds in the pores of said mass to cement said mass into a rigid hightemperature resisting body, the said reacting taking place at a rate and temperature as to assure uniformity of penetration and deposit and fine-grain structure of the deposited tungsten.

3. The method of forming a body of substantially uniform communicating porosity throughout and of predetermined density comprising compacting into a mass of a density smaller than said predetermined density, more than one selected size fractions of a powder of one or more materials of the class of materials consisting of tungsten, niobium, tantalum, zirconium, titanium, vanadium, silicon, rhenium, hafnium, chromium, and molybdenum, the particles of said powder having substantially spherical form, the particles being assembled one size fraction at a time and each of said size fractions being mechanically treated so that the distribution of particles is relatively uniform and mixtures of different size fractions being mechanically treated so that the smaller particles nest throughout in the voids of the larger fractions, whereby a porous mass of substantially uniform porosity is produced, said size fractions being selected so that said mass has said smaller density; and reacting within the pores of said mass one or more of the halides of said one or more materials with hydrogen or the like to deposit, without significant alteration in the geometry and uniformity of the pores, said one or more materials in said mass to cement said mass into a rigid body, the amount of said material deposited being such that said body has said predetermined density.

4. The method of claim 1 wherein the deposited material is the same as the material of the mass.

5. A method for the manufacture of an element of construction resisting thermal shocks and mechanical stresses, e.g. a rocket nozzle or nose by depositing of a binding metal from the gas phase in the interior of a preformed skeleton-like body, characterized in this that a green body is produced by compacting of generally spherical particles of more than one size fractions of a high temperature resisting and mechanically resisting material, e.g. tungsten, to a porous body of corresonding dimensions in such a way that a contiguous, homogeneous pores-space of substantially uniform porosity throughout is formed, the said size fractions being assembled one size fraction at a time, so that the particles of smaller size fractions are effectively nested throughout in the volumes defined between the particles of larger size fractions, and further characterized in this that a gaseous compound of the binding metaL' e.g., tungsten halide, with a reducing agent, e.g., hydrogen, is brought to reaction within the pores of the formed body in such manner that, without significant alteration of the geometry and uniformity of the pores, the binding metal is deposited in the pores and will cement the particles together.

6. The method of claim 5 wherein the material of the green body is a metal which is the same as the binding metal.

7. The method of claim 1 wherein the tungsten halides and the hydrogen are substantially pure, the hydrogen having been obtained by diffusion through a silver palladium membrane or the like.

8. The method of claim 5 wherein the porous mass is formed of at least two size fractions of the particles of generally spherical form, the smaller particles having a diameter of 1/10 to US of the diameter of the larger particles.

9. The method of claim 8 wherein each size fraction is mechanically treated so that the distribution of the size fractions is relatively uniform, and after being so treated one size fraction is then compacted by relatively small pressure and thereafter the other size fraction is added and the particles of the smaller size fraction are caused to nest in the voids of the larger size fraction substantially uniformly by mechanical treatment of the mixture of size fractions and the mixture is compacted by small pressure and thereafter the halides and hydrogen are reacted in the pores of the mixture. t

Claims

2. The method of forming a porous body resistant to high temperatures typically exceeding 6,000*F which comprises compacting more than one selected size fractions of generally spherical particles of tungsten, assembled one size fraction at a time, to produce a porous mass, each of said size fractions being mechanically treated so that the distribution of particles is relatively uniform and mixtures of different size fractions being mechanically treated so that the smaller size fractions nest throughout in the voids of the larger fractions whereby a porous mass of substantially uniform porosity is produced, and thereafter reacting within the pores of said mass at a temperature which does not significantly alter the mechanical properties of said mass, one or more of the class of compounds consisting of tungsten hexafluoride and tungsten hexachloride with hydrogen to deposit tungsten from said compounds in the pores of said mass to cement said mass into a rigid high-temperature resisting body, the said reacting taking place at a rate and temperature as to assure uniformity of penetration and deposit and fine-grain structure of the deposited tungsten.
3. The method of forming a body of substantially uniform communicating porosity throughout and of predetermined density comprising compacting into a mass of a density smaller than said predetermined density, more than one selected size fractions of a powder of one or more materials of the class of materials consisting of tungsten, niobium, tantalum, zirconium, titanium, vanadium, silicon, rhenium, hafnium, chromium, and molybdenum, the particles of said powder having substantially spherical form, the particles being assembled one size fraction at a time and each of said size fractions being mechanically treated so that the distribution of particles is relatively uniform and mixtures of different size fractions being mechanically treated so that the smaller particles nest throughout in the voids of the larger fractions, whereby a porous mass of substantially uniform porosity is produced, said size fractions being selected so that said mass has said smaller density; and reacting within the pores of said mass one or more of the halides of said one or more materials with hydrogen or the like to deposit, without significant alteration in the geometry and uniformity of the pores, said one or more materials in said mass to cement said mass into a rigid body, the amount of said material deposited being such that said body has said predetermined density.
4. The method of claim 1 wherein the deposited material is the same as the material of the mass.
5. A method for the manufacture of an element of construction resisting thermal shocks and mechanical stresses, e.g. a rocket nozzle or nose by depositing of a binding metal from the gas phase in the interior of a preformed skeleton-like body, characterized in this that a green body is produced by compacting of generally spherical particles of more than one size fractions of a high temperature resisting and mechanically resisting material, e.g. tungsten, to a porous body of corresonding dimensions in such a way that a contiguous, homogeneous pores-space of substantially uniform porosity throughout is formed, the said size fractions being assembled one size fraction at a time, so that the particles of smaller size fractions are effectively nested throughout in the volumes defined between the particles of larger size fractions, and further characterized in this that a gaseous compound of the binding metal, e.g., tungsten halide, with a reducing agent, e.g., hydrogen, is brought to reaction within the pores of the formed body in such manner that, without significant alteration of the geometry and uniformity of the pores, the binding metal is deposited in the pores and will cement the particles together.
6. The method of claim 5 wherein the material of the green body is a metal which is the same as the binding metal.
7. The method of claim 1 wherein the tungsten halides and the hydrogen are substantially pure, the hydrogen having been obtained by diffusion through a silver palladium membrane or the like.
8. The method of claim 5 wherein the porous mass is formed of at least two size fractions of the particles of generally spherical form, the smaller particles having a diameter of 1/10 to 1/5 of the diameter of the larger particles.
9. The method of claim 8 wherein each size fraction is mechanically treated so that the distribution of the size fractions is relatively uniform, and after being so treated one size fraction is then compacted by relatively small pressure and thereafter the other size fraction is added and the particles of the smaller size fraction are caused to nest in the voids of the larger size fraction substantially uniformly by mechanical treatment of the mixture of size fractions and the mixture is compacted by small pressure and thereafter the halides and hydrogen are reacted in the pores of the mixture.