CA1176028A - Method and an apparatus for manufacturing metallic composite material bars by unidirectional solidification - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Disclosed are method and apparatus us for manufacturing bars made of an alloy by unidirectional solidification.
The mold is moved relative to a hot source and a cold source disposed below the hot source, the relative positions of the two sources as well as their efficiency and the displacement speed of the mold being set so that is establis-hed within the alloy contained in the mold a planar solidi-fication front with a high thermal gradient at the level of said front, and so that there is produced an orientation of the structure of the alloy which is perpendicular to the solidification front, and, during the whole duration of the solidification, the mold is fed with alloy powder having the required nominal composition at the rate corresponding to the quantity of alloy solidified by unit of time.

Description

:~L'7~i0~8 - 1 - 694 P/10 CA ~DIV) A method and an apparatus for manufacturing metallic composite material bars by unidirectional solidification The invention relates to a method for manufacturing metallic`composite material bars by unidirectional solidifi-cation, and also to an apparatus ~or practicing the method.
It applies to the manufacture by directed solidifi-cation of bars of composite materials re;nforced with fibresor flakes formed during the alloy solidification. The expression "bars" should be here intended in its general meaning, viz. that they are pieces of cylindrical elongated shape the section of which, which is constant, can be lO circular, polygonal or complex and from which are machined the desired articles.
The invention applies in particular to the manufac-ture of bars from the refractory composite materials proposed by Applicant in ~dian Patent No. 928,532 issued June 19, 1973;
15 C~d~ Patent No. 1,052,597 issue~ April 17, 1979 and C~dian Patent Application S.N. 339,708 file~ November 13, 1979 and which c-omprise a complex matrix made of a nickel- and/or iron-, and/or cobalt- based superalloy containing chromium as well as eventually other elements such as tungsten and aluminum and 20 in which is present a reinforcement phase made of mono-crystalline fibres of at least one transition metal mono-carbide. Due to their very good mechanical properties, such materials are particularly suitable as constituent materials for parts subject in operation to high stresses at high temperatures, such as the blades of aircraft turbines.
Such parts are manufactured either from rough casts or in~ots in which is machined the required part, for instance a turbine blade, or directly by casting, the alloy being solidified in a mold having substantially the shape of the required part. In the processes used hitherto, the alloy wh'ich has to be subjected to the unidirectional solidification is previously introduced in one time only in the mold, either by casting or else in the form of a pre-10 alloyed powder, viz. a powder the grains of which are sub-stantially identical and have the nominal composition of the alloy. The mold is then shifted relative to a hot source and a cold source superimposed, the distance between the hot source and the cold source as well as the efficiency 1' 15 of the hot source on the one hand, and the displacement speed of the mold on the other hand, being set so that within the alloy contained in the mold is formed a rigorous-ly planar solidification front with a high thermal gradient at the level of said front, and so as to thereby obtain 20 grains and reinforcement flakes or fibres perpendicular to the solidification front. For materials with monocrystalline fibres of monocarbides like those provided by Applicant, the thermal gradient which is established is of the order of 120 to 200C/cm at the solidification front and the mold 25 is moved at speeds of the order of 1 cm/h.
Hitherto, it has never been possible to manufacture parts of a great length exhibiting over their whole length constant mechanical properties. In fact, and due to the great height of the liquid portion contained in the mold, 30 there appears a segregation phenomenon connected to the convection movements of the liquid, which phenomenon is well known of metal!founders. At the level of the solide-liquid interface, the constituent elements of the alloy are une-qually distributed between the solid phase and the liquid 35 phase, in accordance to their respective coefficients of parting. Thus, for instance, the chromium is incorporated to the solid in formation in a smaller proportion than its proportion in the liquid phase, the latter having therefore ~7~(~;28 3 _ a tendency of becoming richer in chromium in the vicinity of the solidification front; on the contrary, the tungsten is preferentially incorporated to the solid in formation in a higher proportion than its proportion in the liquid phase, the lat-ter growing poorer in tungsten. The result is that, when one wishes to manufacture a large size part and when the mold contains in consequence, at the beginning of the solidification process, a liquid portion of great height, the solidified material which is obtained as the solidifica-10 tion progresses unavoidably exhibits composition variationsbetween the portion which was solidified in the first place and the portion which was solidified in the last place. As regards the particular elements which are considered here by way of example, the latter portion exhibits a chromium 15 content and a tungsten content which are, respectively, substantially higher and lower than the contents present in the portion which was first solidified. The result is that the metallurgical structure is not constant from one end to the other of the manufactured material, the volume fraction 20 of the reinforcement fibres within the matrix, considered in the cross!sections of the material, altering from one end lo the other due to the concentration evolution of the consti-tuent elements of the fibres with, as a consequence, a varia-tion of the mechanical properties of the solidified part.
It is an object of the invention to provide a method for manufacturing alloy parts by unidirectional solidifica-tion, which allows preventing the advent of the segregation phenomenon or at least which strongly limits its effects.
A further object of the invention is to provide a 30 method for manufacturing bars of any length by unidirectional solidification of an alloy, said bars exhibiting nevertheless good mechanical properties remaining constant over all their length.
The method of the invention, according to which the 35 mold is displaced in a downward movement relative to a hot source and a cold source superimposed, the relative position of the two sources as well as their efficiency being set so that a rigorously planar solidification front is established ~1760~

within the alloy as well as a high thermal gradient at the level of said front, whereby the starting alloy is in the form of an alloy powder of the required nominal composition, is characterized in that the mold is permanently supplied 5 with alloy powder at a given flow rate chosen in order to maintain a quantity of liquid alloy substantially constant during the whole solidification process.
Such a method allows maintaining at substantially constant values the concentrations of the various constituents 10 of the alloy at the level of the solidification front, the uneven distribution of the constituents between the solid phase and the liquid phase at the level of the solid-liquid interface being compensated at every moment by the addition of alloy at the nominal composition as the solidification 15 front progresses. Thereby is o~t:ained a part which exhibits, in all its cross-sections, whatever its length, a metallic composition as weel as a metallurgical structure substantially constant.
Generally, according to the method of the invention, 20 there is maintained therefore in the mold a liquid alloy phase exhibiting a composition substantially constant during the whole solidification period.
The mold shape and the solidification speed allow establishing the flow rate of the all~ which is to be intro-? 5 duced in the mold.
An apparatus for carrying out the method of the inven-tion comprises means for introducing the alloy powder in the mold, as the solidification progresses, at a constant flow rate corresponding to the quantity of alloy solidified by 30 unit of time.
Advantageously, said means comprises a distribution device for the alloy powder having the required nominal compo-sition.
Further characteristics and advantages of the inven-35 tion will become more apparent from the following descriptionwhich is given by way of example, reference being made to the accompanying drawing wherein :

1~7~

Figure 1 is a schematic view in lonyitudinal section of a portion of an apparatus according to the invention;
Figure 2 is a cross-sectional view along line 2-2 of Figure l;
Figure 3 is a sectional schematic view of a feed device for the powder to the apparatus of the invention;
Figure 4 is a sectional view along line 4-4 of Figure 3; and Figure 5 is a diagram of the composition of a bar made of a composite super-alloy obtained by the method of the invention.
For the manufacture by casting of alloy parts of any length, with an oriented structure, particularly of the type comprising a complex matrix made of a nickel and/or cobalt-and/or iron-based super-alloy containing chromium as well as other elements such as tungsten and aluminum, and monocrys-talline reinforcement fibres made out in situ in monocarbides of transition metals, one uses a unidirectional solidifica-tiOIl process of a starting alloy in a mold surrounded by a hot source and a cold source placed under the hot source, by displacing the mold relative to the two sources at a constant and appropriate speed, the relative positions of said sources and their efficiency being set so as to establish within the alloy a planar so:Lidification front and a high thermal grade ?5 at said front, and by feeding continuously the mold with alloy powder in a quantity which is function of the solidification progress-.
Figure 1 shows a part of the apparatus according to the invention, viz. the solidification oven as such.
Said oven comprises an upper chamber 10 and a lower chamber 11, the lower end of the wall 12 of the upper chamber 10 being inserted into a plate or frame 13 which is rigid with the lower chamber 11, the latter having two walls between which flows the cooling water. The wall 12 is mounted around a cooling block 14 which is also solid with frame 13, said cooling block being formed by a copper sleeve thro~gh which extend water flow passages, the water arriving through a tubing 15 and being discharged through a tubing 16.

~'7~

The wall 12 of the ~pper chamber 10 is internally coated, above the cooling block 14, with a thermal insulation lining, for example made of a graphite felt, for reducing the lateral thermal losses and comprising a first sleeve 17 5 of smaller diameter than that of the wall 12 and placed on the cooling block 14, a second sleeve 172 spaced apart from sleeve 171 by a graphite sleeve 32 and a sheath 173 surrounding sleeves 171 and 172. The graphite felt lining 17, the sleeve 32 and the cooling block 14 are formed with a bore having a 10 s ze adapted for movement of a mold 19 with a minimum clea-rance.
A piston 20 is slidably mounted longitudinally in the lower chamber 11, with interposition of a sealing joint 23, 24, the mold 19, which is open at its two ends, being fixed 15 by being fitted by its lower end onto the core 21 of a support 22 formed on the upper frontal face of piston 20.
The upper portio~ of wall 12 of the upper chamber 10 is covered by a cap 25 fixed on a flange 26 and having a side wall 27, a bottom 28 and a cover 29 having at its center a 20 tubular coupling 30 provided for communicating with an al.loy feed device for the mold which will be described hereinbelow with reference to Figure 3.
An inductor 31 surrounding wall 12 of the upper chamber forms the hot source of the apparatus, the graphite sleeve 32 25 interposed between the sleeves 171 and 172 f the insulating lining 17 having the function of a resistor.
The mold 19 is formed by a thin walled tube, of thick-ness from 0.5 to 1.5 mm, made of a refractory oxide such as a very high purity alumina (over 99.5%) very slightly porous 30 (less than 10%) and manufactured for example by spraying with an oxy-acethylene torch or a plasma gun a model of the bar to be solidified. A mold thus formed resists chemically to high carbon content materials of those of Applicant when they are in the li~uid state and offers a low thermal resistance which 35 does not prevent the obtention of a high thermal gradient (of the order of 120 to 200DC/cm). Since such a mold does not have a sufficient mechanical strength for being used without pre-vious.cooking, it runs the risk of being deformed by creeping 0~8 at a high temperature. It is foreseen to surround the mold with banding elements 33 (see Figure 2), which may be made as graphite rings stuck onto each other around the mold, or by a sleeve made of a carbon-carbon composite material.
A powder distribution device 34 (Figure 3), connected to the solidification oven through the junction 30, comprises a casing 34 with a bottotn 35 on which is fixed a support bracket 36 for a powder tank 37 provided with an interchan-geable nozzle 38 discharging the powder, an opening 39 for feeding the powder tank 37 being provided in the cover 40 of casing 34. The cover 40 carries a driving motor 41 of adjus-table speed driving a vertical axis 42 housed inside casing 34 and carrying at its other end a rotating horizontal plate 43.
lS In operation of the distributor, a calibrated bead or ribbon of pre-alloyed powder 44 flows through the nozzle 3~3 of the powder tank 37 orito the plate 43, powde~ ,~7nich, while the plaLe ~3 roia,es (Figure 4), is forwaxded by a i)l3 :32 ~5 carried by an arm fixedly mounted onto a pin 47 into the 20 introduction opening of a funnel 48 the discharge channel 49 of which is mounted in the bore of the tubular connection 30 and emerges inside the mold 19. The flow of powder is regula-ted by choosing the diameter of the nozzle 38 and by setting the rotation speed of plate 43.
.25 ~ The inner free volume of the oven can be degased and placed in a reducing atmosphere, for example argon containing 5% of hydrogen, introduced by an input channel 51 extending across the powder distributor cover 34, and discharged by a channel 51' arranged at the lower portion of the lower chamber 30 11 of the oven. With the same aim of "capturing" the oxygen of the oven atmosphere, it is foreseen to place in the thermal insulation lining 17 of the oven upper chamher 10 a crucible 52 filled with a deoxidizing agent, such as Ti-Zr chips (50/50), said crucible being in a location such that when the oven is 35 set in operation, the temperature to which it is exposed is that corresponding to the deoxidizing activity of the material it contains.
An apparatus according to the invention is operated as follows :
On the core 21 of support 22 made of a refractory steel, the cross-section of which is identical to the inner cross-section of the mold 19, -Laking into account the dilatation clearances-, one places a block of alloy, or bar-foot 53, of same composition as the powder and also of same cross-section as the inside of the mold-taking into account the dilatation clearances. The mold 19 is then inserted onto the block 53 and then on the core 21 and after the banding elements 33 are placed around the mold. The piston 20 carrying the mold is moved by means of a rack 61 and a gear 62 coupled with a motor 63, so that the upper face of the bar-foot 53 is at the level of the upper portion of the resistor 32. The chamber is then closed, degased, filled with an argon and hydrogen mixture at a slight over-pressure, the resistor 32 being then progressively raisedto its operational temperature by high frequency induction, provided by the inductor 31 fed by a source 64. The distance between the resistor 32 and the cooling block 14, as well as the heating conditions, are set so that the isotherm corres-ponding to the melting point of the alloy to be solidifiedis placed in the unidirectional and vertical thermal flux zone, that is in the zone where the heat exchanges through the side wall of the apparatus are non-existent due to the presence of the insulating lining 17, and more precisely so that the solid-liquid interface is at a few millimcters below the lower level of resistor 32, the position of the solidification front being indica-ted by a thermocouple 55 the sensing joint 56 of which is positioned immediately above the solidification front level, in the liquid portion of the alloy. The thermocouple 52 is connected to a tempera-ture monitor 65 which adjusts the energy feeding the inductor 31 in order to maintain constant the temperature in the area of the sensin~ joint 56 of the thermocouple 55.
The powder feed channel 49 is placed in the mold with its outlet opening 57 positioned at a distance from the free surface of the liquid alloy contained in the mold such that, on the one hand, the temperature of the area in which V~8 g is placed said outlet opening 57 is not sufficient for the powder grains to melt therein, and, on the other hand, the latter are spread finely shower-wise and are distributed - on all the surface of the liquid alloy.
The mold is then fed with powder by driving in rotation the rotating plate 43, and the mold is simultane-ously moved downwards. The powder feed rate is set so that the upper level of the liquid alloy remains in the same position relative to the fixed elements of the solidifica-tion oven, or in other words so that the volume of the liquid a~loy contained by the mold remains constant.
Taking into account the sclidification speed and the size of the mold, one calculates the quantity of soli-dified alloy by unit of time and one sets accordingly the powder feed rate of the mold by a suitable choice of the size of the nozzle 38, by setting the position of its opening relative to the plate ~3 and the rotation speed of said plate.
After a duration of a few minutes of displacement of the mold, one reaches stationary thermal conditions as well as stationary diffusion conditions of the elements of the alloy from the solid phase to the liguid phase. The small volume of the liquid phase and the constant feed in the liquid portion of constant volume of powder having the !?5 nominal composition of the alloy to be solidified allow maintaining a constant average composition in the liquid in spite of the fact that the distribution of the elements is different in the liquid phase and in the solid phase at the solidification front and in spite of the stirring of the liquid due to convection. The solidified alloy according to the invention thus exhibits much more reduced segregations than an alloy of same nominal composition which would have been solidified by any other known method which does not comprise the metered alloy feed to the mold as the solidifi-35 cation progresses and in which all the alloy mass would beinitially in the liquid s-tate.
The movement of the mold, the powder feed and the heating are interrupted when the surface of the liquid bath reaches the upper end of the mold. The length of the latter and the space available for its displacement are therefore the only limits to the length of the part obtained by uni-directional solidification.

A bar in a nickel-based super-alloy of the following composition (by weight) : base Ni - 10~ Cr - 10% W - 20~ Co -4~ Al - 4.~% Nb - 0;55~ C, is manufactured by using the method of the invention in a mold having a cross-section shown in Figure 2, viz. a cross-section in the shape of a parallelogram of 22 mm x 35 mm with rounded angles of 75.
The mold is placed in the oven and fed with the alloy so that the height of the melted zone, at the maximum operating temperature, viz. 1600~CI is of the order of 50 mm.
The thermal gradient established is of the order of 140C/cm and the solidification speed, in other wDrds, the displace-ment speed of the mold, is of 1.2 cm/h.
Figure 5 shows the representative curves of the content of the bar for each of the elements others than that forming the base, namely the nickel, by plotting in abscissas the solidified length in mm and in ordinate the content in %
by weight of each of the elements. E`rom said curves, it is clear that if one suppresses at the beginning of the bar a length portion equivalent to the height of the liquid zone, viz. about 50 mm, the variation of the contents of the bar obtained in each of the elements is less than 5~ (as a relative value) along the length the bar, and is less than 2 ~as a relative value) if one leaves out the chromium element.
The oriented fibrous structure, which i5 formed by the matrix reinforced by the nicbium monocarbide fibres, is perfect along its whole length and no evolution of the volume frac-tion of the niobium monocarbide fibres is noticeable.
The representative curves of the element concentra-tion as a function of the solidified length all tend towards an asymptote the ordinate of which represents the content of the corresponding alement in the parent alloy. This fact confirms that one can obtain bars of solidified alloy of any length exhibiting no segregation over their length as regards ;~76U~8 -- 11 ~

their metallic composition and their metallurgical struc-ture, and this, while always putting aside the first portion of the solidified zone, that is that corresponding to the height of the liquid ~one.

One solidifies under the same conditions as those of Example 1 a bar made of an alloy of following composition by weight : base Ni - 10% Co - 4% Cr - 10~ W - 16~ Al -4.2~ Nb - 0.46~ C - 2% Mo.
The variations of the contents in each of the elements, including the addition elements, of the bar obtained after solidification are similar to those of Example 1. The fibrous structure of the composite material is without defect through the whole solidified length and no evolution of the volume fraction of the fibres is noticed.

Bars made of an alloy as in Example 1 on the one hand, and of an alloy as in Example 2 on the other hand, of rectangular cross-section of 12 mm x 65 mm, with rounded ends, are obtained by unidirectional solidification under the same conditions as those of Examples 1 and 2.
The contents variations of the addition elements in the bars obtained are similar to those of Examples 1 and 2.
The structure of the obtained composite is also perfectly fibrous, with a constant volume fraction over the whole solidified portion.
COMPARISON EXAMPLE
As a comparison, a bar has been prepared by uni-directional solidification with the same alloy as that indicated in Exarnple 1, having the same cross-section as in said Example and a total length of 250 mm corresponding to a length which can be obtained by using the prior art methods.
A bar has been prepared by unidirectional solidifi-cation according to a usual method without continuous feed ~method A), the total length of the initially melted portion being equal to 250 mm.
On the other hand, a bar of same length has been prepared by unidirectional solidification, but with the ~L~7~

method with continuous feed of a pre-alloyed powder according to the invention (method B), the height of the melted zone being of 50 mm.
In one and the other method, the thermal gradient established was of 140~C/cm, and the solidification speed of 1.2 cm/h.
Cross-sectional cuts have been effected on the bars obtained, and the proportion in weight of some of the elements in each of said cuts has been established.
The results of these tests are shown in the following Table.
TABLE
Comparison of the compositions of alloy bars obtained by unidirectional solidif~cation~ of same total length A- by a standard method without continuous feed (total length of the initially melted portion : 250 mm) B- by the method with continuous feed of a pre-alloyed powder (height of the melted zone : 50 mm~
. _ Distance from the Cr % W % C %
beginning of the solidification A s A s A s (mm) 8,89,1 11,8 9,51 0,61 0,55 _ 9,01 9,54 11,65 9,38 0,57 0,53 100 9,45 1 9,83 1],4 9,50 0,54 0,53 155 10,49,95 10,8 9,38 0,535 0,53 200 10,89,99 10,5 9,40 0,525 0,53 relative compo-sition difference 18% 4,5% 11% 1% 10% 0%
50 and 200 mm (*) (X) .
~ Except for the titration precision

Claims (6)

- 13 - 694 P/10 CA (DIV) THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. An alloy bar with oriented structure comprising a complex matrix made of nickel- and/or iron-, and/or cobalt-based superalloy containing chromium and optionally tungsten and aluminum, and in which is present a reinforcement phase made of monocrystalline fibers of at least one transition metal monocarbide wherein said bar exhibits a constant metallurgical structure in all cross sections thereof throughout its length.

2. An alloy bar according to Claim 1 made from an alloy of following composition (in weight):
base Ni Cr 10%
W 10%
Co 20%
Al 4%
Nb 4.9%
C 0.55%

3. An alloy bar according to Claim 1 made from an alloy of following composition (in weight):
base Ni Co 10%
Cr 4%
W 10%
Al 16%
Nb 4.2%
C 0.46%
Mo 2%

- 14 - 694 P/10 CA (DIV)

4. An alloy bar with oriented structure comprising a complex matrix made of nickel- and/or iron-, and/or cobalt-based superalloy containing chromium and optionally tungsten and aluminum, and in which is present a reinforcement phase made of monocrystalline fibers of at least one transition metal monocarbide wherein said bar exhibits, in all its cross sections, whatever its length, a constant metallic composition as well as a constant metallurgical structure, and thus constant mechanical properties.

5. An alloy bar according to Claim 4 made from an alloy of following composition (in weight):
base Ni Cr 10%
W 10%
Co 20%
Al 4%
Nb 4.9%
C 0.55%

6. An alloy bar according to Claim 4 made from an alloy of following composition (in weight):
base Ni Co 10%
Cr 4%
W 10%
Al 16%
Nb 4.2%
C 0.46%
Mo 2%