EQUIAXED FINE GRAIN QUENCH SURFACE

Abstract: A quench surface rapidly solidifies molten alloy into strip having a microcrystalline or amorphous structure. The surface is composed of a thermally conducting alloy having a homogeneous microstructure consisting of fine equiaxed recrystallized grains. The grains exhibit a tight Gaussian grain size distribution. The average size of said grains being less than 200 mum and none of said grains being larger than 500 mum.

Description: EQUIAXED FINE GRAIN QUENCH SURFACE BACKGROUND OF THE INVENTION 1. Field Of The Invention This invention relates to manufacture of πbbon or wire by rapid quenching of a molten alloy, and more particularly, to characteristics of the surface used to obtain the rapid quench A quench surface having a fine, equiaxed, recrystallized microstructure, exhibiting a tight Gaussian grain size distribution has surprisingly been found to improve the quality of the surface finish of the rapidly solidified strip 2. Description Of The Prior Art Continuous casting of alloy strip is accomplished by depositing molten alloy onto a rotating casting wheel Strip forms as the molten alloy stream is attenuated and solidified by the wheel's moving quench surface For continuous casting, this quench surface must withstand mechanical damage which may arise from cyclical stressing due to thermal cycling duπng casting Means by which improved performance of the quench surface can be achieved include the use of alloys having high thermal conductivity and high mechanical strength Examples include copper alloys of vaπous kinds, steels and the like Alternatively, vaπous surfaces can be plated onto the casting wheel quench surface to improve its performance, as disclosed in European Patent No EP0024506 A suitable casting procedure is set forth in detail in U S Patent 4,142,571, the disclosure of which is incorporated herein by reference Casting wheel quench surfaces of the pπor art generally involve one of two forms monolithic or component Monolithic quench surfaces compπse a solid block of alloy fashioned into the form of a casting wheel that is optionally provided with cooling channels Component quench surfaces compπse a plurality of pieces that, when assembled, constitute a casting wheel, as disclosed in U S Patent No 4,537,239 The casting wheel quench surface improvements of the present disclosure are applicable to all kinds of casting wheels When selecting mateπals for construction of a casting wheel quench surface, certain mechanical properties such as hardness, tensile and yield strength, and elongation have generally been considered, sometimes in combination with thermal conductivity This was done in an effort to achieve the best combination of thermal conductivity and mechanical strength properties possible for a given alloy The reason for this is basically twofold I ) to provide a high quench in the cast, 2) to resist mechanical damage of the quench surface which causes degradation of the stπp's geometric definition Dynamic or cyclical mechanical properties must also be considered in order to develop a quench surface which has supeπor performance characteπstics One consequence of a poor selection of the mateπal is rapid deteπoration of the casting wheel surface due to the formation of pits Pits are small defects that are usually observed when they larger than about 0.1 mm deep, they grow in depth and diameter as casting proceeds These surface irregulanties result in corresponding defects, "pips", in the cast πbbon These pips not only affect the surface finish of the πbbon, but can also reduce the πbbon's usefulness in such applications as transformer cores, antitheft systems and brazed articles The importance of these surface defects to the value of the rapidly quenched πbbon and the customer's satisfaction is evident The surface defects limit the life of the casting wheel quench surface and reduces the surface quality of πbbon cast thereon This, in turn, reduces the usefulness of such πbbon to the customer, whose designs must account for properties associated with the worst surface quality of the πbbon he might receive Even when a good selection of mechanical and thermal properties is made, as is the case with the Cu Cr and Cu Be type alloys, the deteπoration of a casting wheel's quench surface finish progresses rapidly There exists a need in the art for a quench surface that resists rapid deteπoration and produces, for a prolonged peπod of time, πbbon having a surface which is defect free SUMMARY OF THE INVENTION The present invention provides an apparatus for continuous casting of alloy stπp Generally stated, the apparatus has a casting wheel compπsmg a rapidly moving quench surface that cools a molten alloy layer deposited thereon for rapid solidification into a continuous alloy stπp The quench surface is composed of a thermally conducting alloy having a fine, equiaxed, recrystallized microstructure, exhibiting a tight Gaussian grain size distπbution The casting wheel of the present invention optionally has a cooling means for maintaining said quench surface at a substantially constant temperature throughout the time that molten alloy is deposited and quenched thereon A nozzle is mounted in spaced relationship to the quench surface for expelling molten alloy therefrom The molten alloy is directed by the nozzle to a region of the quench surface, whereon it is deposited A reservoir in communication with the nozzle holds a supply of molten alloy and feeds it to the nozzle Preferably, the quench surface is compπsed of fine equiaxed recrystallized grains exhibiting a tight Gaussian grain size distπbution and an average grain size less than 80 μm Use of a quench surface having these qualities significantly increases the service life of the quench surface Run times for casts conducted on the quench surface are significantly lengthened, and the quantity of mateπal cast duπng each run is increased by a factor as high as three or more Ribbon cast on the quench surfaces exhibits far fewer surface defects, and hence, an increased pack factor (% lamination), and the efficiencies of electπcal power distπbution transformers made from such πbbon are improved Run response of the quench surface duπng casting is remarkably consistent from one cast to another, with the result that the run times of substantially the same duration are repeatable and scheduling of maintenance is facilitated Advantageously, yields of πbbon rapidly solidified on such surfaces are markedly improved, maintenance of the surfaces is minimized, and the reliability of the process is increased BRIEF DESCRIPTION OF THE DRAWINGS The invention will be more fully understood and further advantages will become apparent when reference is made to the following detailed descπption and the accompanying drawings, in which Fig 1 is a perspective view of an apparatus for continuous casting of metallic stπp, Fig 2 illustrates the effect of the bimodal grain size distπbution (quantified by the % area of large grains) on the life of hot forged casting wheels having conventional quench surfaces, Fig 3 is the grain size distπbution of "good" and "bad" hot forged wheels, showing the bimodal grain size distπbution, Fig 4 illustrates how the degree of cold work effects the average grain size, Fig 5 is the grain size distπbution obtained by cold working the wheel as descπbed herein, Fig 6 is a micrograph of a cold forged wheel showing the recrystallized microstructure, the average grain size is less than 30μm The normalized πbbon quantity cast for this wheel was 2 9 Fig 7 is a micrograph of a hot forged wheel, the average grain size is less than 30μm The normalized πbbon quantity cast for this wheel was 1 7 Fig 8 is a micrograph of a cold forged and aged wheel, the average grain size is less than 30μm The normalized πbbon quantity cast for this wheel was 0 3 Fig 9 is a grain size distπbution obtained by extrusion, showing a tight Gaussian grain size distπbution, DETAILED DESCRIPTION OF THE INVENTION As used herein, the term "amorphous metallic alloys" means a metallic alloy that substantially lacks any long range order and is characteπzed by X-ray diffraction intensity maxima which are qualitatively similar to those observed for liquids or inorganic oxide glasses. The term microcrystalline alloy, as used herein, means an alloy that has a grain size less than 10 μm (0.0004 in ). Preferably such an alloy has a grain size ranging from about 100 nm (0.000004 in.) to 10 μm (0.0004 in ), and most preferably from about lμm (0.00004 in.) to 5 μm (0.0002 in ). Grain size as used herein is taken to have been determined by an image analyzer looking directly at an alloy sample that has been polished and correctly etched to reveal grain boundaries. The average grain size was determined using five different locations within the sample chosen at random. In all cases the magnification was reduced to that at which the largest grains in the sample fit completely within the field of view. If there were any uncertainties, the grain size was determined at different magnifications to ensure it did not change with magnification. As used herein, the term "strip" means a slender body, the transverse dimensions of which are much smaller than its length. Strip thus includes wire, πbbon, and sheet, all of regular or irregular cross-section. The term "rapid solidification", as used herein throughout the specification and claims, refers to cooling of a melt at a rate of at least about 10 4 to 10 6 °C/s. A variety of rapid solidification techniques are available for fabricating strip within the scope of the present invention such as, for example, spray depositing onto a chilled surface, jet casting, planar flow casting, etc. As used herein, the term "wheel" means a body having a substantially circular cross section having a width (in the axial direction) which is smaller than its diameter In contrast, a roller is generally understood to have a greater width than diameter. The term "thermally conducting", as used herein, means that the quench surface has a thermal conductivity value greater than 40 W/m K and less than about 400 W/m K, and more preferably greater than 60 W/m K and less than about 400 W/m K, and most preferably greater than 80 W/m K and less than 400 W/m K As used herein the term "normalized ribbon quantity cast" refers to the quantity/mass of ribbon that it was possible to cast on a particular wheel, normalized to a standard wheel. The term "solution heat treatment", as used herein, means heating the alloy to a temperature at which all the alloy additions are in solution. This often results in recystallization occurring once the alloy additions are in solution. The actual solution heat treatment temperature depends upon the alloy. Copper beryllium alloy 25 is usually solution treated within the range 745 to 810°C. After solution heat treatment, the alloy is rapidly cooled to maintain the alloy additions in solution. In this state, the alloy is soft and ductile and easily worked As used herein the term "aging" means the low temperature exposure used to precipitate alloy additions from the solution heat treated alloy. The precipitation of strengthening phases hardens the alloy. Aging times and temperature are optimized to obtain the maximum hardness and, hence, strength. The copper beryllium alloy 25 is usually aged at 260 to 370°C for 1/2 to 4 hours. Excessive aging time results in loss of hardness, strength and ductility. Because copper beryllium alloys are usually sold in the solution heat treated condition, aging of copper beryllium alloys is usually referred to simply as "heat treatment". The term "Gaussian ", as used herein, means a normal standard distribution around an average value. For certain cases close to zero in the examples the distribution is positively skewed, because the grains can not have negative values. Such cases in this work are still referred to for simplicity as a Gaussian distribution. As used herein the term "tight" means that there is very little variance around the Gaussian or normal distribution. The term narrow Gaussian distribution could also be used as opposed to a wide Gaussian distribution. In this specification and in the appended claims, the apparatus is described with reference to the section of a casting wheel which is located at the wheel's periphery and serves as a quench surface. It will be appreciated that the principles of the invention are applicable, as well, to quench surface configurations such as a belt, having shape and structure different from those of a wheel, or to casting wheel configurations in which the section that serves as a quench surface is located on the face of the wheel or another portion of the wheel other than the wheel's peπphery The present invention provides a quench surface for use in rapid solidification, a process for using the quench surface in the rapid solidification of metallic stπp, and a process for making the quench surface Referring to Fig 1, there is shown generally at 10, an apparatus for rapid solidification of metallic stπp Apparatus 10 has an annular casting wheel 1 rotatably mounted on its longitudinal axis, reservoir 2 for holding molten metal and induction heating coils 3 Reservoir 2 is in communication with slotted nozzle 4, which is mounted in proximity to the surface 5 of annular casting wheel 1 Reservoir 2 is further equipped with means (not shown) for pressuπzing the molten metal contained therein to effect expulsion thereof though nozzle 4 In operation, molten metal maintained under pressure m reservoir 2 is ejected through nozzle 4 onto the rapidly moving casting wheel surface 5, whereon it solidifies to form stπp 6 After solidification, stπp 6 separates from the casting wheel and is flung away therefrom to be collected by a winder or other suitable collection device (not shown) The mateπal of which the casting wheel quench surface 5 is compπsed may be copper or any other metal or alloy having relatively high thermal conductivity This requirement is particularly applicable if it is desired to make amorphous or metastable stπp Preferred mateπals of construction for surface 5 include precipitation hardened copper alloys, such as chromium copper or beryllium copper, dispersion hardened alloys, and oxygen-free copper If desired, the surface 5 may be highly polished or chrome-plated or the like to obtain stπp having smooth surface characteπstics To provide additional protection against erosion, corrosion or thermal fatigue, the surface of the casting wheel may be coated with a suitable resistant or high-melting mateπal Typically, a ceramic coating or a coating of corrosion-resistant, high-melting temperature metal is applicable, provided that the wettabi ty of the molten metal or alloy being cast on the chill surface is adequate The deposition of molten alloy onto the quench surface as the wheel rotates during casting results in a large radial thermal gradient near the surface and large thermal cyclic stresses These effects may combine to mechanically degrade the quench surface during casting We have discovered that the problems of mechanical degradation descπbed above can be minimized by the use of a quench surface compπsed of fine, equiaxed, recrystallized grains having a tight Gaussian gram size distπbution with substantially no gram larger than 500 μm Copper based alloys typically have a bimodal grain size distπbution In fact, copper alloys are the only alloys for which the Ameπcan Society of Testing & Measurement gram size standard, ASTM E 112, permits the average grain size to be specified by two sizes Of the two sizes specified, one size is for the fine grains and one size is for the large grams Typical values for these sizes would be 100 μm and 600 μm, respectively For copper alloys, a range m gram sizes of about 5 to 1000 μm is normal The large gram size, commonly occurring in copper alloys because of the bimodal gram size distπbution, is detπmental to the durability of the casting wheel A seπes of copper casting wheels fabπcated by hot forging were investigated in detail All had a typical bimodal distπbution typified by the ASTM gram size of 20 and 500 μm It was found possible to quantify the degree of bimodal distπbution and to take some account of the large gram size by using an image analyzer to determine the percentage of the casting wheel mateπal with a gram size above 250 μm As shown in Fig 2, the hot forged wheels with a high percentage of large grains had a small normalized πbbon quantity cast, while the ones with a small percentage had a much larger normalized πbbon quantity cast Fig 3 depicts the gram size distribution of "good" and "bad" wheels While each of the "good" and "bad" wheels have bimodal distπbutions, the wheel with the higher normalized quantity cast (1 4 compared to 0 04) has fewer large grains Clearly large grams and a bimodal grain size distπbution are deleteπous to quench surface performance in the continuous casting of metal or alloy stπp Under these circumstances, the specific manner in which quench surface degradation occurs is through the formation of very small cracks in the surface thereof Subsequently deposited molten metal or alloy then enters these small cracks, solidifies therein, and is pulled out, together with adjacent quench surface mateπal, as the cast stπp is separated from the quench surface during operation The degradation process is degenerative, growing progressively worse with time Cracked or pulled out spots on the quench surface are called "pits", while the associated replicated protrusions attached to the underside of the cast stπp are called "pips " It should be beneficial to reduce the bimodal distπbution, by reducing the area of large grams further However, it is difficult to obtain essentially a 100% fine gram size with conventional hot forgmg processes Conventional hot forgmg usually involves working the metal by discrete hammer blows mto an annular quench surface, to prepare it for subsequent heat treatment in order to develop high strength The limitation of this mechanical working method is largely its discrete, incremental nature That is, not all volume elements of the quench surface are equally worked and subsequent bimodal gram size distributions can occur, with the occurrence of large grams in a matrix of fine grams Alternate fabπcation routes were therefore explored These included forward and back extrusion, flow forming and hot and cold forgmg Several provided an homogenous fine grained microstructure While some of these improved wheel life, it was surpnsingly found that even with an extremely fine (<30 μm) gram size a very low normalized πbbon quantity cast could be obtamed Even with a fine uniform gram size, performance was found to depend on the microstructure within the gram Good, medium or very poor wheel life was obtamed even though the average gram size of each of the wheels was less than 30μm and no gram exceeded 250 μm Surpnsingly, the best results were obtamed with techniques that formed fine, equiaxed, recrystallized grains with a tight Gaussian gram size distπbution The benefits of such a microstructure are not limited to longer wheel life, but also mclude better equipment utilization and the production of πbbon havmg a supeπor surface finish In "die case of πbbon made from magnetic alloys, a better surface finish provides a higher packing factor, and a more efficient transformer The benefits associated with improved πbbon quality have been found to significantly increase once the πbbon is made effectively "pip" free The following examples are presented to provide a more complete understanding of die invention The specific techniques, conditions, mateπals, proportions and reported data set forth to illustrate the principles and practice of the invention are exemplary and should not be construed as limiting the scope of the invention EXAMPLE 1 An ingot of the copper beryllium alloy 25 was hot side forged at 700°C and pierced, after which it was hot forged and then cold forged to the final, desired casting wheel size Specifically, the billet was hot forged to an intermediate size and then subjected to a 30% cold reduction to the final wheel size Fig 4 shows the average gram size obtamed for samples given a standard hot forge and then cold forged to varying reductions pπor to a standard solution heat treatment The gram size obtamed remains constant for a large range of cold work and can be expected to only change slightly outside the immediate range investigated Fig 4 The 30% cold worked casting wheel was then given a standard solution heat treatment and aging pπor to machining to the exact wheel dimensions and tolerances The resultant Gaussian gram size distπbution is shown in Fig 5 These fine, equiaxed, recrystallized grams, shown in Fig 6, resulted m this wheel havmg an extremely long life The wheel descπbed by Figs 5 & 6 had a normalized πbbon quantity cast of 2 9, which is approximately twice the value of the "best" hot forged wheel descπbed m In most cases, the πbbon produced using this wheel had no pips As a result, its lammation factor was mcreased The desirability of this πbbon is, therefore, evident Additional casting wheels were fabπcated by the process descπbed above In all cases, the wheel microstructure was compπsed of fine, recrystallized, equiaxed grains exhibiting a tight Gaussian gram size distπbution These casting wheels all demonstrated supeπor castmg performance as measured by the normalized πbbon quantity cast This information is given in Table 1 Table 1 Rim Av. Grain Size* Microstructure Normalized ribbon Identiflcatio [microns) quantity cast 4-2 32 recrystallized, equiaxed, Gaussian 3 0 4-3 38 recrystallized, equiaxed, Gaussian 2 9 4-5 35 recrystallized, equiaxed, Gaussian 2 0 4-6 32 recrystallized, equiaxed, Gaussian 3 3 4-8 35 recrystallized, equiaxed, Gaussian 3 1 * The gram sizes reported Table 1 were obtamed usmg plastic replicas of the wheel surface, which has the advantage of being a non destructive technique This technique gives a slightly larger gram size (~ +10μm for these microstructures) than the destructive technique used herein for all the other gram size measurements EXAMPLE 2 An mgot of the copper beryllium 25 alloy was hot side forged at 700°C and pierced, as m example 1 In this example, the billet was then hot forged all the way to the final castmg wheel size. An homogeneous microstructure was produced with a very fine average gram size, less than 3 Oμm However, because of the absence of cold work, the grains were not all equiaxed, annealing twins were found within the grams and the gram size distnbution was not Gaussian m shape The microstructure of this wheel is shown in Fig 7. Even though the microstructure was homogeneous and the average gram size was very fine (less than 3 Oμm), the normalized πbbon quantity cast of the casting wheel was only 1 7 This value for the normalized πbbon quantity cast was much less than the 2 9 value obtamed in Example 1 when the wheel was processed substantially the same way, except for the final cold work EXAMPLE 3 An mgot of the copper beryllium alloy 25 was hot side forged at 700°C and pierced The billet was hot forged to an intermediate size and then given a 30% cold reduction to the final wheel size as m Example 1 After the cold work, the mateπal was aged Unlike the solutionized and aged mateπal of Example 1, a recrystallized microstructure was not produced m this case Instead, the wheel had a fine homogenous microstructure with highly deformed grams, which had an average gram size of 15 μm and a Gaussian grain size distribution with no gram larger than 200 μm This homogenous fine microstructure shown m Fig 8 might be expected to have a very high normalized πbbon quantity cast But the casting wheel exhibited an extremely poor normalized πbbon quantity cast value of 0 3, which is much less than that of the average standard wheel, which has a significantly larger grain size The wheels descπbed m Example 1 , 2 and 3 all exhibit an average gram size less than 3 Oμm, but have very different microstructures Only the wheel of Example 1 produced in accordance with the present invention and havmg a microstructure characteπzed by fine, equiaxed, recrystallized grains with a tight Gaussian gram size distπbution has supeπor casting performance EXAMPLE 4 Casting wheels were formed by the direct hot extrusion of a tube An mgot of the copper beryllium alloy 25 was upset hot forged to fit within the extrusion container It was then pierced, while still hot, to the internal diameter of the tube to be extruded After piercmg, the billet was cooled, inspected and then reheated to the extrusion temperature of 650°C The size of the extrusion container was chosen to give a reduction ratio of around 10 1, to ensure that a uniformly high deformation was given to the mgot. The extruded tube was given a standard solution heat treatment and agmg It was then sliced, each slice was machined to the exact dimensions and tolerances of the casting wheel The resultant microstructure was found to be equiaxed and was characteπzed by a tight Gaussian gram size distπbution, as shown m Fig 9 The grams were recrystallized and, as such, were effectively free of dislocations associated with both cold and hot working of these alloys EXAMPLE 5 An mgot of the copper beryllium alloy 25 was hot upset forged, pierced and then hot forward extruded to a tube us g the procedure descπbed m Example 4 This tube was then cold flow formed to the required dimensions for a casting wheel, achievmg a 50% reduction As Fig 4 shows a cold reduction of 20 to 70% could be used to achieve the optimum gram size The flow formed tube was given a standard solution heat treatment, aged and machined to the required tolerances The microstructure consisted of equiaxed grains with a tight Gaussian gram size ώstπbution and an average gram size of approximately 30μm Other mechanical working processes can be used instead of flow forming One is cold saddle forgmg, which has been found to result in recrystallized grains with an extremely tight Gaussian gram size distπbution with an average gram size of 20 μm This wheel had a high normalized πbbon quantity cast value of 2 0 Another mechanical working process is nng rolling, m which an annular quench surface is subjected to continuous mechanical deformation throughout each element of volume These continuous deformation processes produce a very fine, uniform gram size m accordance with the present invention In addition to the mechanical deformation processes descπbed above, vaπous heat treatment steps, earned out either between or during the mechanical deformation processes, may be utilized to facilitate processing and/or to recrystalhze the quench surface grains, and to produce the hardening phases m the quench surface alloy Havmg thus descπbed the invention m rather full detail, it will be understood that such detail need not be stπctly adhered to but that vanous changes and modifications may suggest themselves to one skilled in the art, all falling within the scope of the present invention as defined by the subjomed claims

Claims: What is claimed is: 1 A quench surface for rapid solidification of molten alloy into strip having a microcrystalline or amorphous structure, said quench surface being composed of a thermally conducting alloy having a microstructure consisting of fine, equiaxed, recrystallized grains, the average size of said grams being less than 200 μm and none of said grains bemg larger than 500μm, said grains having a tight Gaussian grain size distπbution 2 A quench surface as recited in claim 1 , wherein said thermally conducting alloy is copper-based 3 A quench surface as recited in claim 2, wherein said thermally conducting alloy is a precipitation-hardened copper alloy 4 A quench surface as recited in claim 2, wherein said thermally conductmg alloy is a dispersion-hardened copper alloy 5 A quench surface as recited in claim 2, wherein said thermally conducting alloy is a beryllium copper alloy 6 A quench surface as recited in claim 1, said alloy having a substantially homogenous microstructure wherein said grains have an average gram size less than 100 μm 7 A quench surface as recited in claim 1, said alloy having a substantially homogenous microstructure wherein said grains have an average grain size less than 30 μm 8 A mechanical forming/heat treating process for making the quench surface of claim 1 , wherem said quench surface is subjected to extrusion and then ring rolling pπor to the final solution heat treatment step 9 A process as recited by claim 1 1 , wherein said quench surface is extruded at a low temperature and medium extrusion ratio pπor to said final solution heat treatment and agmg step 10 A process as recited by claim 1 1 , wherein said quench surface is subjected to hot forging and then cold forging prior to the final solution heat treatment and aging step

Inventors: CHANG CHIN FONG, DECRISTOFARO NICHOLAS J, LIEBERMANN HOWARD H, RAYBOULD DEREK, TELLER DAVIS, CHANG, CHIN, FONG, DECRISTOFARO, NICHOLAS, J., LIEBERMANN, HOWARD, H., RAYBOULD, DEREK, TELLER, DAVIS
Applicants: ALLIED SIGNAL INC, ALLIEDSIGNAL INC.
Application year: 1997
Main classification: B22D11
IPC codes: B22D11