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Title:
IMPROVED RECYCLING METHOD FOR AL-B4C COMPOSITE MATERIALS
Document Type and Number:
WIPO Patent Application WO/2005/103311
Kind Code:
A1
Abstract:
A method is described for reclaiming an Al-B4C composite scrap material. The method involves heating a liquid pool of molten aluminum while also pre-heating the scrap material. The scrap material is then added to the molten aluminum and a predetermined melt temperature is maintained in the liquid pool until all of the scrap material melts into the molten aluminum to form a resultant composite melt. Finally, the resultant composite melt is stirred to promote uniformity. A method is also described for preparing a B4C-containing aluminum cast composite products that involves preparing a mixture of free-flowing B4C particles and molten aluminum and stirring the mixture to wet the aluminum to the B4C particles. The mixture is then cast into a cast composite material and processed to form the cast composite product and Al-B4C composite scrap material. The scrap material is then reclaimed by the method described above.

Inventors:
CHEN XIAO-GUANG (CA)
FORTIN JEAN-YVES (CA)
Application Number:
PCT/CA2005/000609
Publication Date:
November 03, 2005
Filing Date:
April 21, 2005
Export Citation:
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Assignee:
ALCAN INT LTD (CA)
CHEN XIAO-GUANG (CA)
FORTIN JEAN-YVES (CA)
International Classes:
B22D21/04; C22B21/00; C22C1/02; C22C1/10; C22C21/00; C22C32/00; G21F1/08; (IPC1-7): C22C21/00; B22D21/04; C22C1/02; G21F1/08
Foreign References:
US5722033A1998-02-24
US4992241A1991-02-12
US6223805B12001-05-01
US3955970A1976-05-11
US5122181A1992-06-16
Other References:
See also references of EP 1737993A4
Attorney, Agent or Firm:
Gale, Edwin J. (Box 3432 Station, Ottawa Ontario K1P 6N9, CA)
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Claims:
CLAIMS :
1. A method for reclaiming an AlB4C composite scrap material, comprising: a) heating a liquid pool of molten aluminum to a predefined pool temperature; b) preheating the scrap material to a predefined preheat temperature; c) adding the preheated scrap material to the molten aluminum in a mass ratio of from 0.3:0.7 to 0.3:0.7 scrap material to molten aluminum; d) maintaining a predetermined melt temperature in the liquid pool until all of the scrap material melts into the molten aluminum to form a resultant composite melt; and e) stirring the resultant composite melt to promote uniformity.
2. The method of claim 1 wherein the scrap material is preheated to a temperature of less than 6000C.
3. The method of claim 1 wherein the temperature of the combined molten pool of aluminum and melted scrap material is below 7700C.
4. The method of claim 3 wherein the temperature of the combined molten pool of aluminum and melted scrap material is below 74O0C.
5. The method of claim 1 wherein the liquid pool of molten aluminum further comprises up to 0.2 to 5% by weight of titanium. 6.
6. The method of claim 5 wherein additional boron carbide powder is added during or following the step of stirring the resulting composite.
7. A method of preparing a B4Ccontaining aluminum cast composite products comprising: a) preparing a mixture of freeflowing B4C particles and molten aluminum by dispersing the B4C particles in molten aluminum alloy; b) stirring the mixture to wet the aluminum to the B4C particles; c) casting the mixture into a cast composite material; d) processing the cast composite material to form products and resulting AlB4C composite scrap material; e) heating a liquid pool of molten aluminum to a predefined pool temperature; f) preheating the scrap material to a predefined preheat temperature; g) adding the preheated scrap material to the molten aluminum in a mass ratio of from 0.3:0.7 to 0.7:0.3 scrap material to molten aluminum; h) maintaining a predetermined melt temperature in the liquid pool until all of the scrap material melts into the molten aluminum to form a resultant composite melt; and i) stirring the resultant composite melt to promote uniformity and casting as a further cast composite product. 8. The method of claim 7 in which additional boron carbide powder is added before casting the further cast composite product but during or following the step of stirring the resultant composite melt.
Description:
IMPROVED RECYCLING METHOD FOR AL-B4C COMPOSITE MATERIALS

TECHNICAL FIELD

The present invention relates to methods for recycling boron-based neutron absorber materials, and in particular Al-B4C composite scrap materials.

BACKGROUND ART There is a great interest in the nuclear energy industry for construction materials which will absorb, and therefore not release, neutrons, e.g. in containers for waste fuel. These containers are predominantly made of aluminum (Al) -based materials, and boron (B) is a commonly used element for neutron absorbing. Boron can be typically incorporated into Al as B4C, TiB2 or simply B that forms AlB2 or AIB12 in an Al-matrix. The manufacture processes for making such storage containers includes methods of direct chill (DC) casting, extrusion and rolling. These methods quite often produce process scraps of Al-B4C composite materials that can make up to 65% of the original source material. In the interest of economic savings and waste reduction, it is therefore of great interest to find a way to reclaim the valuable process scrap. However, B4C particles tend to be thermodynamically unstable in liquid aluminum, causing interfacial reactions between B4C and Al. This significantly reduces the fluidity and castability of the liquid composite during remelting, making the process of reclaiming scrap materials and their subsequent casting extremely difficult. Boron-containing, aluminum materials are also highly reactive in the molten state, and the reactivity is strongly temperature and time dependent. Therefore, in attempts to recycle the scrap material by simply melting, the surface temperature of the scrap becomes elevated (e.g. more than about 7700C), resulting in the B4C- containing refractory reacting with the aluminum matrix, rendering the material useless for subsequent casting, as fluidity becomes reduced. Attempts to combine "virgin", or unused, cast composite material and composite scrap materials have also been unsuccessful since the virgin cast composite has to be heated to a relatively high temperature to permit a reasonable quantity of scrap to be incorporated into the melt within a reasonable time. This heating tends to cause the virgin composite to deteriorate. Alternately, the temperature of the virgin composite can be kept at a lower level, but in this case, the incorporation rate of scrap material must be reduced, resulting in an increase in the time needed to recycle a given quantity of scrap material, and again the material tends to deteriorate. US Patent No. 3,955,970 (Claxton et al.) teaches a continuous melting process involving submerging scrap material into molten aluminum at ratios of from 1:10 to 1:50 scrap material to molten aluminum. Stirring is used to incorporate the solid scrap into the molten aluminum. There is no specific teaching of ways to prevent reactions between the B4C in the scrap material and the molten aluminum matrix. US Patent No. 4,571,258 also teaches a method of reclaiming scrap material by submergence in molten aluminum, in this case the scrap being light gauge aluminium. This patent is silent on dealing with scrap material that contains B4C and methods of preventing B4C degradation or reaction with molten aluminum. US Patent No. 6,223,805 describes a method for recycling metal matrix composites and includes, as options, mixing of the composite with "virgin" composite or with matrix metal. The patent focuses on a method of eliminating inclusions in the recycled material. It is therefore highly desirable to establish a method of reclaiming AI-B4C composite scrap material while maintaining integrity of the B4C and fluidity in the resultant composite product.

DISCLOSURE OF INVENTION The present invention creates a unique way to reclaim Al-B4C composite scrap material and to remelt Al-B4C composite materials for shape casting. The present invention thus provides a method for reclaiming an AI-B4C composite scrap material that comprises heating a liquid pool of molten aluminum to a predefined pool temperature while also pre-heating the scrap material to a predefined pre-heat temperature. Next the pre-heated scrap material is added to the molten aluminum in a mass ratio of from 0.3:0.7 to 0.7:0.3 scrap material to molten aluminum. A predetermined melt temperature is maintained in the liquid pool until all of the scrap material melts into the molten aluminum, to form a resultant composite melt and finally, the resultant composite melt is stirred to promote uniformity. The present invention also provides a method of preparing a B4C-containing aluminum cast composite product that involves preparing a mixture of free-flowing B4C particles and molten aluminum by dispersing the B4C particles in molten aluminum alloy and stirring the mixture to wet the aluminum to the B4C particles. The mixture is then cast into a cast composite material and further processed into products which generates Al-B4C composite scrap material. The scrap is then reclaimed by heating a liquid pool of molten aluminum to a predefined pool temperature while also pre-heating the scrap material to a predefined pre-heat temperature. The pre-heated scrap material is added to the molten aluminum in a mass ratio of from 0.3:0.7 to 0.7:0.3 scrap material to molten aluminum and a predetermined melt temperature is maintained in the liquid pool until all of the scrap material melts into the molten aluminum to form a resultant composite melt. Finally, the resultant composite melt is stirred to promote uniformity and cast as a new cast product.

BRIEF DESCRIPTION OF DRAWINGS The present invention will be described in conjunction with the following figures:

Figs. IA, IB, 1C and ID are schematic diagrams showing the steps involved in the method of the present invention;

Fig. 2 is a plot of composite fluidity vs. time illustrating the effect of a short overheat on fluidity;

Fig. 3 is a plot of composite fluidity vs. time illustrating the effect of holding temperature on fluidity; and

Fig. 4 is a plot of composite fluidity vs. time illustrating the effect of titanium additions on fluidity for different holding temperatures while reclaiming material from 15% to 10% B4C. BEST MODES FOR CARRYING OUT THE INVENTION The present invention focuses on improving the quantity and quality of boron-containing aluminum scrap material that can be reclaimed for reuse. To date, several approaches to reclaiming scrap material have been proposed and tested on laboratory scale. Some of these approaches are outlined in Table I. As seen in the table, the replacing and remelting methods are very sensitive to the melt temperature and duration. Local overheating and long melting times can cause loss of fluidity and general B4C deterioration.

Table I

The dilution approach, by contrast, has shown good results in remelting and recycling scrap Al-B4C materials. In the present invention, a molten aluminum alloy is provided at a temperature determined by the desired scrap incorporation rate and so that the temperature of the mixture after incorporation, melting and mixing of the scrap does not allow for B4C degradation. The dilution process consists of four basic steps, which are illustrated in Figures IA, IB, 1C and ID. Firstly, as seen in Fig. IA, a liquid pool of molten aluminum is formed in a quantity that will make up 0.3 to 0.7 of the total melt after incorporation of the scrap material. The curved lines shown in the drawing represent heating applied to the container. Next, scrap material, preferably in the form of an Al-B4C block as seen in Fig. IB, is preheated to a predetermined temperature. The preheated block of scrap material is added to the molten aluminum and allowed to melt, as seen in Fig. 1C, until the block totally melts in the liquid pool. Finally, as shown in Fig. ID, the resultant composite melt is stirred to form a uniform composite product. Stirring aids to shorten process time, but is only conducted after the entire scrap has melted. By controlling the temperature of the liquid pool there is no risk of overheating Al-B4C material and causing undesirable material degradation. As well, the relatively short melting time required prevents the chance of reactions between B4C and aluminum. Any simple furnace and equipment well known in the art can be used to carry out the present invention and still provide excellent fluidity and castability. In turn, ease of castability leads to less time required for casting. The temperature of the molten aluminum before adding the scrap material, and the temperature of the pre-heated block of scrap material should be such that the temperature of the resultant composite melt (that is, the molten aluminum alloy from the original bath plus the matrix alloy from the scrap and any boron carbide particles dispersed in the molten composite) is preferably less than 77O0C and more preferable below 7400C, but more than the solidus, and preferably more than the liquidus temperature. Preferably, the block of B4C-containing scrap material is preheated to a temperature of less than 600°C, more preferable below 5000C. Based on these requirements, it can be seen that the temperature of the molten aluminum alloy in the original bath may have to be elevated to achieve the final balance temperature with the amount of scrap added. For this reason, a process involving unused cast composite material as the original bath is not viable. To ensure that heat is transferred quickly though the mixture while melting it is important to have liquid metal present in the mixture at all times and therefore the temperature of the mixture should be maintained above its solidus and more preferably above its liquidus temperature. The importance of this temperature control is shown in Figures 2 and 3 which are plots of composite fluidity, measured by the distance that the composite will travel up a linear mould of specific design, versus holding time. It is clear from Figure 2 that even a small increase in molten composite temperature above 7700C has a significant effect on fluidity. Furthermore the plot shows that the alternate approaches summarized in Table 1, such as mixing with new composite material ("replacing") or simple remelting, where the temperature in part will exceed 77O0C, will be detrimental to maintaining good fluidity. In Figure 3, it can be seen that a holding temperature of 7700C retains acceptable fluidity for at least 40 minutes, which is a minimum useful holding time for casting. Lower temperatures yield much improved stability, and a temperature of 8000C (i.e. in excess of the preferred upper limit of 7700C) causes a rapid degradation of fluidity. It should be noted that the present invention provides a much higher scrap material addition rate than proposed in the prior art. This allows larger quantities of scrap to be reclaimed at a time, providing higher levels of efficiency. Additionally, since the resultant composite product is less diluted than that of submergence methods, less downstream processing is required to meet neutron absorptivity requirements for turning the product into neutron absorbing containers. The mass ratio of scrap material to molten aluminum is at least 0.3:0.7 and may be as high as 0.7:0.3. This means that the mixture cannot be stirred until the scrap and aluminum have equilibrated, i.e. until all the scrap has melted. The ratio results in a product having sufficient B4C to be readily useable. A preferred feature of the invention is the addition of Ti in the range of 0.2 to 5.0%, and more preferable range of 0.5 to 1.5% by weight of titanium to the molten aluminum pool. This improves fluidity of the resulting composite melt and provides further stabilization of B4C in liquid aluminum. Figure 4 shows a plot of composite fluidity at various holding temperatures with and without Ti additions as a function of time. For holding temperatures of 7400C or less the addition of Ti enhances the stability of the composite to a small extent. For a holding temperature of 7700C (the upper preferred limit), addition of Ti has a significant effect on stability. One characteristic of the process of the present invention is that it is carried out as a batch process. A continuous process, such as those used in typical scrap recycling where scrap is continuously added and product periodically removed, has problems in that it requires that a quantity of already melted Al-B4C composite be retained at a high temperature for a significant period of time. This invariably leads to undesirable reactions between B4C and Al, resulting in loss of fluidity and B4C degradation. The resultant composite materials produced by the present invention can also be produced as remelting ingots that can be used to manufacture shape castings for neutron absorbing containers in aluminum foundries. Thus, the dilution process can be directly applied to the remelting practice in aluminum foundries . The resultant product can optionally be modified using known methods to restore and enhance neutron absorptivity to a higher level. For example, additional boron carbide powder can be incorporated by mixing into the fully melted mass provided that such mixing is completed in the a relatively short time between melting and casting, specifically during or immediately following the step of mixing the melted product. The presence of Ti (as in the preferred embodiments of this invention) allows for stabilization of the boron carbide in such mixtures. This detailed description of the methods and products is used to illustrate the prime embodiment of the present invention. It will be obvious to those skilled in the art that various modifications can be made in the present method and that various alternative embodiments can be utilized. Therefore, it will be recognized that various modifications can be made in both the method and products of the present invention and in the applications to which the method and products are applied without departing from the scope of the invention, which is limited only by the appended claims.