CA1155631A - Method and apparatus for hot-forming metals phone to crack during rolling - Google Patents

Method and apparatus for hot-forming metals phone to crack during rolling

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Publication number
CA1155631A
CA1155631A CA000361326A CA361326A CA1155631A CA 1155631 A CA1155631 A CA 1155631A CA 000361326 A CA000361326 A CA 000361326A CA 361326 A CA361326 A CA 361326A CA 1155631 A CA1155631 A CA 1155631A
Authority
CA
Canada
Prior art keywords
bar
cast
copper
cross
hot
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000361326A
Other languages
French (fr)
Inventor
Ronald D. Adams
Enrique H. Chia
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Southwire Co LLC
Original Assignee
Southwire Co LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Southwire Co LLC filed Critical Southwire Co LLC
Application granted granted Critical
Publication of CA1155631A publication Critical patent/CA1155631A/en
Expired legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B3/00Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/003Rolling non-ferrous metals immediately subsequent to continuous casting, i.e. in-line rolling
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22DCASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12Accessories for subsequent treating or working cast stock in situ
    • B22D11/1206Accessories for subsequent treating or working cast stock in situ for plastic shaping of strands
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B13/00Metal-rolling stands, i.e. an assembly composed of a stand frame, rolls, and accessories
    • B21B13/18Metal-rolling stands, i.e. an assembly composed of a stand frame, rolls, and accessories for step-by-step or planetary rolling; pendulum mills
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B3/00Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/001Aluminium or its alloys
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B3/00Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B2003/005Copper or its alloys

Abstract

TITLE
METHOD AND APPARATUS FOR HOT-FORMING METALS
PRONE TO CRACK DURING ROLLING
INVENTOR
Ronald Dean ADAMS and Enrique Henry CHIA

ABSTRACT

A method of and apparatus for continuously casting a molten metal in a casting means to obtain a solidified cast bar at a hot-forming temperature, passing the cast metal at a hot-forming temperature from the casting means to a hot-forming means, and hot forming the cast bar into a wrought product by a two-stage reduction of its cross-sectional area while it is still at a hot-forming temperature, including, in the first stage, the step of forming a shell of finely distributed recrystallized grains in the surface layers of the cast bar by a selected small amount of deformation of the cast bar in its as-cast condition prior to the second stage in which substantial reduction of its cross-sectional area forms the wrought product. The shell of fine grains formed on the cast bar during the first stage of deformation permits substantial reduction of the cross-sectional area of the cast bar during the second stage of deformation without the cast bar cracking, even when the cast bar has a high impurity content.

Description

1 155~31 BACKGROUND OF THE INVENTION
The present invention relates to the hot forming of metals, and more particularly relates to the continuous casting and hot forming of the as-cast bars of certain impure metals prone to crack during hot-rolling.
It is well known that many metals, such as copper, may be continuously cast, either in stationary vertical molds or in a rotating casting wheel, to obtain a cast bar which is then immediately hot formed, while in a substantially as-cast condition, by passing the cast bar exiting the mold to and through the roll stands of a rolling mill while the cast bar is still at a hot-forming temperature. It is also well known that the as-cast structure of the metal bar is often such that cracking of the cast bar during hot forming may be a problem if the cast bar is required to be directly hot formed into a semi-finished product, such as redraw rod, during which the initially large cross-sectional area of the cast bar is substantially reduced by a plurality of deformations along different axes to provide a much smaller cross-sectional area in the product.
While this problem could be avoided by casting a cast bar having an initially small cross-sectional area which need not be substantially reduced to provide the desired cross-sectional area of the final product, this approach is not commercially practical since high casting outputs, and therefore low costs, can be readily achieved only with cast bars having large cross-sectional areas which are rapidly reduced to the sma~ler cross-sectional areas of the products, such as 3/8" diameter rod for drawing into wire, by a minimum number of severe deformations. Thus, the problem of a cast bar cracking during hot forming must be solved within the commercial context of cast bars having initially large cross-sectional areas which are then hot formed into products having small cross-sectional areas by a series of reductions which often are substantial enough to cause cracking of the cast bar under certain conditions.
This problem has been overcome in the prior art for r~
- ~i ~J~
, 1"

1 ~5631 relatively pure electrolytically-refined copper having low impurity levels such as 3-10 ppm lead, 1 ppm bismuth, and 1 ppm antimony. For example, U.S. Patent No. 3,317,994, and U.S. Patent No. 3,672,430 disclose that this cracking problem can be overco~e by conditioning such relatively pure copper cast bar by initial large reductions (e.g. 36~) of the cross-sectional area in the initial roll stands sufficient to substantially destroy the as-cast structure of the cast bar.
The additional reductions along different axes of deformation, which would cause cracking of the cast bar but for the initial destruction of the as-cast structure of the cast bar, may then safely be performed. This conditioning of the cast bar not only prevents cracking of the cast bar during hot forming but also has the advantage of accomplishing a large reduction in the cross-sectional area of the cast bar while its hot-forming temperature is such as to minimize the power required for the reduction.
The prior art has not, however, provided a solution to the cracking problem described above for metals, such as fire-refined copper, containing a high degree of impurities.
This is because the large amount of impurities in the grain boundaries of the as-cast structure cause the cast bar to crack when an attempt is made to substantially destroy the as-cast structure with the same large initial reduction of the cross-sectional area of the cast bar that is known to be effective with low impurity metals. Moreover, the greater the percentage of impurities in the cast bar, the more likely it is that cracks will occur during hot forming.
Thus, although there is no requirement for high-purity electrolytically-refined copper (except for specialized uses such as magnet wire) it has heretofore been necessary to use such highly refined copper in order to be able to use and obtain the many advantages of tandem continuous casting and hot-forming apparatus. As a result, a substantial refining cost is added to the price of many final copper products even though high purity is not required to meet conductivity or other specifications. For example, fire-refined copper wire ; : ~

1 1556~1 having a moderately high degree of impurities can meet the IACS conductivity standard for household electrical wiring and can be produced most economically if the rod to be drawn into such wire can be produced using known continuous casting and hot-forming apparatus.
SUMMARY OF THE INVENTION
The present invention solves the above-described cracking problem of the prior art by providing a method of continuously casting and hot forming both low and high impurity metal without substantial cracking of the cast bar occurring during the hot rolling process. Generally described, the invention provides, in a method of continuously casting molten metal to obtain a cast bar with a relatively large cross-sectional area, and hot forming the cast bar at a hot-forming temperature into a product having a relatively small cross-sectional area by substantial reduction of the cross-sectional area of the cast bar which would be such that the as-cast structure of the cast bar would be expected to cause the cast bar to crack, the additional step of first forming a shell of finely distributed recrystallized grains at least in the surface layers of the cast bar prior to later substantial reduction of`the cross-sectional area of the cast bar, said shell being formed by relatively slight deformations of the cast bar while at a hot-forming temperature.
The slight deformations are of magnitude (preferably 5 ; to 20~) which will not cause the cast bar to crack, but which in combination with the hot-forming temperature of the cast bar will cause the cast bar to have a shell of finely distributed recrystallized grains of a thickness sufficient (about 10% of total area) to prevent cracking of the cast bar (even when having moderately high impurities) during the subsequent substantial deformations. The surface shell of fine grains provided by the invention allows substantial reduction of the cross-sectional area of the bar in a subsequent pass, even in excess of 40%, without cracking occurring and even though the cast bar has a relatively high amount of impurities.

. .

- 1155~31 For example, the present invention allows a copper cast bar having a cross-sectional area of 5 square inches, or more, and containing as much as 50-200 ppm of impurities, such as lead, bismuth, iron and antimony, to be continuously hot formed into wrought copper rod having a cross-section area of 1/2 square inch, or less, without cracking.
Thus, most broadly stated, the present invention provides a method of continuously casting a copper bar and subsequently hot-forming said cast copper bar while in substantially its as-cast condition by a plurality of substantial compressions, characterized by condition7ng the copper bar for hot-forming by forming a shell of finely distributed recrystallized grains at least on the surface of said copper bar by compressing said bar with a preliminary slight compression following casting of said copper bar but prior to said plurality of substantial compressions.
In its broadest apparatus aspects the present inventon includes means for continuously casting either fire-refined copper, re-melted copper scrap or tough pitch grade copper into a copper bar, and means for subsequently hot-forming the copper bar while in substantially its as-cast condition by a plurality of sustantial compressions; characterized by means for conditioning the cast copper bar prior to hot-forming thereof so as to prevent cracking when subjected to said substantial compressions, said conditioning means including means for slightly compressing the cast copper bar to the extent necessary to form a shell of finely distributed recrystallized grains at least on the surface thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1 is a schematic representation of casting and forming apparatus for practicing the method of the present invention.
Fig. 2. is a cross-section of a cast bar in substantially an as-cast condition (in this case with columnar grains).
Fig. 3 is a cross-section of the cast bar shown in Fig.
2 following one slight reduction of the cross-section.

1 15~631 Fig. 4 is a cross-section of the cast bar shown in Fig.
2 following two perpendicular slight compressions to form a complete shell of finely distributed grains near the surface of the bar.
Fig. 5 is a cross-section of the cast bar shown in Fig.
2 following the two slight compressions and one severe hot-forming compression.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now to the drawing, in which like numerals refer to like parts throughout the several views, Fig.
schematically depicts an apparatus for practicing the method of the present invention. The continuous casting and hot-forming system (10) includes a casting machine (12) which includes a casting wheel (14) having a peripheral groove therein, a flexible band (16) carried by a plurality of guide wheels (17) which bias the flexible band (16) against the casting wheel (14) for a portion of the circumference of the casting wheel (14) to cover the peripheral groove and form a mold between the band (16) and the casting wheel (14). As molten metal is poured into the mold through the pouring spout (19), the casting wheel (14) is rotated and the band (16) moves with the casting wheel (14) to form a moving mold. A
cooling system (not shown) within the casting machine (12) causes the molten metal to solidify in the mold and to exit the casting wheel (14) as a solid cast bar (20).
From the casting machine (12), the cast bar (20) passes through a conditioning means (21), which includes roll stands (22) and (23). The conditioning roll stands (22) and (23) lightly compress the bar which recrystallizes in the area compressed to form a shell of finely distributed grain structure at the surface of the bar (20). After conditioning, the bar (20) is passed through a conventional rolling mill (24), which includes a plurality of roll stands (25), (26), (27) and (28). The roll stands of the rolling mill (24) provide the primary hot forming of the cast bar by compressing the conditioned bar sequentially until the bar is reduced to a desired cross-sectional size and shape.

:

The grain structure of the cast bar (20) as it exits from the casting machine (12) is shown in Fig. 2. The molten metal solidifies in the casting machine in a fashion that can be columnar, or equiaxed, or both, depending on the cooling rate. This as-cast structure can be characterized by large grains (30) extending radially from the surfaces of the bar (if columnar) and separated from each other by grain boundaries (31). Most of the impurities present in the cast bar are located alony the grain and dendrite boundaries (31).
If the molten copper poured through the spout (19) into the casting wheel (14) were only fire-refined, and not electrolytically-refined, and the cast bar (20) was passed immediately to the rolling mill (24) without passing through the conditioning means (21), the impurities along the boundaries (31) of the cast bar (20) would cause the cast bar to crack at the boundaries upon deformation by the roll stands of the rolling mill (24) when following the teachings of the prior art as illustrated in U.S. Patent No. 3,317,994.
The conditioning means (21) of the present invention prevents such cracking by providing a sequence of preliminary light compressions as shown in Fig. 3 and Fig. 4, wherein the result of the compression is shown and the previous shape of the cast bar is shown in broken lines. Fig. 3 shows the result of a 7% reduction provided by the roll stand (22) along a horizontal axis of compression (33). The columnar and/or equiaxed as-cast grain structure of the cast metal has been recrystallized into a layer of equiaxed grains (35) covering a portion of the surface of the cast bar (20). The interior of the ba-f may still have an as-cast structure.
In Fig. 4 the bar t20) has been subjected to a second 7%
reduction by the roll stand (23) along a vertical axis of compression (33) perpendicular to the axis of compression of roll stand (22). The volume of recrystalliæed finely distributed grains (35) now forms a shell (36) around the entire surface of the bar (20), although the interior of the bar retains some as-cast structure.
It will be understood that the formation of the shell 115563~L

may be accomplished by a conditioning means comprising any number of roll stands, preferably at least two, or any other type of forming tools, such as extrusion dies, multiple forging hammers, etc. so long as the preliminary light deformation of the metal results in a shell of recrystallized grains covering substantially the entire surface of the bar, or at least the areas subject to cracking when subject to the first heavy reduction.
The individual slight compressions should be between 5-20% reduction, preferably about 7% to 10%, so as not to crack the bar during conditioning. The total deformation provided by the conditioning means (21) must provide a shell (36) of sufficient depth (at least about 10%) to prevent cracking of the bar during subsequent severe deformation of the bar when passing through the roll stands (25-28) of the rolling mill (24).
When the shape of the bar in its as-cast condition includes prominent corners such as those of the bar shown in Fig. 2, the shape of the compressing surfaces in the roll stands (22) and (23) may be designed to avoid excessive compression of the corner areas as compared to the other surfaces of the cast bar, so that cracking will not result at the corners during conditioning.
Fig. 5 shows a cross-section of the cast bar (20) following a substantial reduction of the cross-sectional area by the first roll stand (25) of the rolling mill (24). The remainng as-cast structure in the interior of the bar (20) has been recrystallized to form finely distributed equiaxed grains (35).
When a shell (36) has been formed on the surface of the bar (20), a high reduction may be taken at the first roll stand (25) of the rolling mill (24). It has been found that such initial hot-forming compression may be in excess of 40%
following conditioning according to the present invention.
The ability to use very high reductions during subsequent hot-forming means that the desired final cross-sectional size and shape may be reached using a rolling mill having a few 1~55631 roll stands. Thus, even though a conditioning means according to the present invention requires one or two roll stands, the total amount and therefore cost of the conditioning and hot-forming apparatus may be reduced.
The method of the present invention allows continuous casting and rolling of high impurity metals, such as fire-refined copper generally including from 50 to 200 ppm lead, bismuth, iron and antimony without cracking the bar.
Furthermore, cracking is prevented throughout the hot-forming temperature range of the metal. In addition, the method of the present invention is effective for processing electrolytically-refined copper as well. Thus, the same casting and hot-forming apparatus may be used to produce metals of varying purity depending on the standards which must be met for a particular product. It is no longer necessary to add the cost of additional refining to the cost of the final product when a highly pure product is not specifically required.
If it is desired to reduce even further the possibility of cracking, eliptically shaped rolling channels may be provided for all of the roll stands (22), (23) and (25-28) in order to provide optimal tangetial velocities of the rolls in the roll stands with respect to the cast metal, as dislcosed in U.S. Patent No. 3,317,994. However, such measures are usually not needed to avoid cracking if the present invention is practiced as described herein on metals having impurity levels as described above.
It will be understood by those skilled in the art that the roll stands of the conditioning means (21) may be either a separate component of the system or may be constructed as an integral part of a rolling mill.
While this invention has been described in detail with particular reference to preferred embodiments thereof, it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described herein before and as defined in the appended claims.

Claims (26)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. A method of continuously casting a copper bar and subsequently hot-forming said cast copper bar while in substantially its as-cast condition by a plurality of substantial compressions, characterized by:
conditioning the copper bar for hot-forming by forming a shell of finely distributed recrystallized grains at least on the surface of said copper bar by compressing said bar with a preliminary slight compression following casting of said copper bar but prior to said plurality of substantial compressions.
2. A method as claimed in claim 1 characterized in that said slight compression reduces the cross-sectional area of said cast copper bar by between 5 and 20 percent.
3. A method as claimed in claim 2, further characterized in that said slight compression reduces the cross-sectional area or said cast copper bar by between 7 and 10 percent.
4. A method as claimed in claim 1, 2 or 3, characterized in that the first of said plurality of substantial compressions reduces the cross-sectional area of the cast bar by in excess of 40 percent.
5. A method as claimed in claim 1, characterized in that the conditioning and the hot forming of said copper bar take place within a single rolling mill having a plurality of roll stands and the first one of said plurality of roll stands conditions the cast bar by reducing its cross-sectional area by about 5 to 20 percent, and the second of said roll stands hot forms said bar to reduce its cross-sectional area by at least 40 percent and the remaining roll stands further reduce the cast bar to the desired final size.
6. A method as claimed in claim 1, characterized in that said slight compression comprises a first 7 percent reduction of the cross-section of said bar followed by a second 7 percent reduction along an axis of compression which is 90°
removed from said first 7 percent reduction thereby forming a shell around the entire surface of the bar.
7. A method as claimed in claim 1, 2 or 3, characterized in that said copper bar is cast from fire-refined copper.
8. A method as claimed in claim 5 or 6, characterized in that said copper bar is cast from fire-refined copper.
9. A method as claimed in claim 1, 2 or 3, characterized in that the first of said plurality of substantial compressions reduces the cross-sectional area of the cast bar by in excess of 40 percent, and that said copper bar is cast from fire-refined copper.
10. A method as claimed in claim 1, 2 or 3 characterized in that the said copper bar is cast from fire-refined copper.
11. A method as claimed in claim 5 or 6 characterized in that the said copper bar is cast from fire-refined copper.
12. A method as claimed in claim 1, 2 or 3, characterized in that the first of said plurality of substantial compressions reduces the cross-sectional area of the cast bar by in excess of 40 percent, and that the said copper bar is cast from fire-refined copper.
13. A method as claimed in claim 1, 2 or 3, characterized in that the said copper bar is cast from tough pitch grade copper.
14. A method as claimed in claim 5 or 6, characterized in that the said copper bar is cast from tough pitch grade copper.
15. A method as claimed in claim 1, 2 or 3, characterized in that the first of said plurality of substantial compressions reduces the cross-sectional area of the cast bar by in excess of 40 percent, and that the said copper bar is cast from tough pitch grade copper.
16. Apparatus, particularly suitable for carrying out a method of continuously casting and hot-forming a copper bar comprising means for continuously casting either fire-refined copper, re-melted copper scrap or tough pitch grade copper into a copper bar, and means for subsequently hot-forming the copper bar while in substantially its as-cast condition by a plurality of substantial compressions; characterized by:
means for conditioning the cast copper bar prior to hot-forming theeof so as to prevent cracking when subjected to said substantial compressions, said conditioning means including means for slightly compressing the cast copper bar to the extent necessary to form a shell of finely distributed recrystalized grains at least on the surface thereof.
17. Apparatus as claimed in claim 16, characterized in that said means for slightly compressing includes means for reducing the cross-sectional area of the cast copper bar by between 5 and 20 percent.
18. Apparatus as claimed in claim 16 or 17, characterized in that said means for slightly compressing includes means for providing a first 7 percent reduction of the cross-sectional area of the cast copper bar followed by a second 7 percent reduction along an axis of compression which is 90 removed from the axis of compression of said first reduction.
19. Apparatus as claimed in claim 16, characterized in that said conditioning means and said hot-forming means are positioned in a single rolling mill having a plurality of roll stands, the first of said roll stands being arranged to reduce the cross-sectional area of the cast copper bar by between 5 and 20 percent, and the second of said roll stands being arranged to further reduce the cross-sectional area of the cast copper bar by at least 40 percent.
20. A method of hot rolling, directly inline with a continuous caster, a continuous bar of high impurity copper without cracking said bar during heavy reduction from the predominately as cast condition, comprising:
(a) providing as a starting material, a molten flow of high impurity copper; then (b) continuously casting said molten flow into a continuous bar and directing the advancing solidified bar to an inline continuous hot rolling mill, said bar being in the as cast condition and at a hot-forming temperature; then (c) conditioning said bar immediately precedent to subjecting said bar to heavy reduction in said rolling mill, said conditioning being characterized in that said bar is preliminarily subjected to light reduction sufficient to cause recrystallization in a relatively thin surface shell within said bar but otherwise leaving said bar in a predominately as cast condition; and then (d) subjecting said bar to heavy reduction in at least the first roll stand following conditioning, said heavy reduction being sufficient to cause substantially complete recrystallization throughout the entire cross-section of said bar after conditioning.
21. The method of claim 20 wherein said high impurity copper contains at least about 50 ppm impurities.
22. The method of claim 21 wherein said impurities are in the range of about 50 to 20 ppm of one or more of the impurities lead, bismuth, iron, and antimony.
23. The method of claim 22 whrein the cross-sectional area of said surface shell resulting from step (c) constitutes about 10% of the cross-sectional area of said bar.
24. The method of claim 21, 22 or 23 wherein the cumulative reduction of the bar cross-section during said conditioning is in the range of about 5 to 20%.
25. The method of claim 21, 22 and 23 wherein the cumulative reduction of the bar cross-section during said conditioning is in the range of about 5 to 20% and comprises a first reduction of about 7% along a first axis of compression and a second reduction of about 7% along a second axis of compression being 90° removed from said first axis.
26. The method of claim 21, 22 or 23 wherein the cumulative reduction of the bar cross-section during said conditioning is in the range of about 5 to 20% and said heavy reduction of step (d) is at least about 40%.
CA000361326A 1979-10-01 1980-10-01 Method and apparatus for hot-forming metals phone to crack during rolling Expired CA1155631A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/080,368 US4352697A (en) 1979-10-01 1979-10-01 Method of hot-forming metals prone to crack during rolling
US80,368 1979-10-01

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JP (1) JPS5689304A (en)
AU (1) AU542104B2 (en)
BE (1) BE885498A (en)
CA (1) CA1155631A (en)
DD (1) DD154106A5 (en)
DE (1) DE3037098C2 (en)
ES (1) ES495542A0 (en)
FR (1) FR2466285B1 (en)
GB (1) GB2059306B (en)
MX (1) MX154712A (en)
PH (1) PH16201A (en)
SE (1) SE500291C2 (en)
SU (1) SU1279517A1 (en)
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AU542104B2 (en) 1985-02-07
DE3037098C2 (en) 1986-07-17
ES8107066A1 (en) 1981-10-01
FR2466285B1 (en) 1985-06-21
SE8006840L (en) 1981-04-02
US4352697A (en) 1982-10-05
GB2059306B (en) 1983-05-11
JPS5689304A (en) 1981-07-20
BE885498A (en) 1981-04-01
SU1279517A3 (en) 1986-12-23
DE3037098A1 (en) 1981-04-16
SU1279517A1 (en) 1986-12-23
ES495542A0 (en) 1981-10-01
AU6286780A (en) 1981-04-09
PH16201A (en) 1983-08-02
MX154712A (en) 1987-12-03
GB2059306A (en) 1981-04-23
DD154106A5 (en) 1982-02-24
ZA806074B (en) 1981-10-28
ZM9580A1 (en) 1981-10-21
FR2466285A1 (en) 1981-04-10
SE500291C2 (en) 1994-05-30

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