CA2093632C - Coolant controlled ir (infrared) heat treat apparatus - Google Patents

Coolant controlled ir (infrared) heat treat apparatus

Info

Publication number
CA2093632C
CA2093632C CA002093632A CA2093632A CA2093632C CA 2093632 C CA2093632 C CA 2093632C CA 002093632 A CA002093632 A CA 002093632A CA 2093632 A CA2093632 A CA 2093632A CA 2093632 C CA2093632 C CA 2093632C
Authority
CA
Canada
Prior art keywords
lamp
conduit
infrared
temperature
interior
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 - Fee Related
Application number
CA002093632A
Other languages
French (fr)
Other versions
CA2093632A1 (en
Inventor
John Roy Eppeland
James E. Heath
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.)
BGK Finishing Systems Inc
Original Assignee
BGK Finishing Systems Inc
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 BGK Finishing Systems Inc filed Critical BGK Finishing Systems Inc
Publication of CA2093632A1 publication Critical patent/CA2093632A1/en
Application granted granted Critical
Publication of CA2093632C publication Critical patent/CA2093632C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27DDETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D99/00Subject matter not provided for in other groups of this subclass
    • F27D99/0001Heating elements or systems
    • F27D99/0006Electric heating elements or system
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/1836Heating and cooling the reactor
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/18Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
    • B01J8/24Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
    • B01J8/42Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique with fluidised bed subjected to electric current or to radiations this sub-group includes the fluidised bed subjected to electric or magnetic fields
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27FURNACES; KILNS; OVENS; RETORTS
    • F27BFURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B15/00Fluidised-bed furnaces; Other furnaces using or treating finely-divided materials in dispersion
    • F27B15/02Details, accessories, or equipment peculiar to furnaces of these types
    • F27B15/14Arrangements of heating devices
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05BELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B3/00Ohmic-resistance heating
    • H05B3/0033Heating devices using lamps
    • H05B3/0038Heating devices using lamps for industrial applications
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00026Controlling or regulating the heat exchange system
    • B01J2208/00035Controlling or regulating the heat exchange system involving measured parameters
    • B01J2208/00044Temperature measurement
    • B01J2208/00061Temperature measurement of the reactants
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00106Controlling the temperature by indirect heat exchange
    • B01J2208/00168Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00194Tubes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008Controlling the process
    • B01J2208/00017Controlling the temperature
    • B01J2208/00433Controlling the temperature using electromagnetic heating
    • B01J2208/0046Infrared radiation

Abstract

An apparatus is disclosed for heat treating a product. The apparatus includes an infrared lamp assembly having an infrared lamp (46) disposed within the interior of a quartz conduit (37). Air is admitted to the interior of the conduit at a controlled rate to cool the conduit while minimizing adverse impacton the efficiency of the infrared lamp.

Description

WO g2/06780 PCr/USgl/07537 Coolant controlled 1nfr~red heat treat ~pparatus _______________________________ ________ I. ~G~OUND O~ THE lNv~ lON
1. Field of the Invention This invention pertains to improvements in controlled heat treating. More particularly, this invention pertains to an infrared hub treat source with controlled cooling.
2. DescriPtion of the Prior Art The use of fluidized bed furnaces for heat treating a product is well known. Such furnaces generate an extremely hot bed of fluidizing particles such as aluminum oxide. The furnaces csn be used for both continuous ~ oc~sing of a product or batch ~o~ssing of products.
U.S. Patent No. 4,752,061 te~ches a fluidized bed furnace which uses infrared radiation as the heating source. One advantage of using infrared radiation as the heating source is that it permits the use of inert gases to fluidize the particles in the furnace. As a result, a controlled atmosphere can be provided surro~n~in~ the product being heat treated in the furnace.
The aforesaid U.S. Patent No. 4,752,061 places infrared lamps out of the bed h~hi n~ a quartz wall or screen. As a result, the distance from the infrared lamps to the bed results in a high temperature gradient with too little of the energy source contributing to the fluidization of the bed. This leads to significant energy inefficiency. Also, the infrared lamps may be in close proximity to the stainless steel retort. This could result in partial melting of the retort.
In the present invention, infrared lamp heat Itreating assemblies are utilized including infrared sources disposed wi*hin transparent conduits. The present invention utilizes means for admitting the cooling fluid to the interior of the conduits.

209~6~2 II. SUMMARY OF THE l~v~lION
According to a preferred embodiment of the present invention, an apparatus is disclosed for heat treating a product. The apparatus includes an infrared lamp as~embly having an infrared lamp disposed within an infrared transparent conduit. A cooling fluid i9 applied to the interior of the conduit to cool the conduit walls. The admission of the cooling fluid is controlled to minim; ze adverse effects of the fluid on the efficiency of the source of infrared radiation.
More particularly, the invention in one broad aspect provides an infrared heat treating apparatus comprising an infrared radiation emitting infrared lamp extending along a longitudinal dimension from a first lamp end at one end of the dimension to a second lamp end at an opposite end of the dimension. An infrared transparent conduit extends from a first conduit end to a second conduit end and has wall means for defining a conduit interior, the lamp being disposed within the interior in spaced relation to the wall means. The conduit is open at both the first and second conduit ends and means is provided for admitting a cooling fluid to the interior by admission of the fluid into the first conduit end at a flow rate controlled in response to measured parameters with the fluid flowing through the conduit between the lamp and the wall means and discharged from the conduit at the second conduit end.
III. BRIEF DESCRIPTION OF THE DRAWINGS
- Fig. 1 is a side elevation view of a fluidizing bed furnace according to the present invention, with a portion of an outer skin removed to expose certain interior elements of the furnace.
Fig. 2 is an enlarged view of certain of the -interior elements of the furnace of Fig. 1, with bus plates r shown removed.
Fig. 3 is a side elevation view, shown partially in section, showing connection of infrared heating elements to /~
bus plates. -Fig. 4 is a side elevation schematic representation of the furnace of the present invention.
Fig. 5 is an end elevation view, shown schematically, of the furnace of the present invention.
Fig. 6 is a top plan view, shown schematically, of the furnace of the present invention. -2A ~ 9`~ ~
IV. DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the various figures in which identical elements are numbered identically throughout, the description of the preferred embodiment will now be given with reference to a furnace 10. Shown best in Figs. 4 and 5, the furnace 10 includes a retort 12, which is preferably formed of R330 stainless steel or the like.
The retort 12 includes a bottom wall 14, end walls 15, 16 and side walls 17, 18. Walls 14 - 18 WO92~K780 PCT/US91/07537 3 2~93632 cooperate to define a retort interior 20. A cover (not shown in the Figures) may be pro~ided to co~er the top of the retort 12.
The furnace 10 also includes an outer shell 22 shown best in Figs. 5 and 6. Outer shell 22 includes a first outer shell wall 24 covering wall 17, and a second outer shell wall 26 covering wall 18. In Fig. 1, a central portion of shell wall 24 has been removed to eYpose wall 17. Wall 24 and wall 17 cooperate to define an exhaust plenum 28. Walls 26 and 18 cooperate to define an inlet plenum 30.
As best shown in Figs. 4 and 6, interior divider wall~ 31 and 32 are provided within the interior 20. Walls 31, 32 extend between side w811s 17 and 18 and are parallel to end walls 15 and 16. The divider walls 31, 32 extend from floor 14 partially toward the top of the retort 12. Walls 31, 32 divide retort interior 20 into a fluidizing chamber 2OA ~ a first overflow chamber 20b, and a second overflow chamber 20c (see Fig. 4).
A plurality of quartz tubes 36 are plurality exten~ing between snd through walls 17 and 18. As shown, the tubes 36 are disposed in parallel alignment, generally perpendicular to side walls 17, 18 and parallel to the floor 14 of the retort 12. The tubes 36 are disposed within the fluidizing portion 20a of interior 20, and are located beneath a predetermined elevation 38 (see Fig. 4) of fluidizing particles to be retAjne~ within the chamber 20a.
Fig. 3 shows attachment of the tube 36 to side wall 17. The quartz tube 36 is similarly attached to side wall 18. As shown in Fig. 3, the tube 36 extends through side wall 17, and is connected to the side wall 17 by a steel mounting clamp 40. The clamp 40 houses a plurality of ceramic washers 42. The clamp 40 is attached to side wall 17 by bolts 44.

WOg2/06780 PCT/US91/07~37 An infrared lamp 46 is disposed within each of tubes 36, as best shown in Figs. 2, 3, 5 and 6, (for clarity, lamps are not shown within the tubes 36 in Figs. 1 and 4). The lamp 46 is completely contained between walls 17, 18, and is retAine~ in co~Yi alignment within tube 36 by a mounting clip 48.
To provide electrical energy to the plurality of lamps 46, a plurality of bus bar plates 50 sre provided. (For clarity bus bar plates are not shown in Figs. 1 and 4.) As shown in Fig. 2, nine bus bar plates are provided for each side 17, 18 of the retort 12. In the schematic representation of Fig. 6, eight bus bar plates are shown on each side.
The bus bar plates 50 are electrically conductive plates of metal. Each plate 50 is connected to a separately controllable source (not shown) of electricsl power to enerqize the plate 50.
The plates 50 are secured to the walls 17, 18 by bus bar plate mounts 52 (see Fig. 3), which are preferably ceramic. A lead 54 connects the infrared lamp 46 to the bus bar plate 50. The lead 54 is connected to the bus bar plate 50 by a nut and bolt combination 56.
As best shown in Fig. 2, a plurality of lamps 46 are covered by any given bus bar plate 50. In the e~pAnAed view of Fig. 2, each of the bus bar plates 50 is removed from covering the lamps 46 and tubes 36. The positioning of the bus bar plates 50 over the lamps 46 in Fig. 2 is shown in phantom lines. As a result of having a plurality of lamps 46 covered by a plurality of different bus bar plates 50, the length of the fluidizing chamber 20a can be divided into a plurality of zones. Each bus bar plate 50 with its associated lamps 46 constitutes a given zone. By separately regulating a current to each bus bar plate 50, the intensity of the lamps connected to each bus bar plate 50 can be separately controlled. As a result, a WO9~4Kq80 PCT/US91/07537 i~O~3~

temperature gradient can be created across the length of the chA~h~r 20a.
Shown in Figs. 1, 4 and 5, a stainless steel screen 60 is placed above the lamps 46 and quartz tubes 36. The screen 60 prevents a product that is being heat treated from falling onto the quartz tubes 36 and possibly damaging them.
Fluidizing tubes 62 are provided disposed between the floor 14 and the quartz tubes 36. The tubes 62 are connected via conduit 64 to a source (not shown) of a fluidizing gas. The fluidizing gas may be air or any inert gas such as nitrogen. The fluidizing tubes 62 may be such as those shown and d~scribed in u.S. Patent No. 4,752,061 and indicated by reference numerals 98 therein.
A coolant mechAnism is provided to pass a cooling fluid (preferably air) through the tubes 36 to cool the infrared lamps 46. A blower 70 is provided connected to inlet plenum 30. An exhaust fan (not shown) may be connected through an exhaust conduit 72 to eYhAt~st plenum 28. As a result, cooling air may be forced from plenum 30 through each of tubes 36 into plenum 28 and out exhaust conduit 72.
A bed of fluidizing particles (preferably granular aluminum oxide) is provided within the retort 12. A first layer 80 of coarse particle (preferably of 12 grit size) is provided covering the fluidizing tubes 62 and terminating beneath the quartz tubes 36. Finer aluminum oxide sand (preferably of 100 grit size) rests on top of the coarser sand 80, and terminates at level 38. The coarser sand 80 diffuses the fluidizing gas from the fluidizing tubes 62, and distributes it evenly to the quartz tubes 36.
In operation, the infrared lamps 46 may heat from 0 -4000 F. The aluminum oxide will heat from 0 -2100 F. A controller 100 (schematically shown in Fig.
2) is connected through control lines 102 to each of bus WOg2/06780 PCT/US91/07537 plates 50. Through operation of controller 100, the potential on each of bus plates 50 may be separately controlled. Accordingly, the plurality of infrared lamps 46 are divided into a plurality of separately controllable zones.
In operation, the lamps 46 heat the aluminum oxide. The fluidizing gas from tubes 62 fluidizes the aluminum oxide. The divider walls 31, 32 capture within chambers 20b and 20c any aluminum oxide which spills out of the fluidizing chamber 20a.
Each of lamps 46 and tubes 36 compri~e a lamp assembly 37 (shown numbered in Figs. 3, 5 and 6). As previously inAic~ted, a cooling gas is passed through the lamp aQsemblies 37. In operation, the temperature of the apparatus c~n be quite high. For example, the temperature surrounding the assemblies 37 will commonly exceed 2,100 F. At temperatures in excess of 1,500 F, the quartz tubes 36 may deteriorate. For example, from 1,500 to 1,800 F, quartz softens and sags.
The air passing through the quartz tubes 36, cools the quartz tubes 36 to prevent sagging. However, the air flow can adversely effect the efficiency of the infrared lamps 46. Accordingly, air flow through the quartz tubes 36 must be balanced to provide sufficient cooling to prevent the quartz tubes 36 from sagging while minimizing the adverse impact on the efficiency of the lamps 46.
To achieve the desired hAlAncing, air flow through quartz tubes 36 is preferably only provided when the temperature of fluidized the bed 38 exceeds a predetermined temperature in a preferred embodiment, the predetermined temperature is 1,500 F.
The amount of air flow through the tubes 36 is selected to balance the thermal energy on the tubes 36.
Namely, the bed 38 draws thermal energy from the tubes 36. If the thermal energy drawn from the tubes 36 is insufficient to keep the temperature of the tubes 36 WO ~06780 PCT/US91/07~37 ~_ 7 2 09 3 6 3 2 below the predeterri n~d temperature, air flow is passed through the tubes 36 at a rate selected to draw energy away from the tubes 36. The amount of air flow is a function of the length of the tubes 36, the voltage across the lamps 46 and the ambient temperature (i.e., the temperature of the bed in the immedi~te vicinity of the tubes 36). The actual amount of sir flow is empirically derived for a given apparatus 10 and will vary with the operating process in which it is used.
To achieve the balancing, a thermocouple 100 (schematically shown only in Fig. 5) $s provided for sensing the temperature within bed 38 in the vicinity of the tubes 36. ThermGcou~le 100 provides a signal to a controller 102. The controller 102 also receives an input from a voltage censor 104 which een~s a voltage across the lamps 46. Comparing the voltage on the lamps 46 and the temperature within bed 38, the controller 102 operates blower ?0 to force coolant gas through the quartz tubes 36 when the temperature within the bed 38 exceeds the predetermined temperature. The air flow through the quartz tubes 36 is selected to be an increasing function of the voltage across the lamps 46 and to be increasing with the increased temperature measured by thermocouple 100. The increasing function 2~ is selected for the air flow to be the minimum air flow necessary to prevent deterioration of the quartz tubes 36.
Through the foregoing detailed description of the present invention, it has been shown how the invention has been obtained in a preferred manner.
However, modifications and equivalents of the disclosed concepts, such as those which will readily occur to one skilled in the art, are inte~A~ to be included within the scope of this invention.

Claims (12)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:
1. An infrared heat treating apparatus comprising:
an infrared radiation emitting infrared lamp extending along a longitudinal dimension from a first lamp end at one end of said dimension to a second lamp end at an opposite end of said dimension;
an infrared transparent conduit extending from a first conduit end to a second conduit end and having wall means for defining a conduit interior, said lamp disposed within said interior in spaced relation to said wall means;
said conduit open at both said first and second conduit ends;
means for admitting a cooling fluid to said interior by admission of said fluid into said first conduit end at a flow rate controlled in response to measured parameters with said fluid flowing through said conduit between said lamp and said wall means and discharged from said conduit at said second conduit end.
2. An apparatus according to claim 1 wherein said conduit wall means is deformable in response to a heat generated by said lamp when a temperature at said wall means exceeds a predetermined minimum temperature;
control means for admitting said cooling fluid to said interior when said temperature at said wall means exceed said predetermined minimum.
3. An infrared heat treating apparatus according to claim 1 wherein said lamp of infrared radiation has an intensity proportional to a voltage applied to said lamp;
control means for controlling admission of said cooling fluid to said interior with said control means admitting said fluid at a rate responsive to a voltage applied to said lamp.
4. An apparatus according to claim 1 wherein said conduit is quartz.
5. An infrared heat treating apparatus comprising:
a source of infrared radiation including an infrared radiating lamp;

an infrared transparent conduit having wall means for defining a conduit interior, said lamp disposed within said interior;
means for admitting a cooling fluid to said interior;
said conduit wall means deformable in response to a heat generated by said lamp when a temperature at said wall means exceeds a predetermined minimum temperature;
measuring means for measuring a temperature at said wall means;
control means responsive to said temperature at said wall means as measured by said measuring means for admitting said cooling fluid to said interior when said temperature at said wall means exceeds said predetermined minimum temperature, with said control means further selected to admit said cooling fluid at a minimum rate sufficient for said wall means to be cooled below a temperature at which deformation of said wall means occurs and with said control means substantially reducing said rate when said temperature is less than said predetermined minimum to a rate selected to avoid inefficiency of said infrared lamp.
6. An infrared heat treating apparatus comprising:
a source of infrared radiation including an infrared radiating lamp;
an infrared transparent conduit having wall means for defining a conduit interior, said lamp disposed within said interior;
said lamp has an intensity proportional to a voltage applied to said lamp;
measuring means for measuring said voltage applied to said lamp;
control means for controlling admission of said cooling fluid to said interior with said control means including means for admitting said fluid at a rate responsive to said voltage applied to said lamp as measured by said measuring means with said rate increasing in response to an increase in said voltage.
7. An apparatus according to claim 5 wherein said conduit is quartz.
8. An apparatus according to claim 5 wherein said source is an infrared lamp.
9. An apparatus according to claim 6 wherein said conduit is quartz.
10. An apparatus according to claim 6 wherein said source is an infrared lamp.
11. An infrared heat treating apparatus according to claim 5 wherein said lamp has an intensity proportional to a voltage applied to said lamp;
said control means further including means for controlling admission of said cooling fluid to said interior with said control means admitting said fluid at a rate responsive to a voltage applied to said lamp, with said rate increasing in response to an increase in said voltage.
12. An infrared heat treating apparatus according to claim 6 further comprising:
means for measuring a temperature at said wall means;
said conduit wall means deformable in response to a heat generated by said lamp when a temperature at said wall means exceeds a predetermined minimum temperature;
said control means including means responsive to said temperature at said wall means for admitting said cooling fluid to said interior when said temperature at said wall means exceeds said predetermined minimum, with said control means further selected to admit said cooling fluid at a minimum rate sufficient for said wall means to be cooled below a temperature at which deformation of said wall means occurs and with said control means substantially reducing said rate when said temperature is less than said predetermined minimum to a rate selected to avoid inefficiency of said infrared lamp.
CA002093632A 1990-10-16 1991-10-15 Coolant controlled ir (infrared) heat treat apparatus Expired - Fee Related CA2093632C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59839190A 1990-10-16 1990-10-16
US598,391 1990-10-16

Publications (2)

Publication Number Publication Date
CA2093632A1 CA2093632A1 (en) 1992-04-17
CA2093632C true CA2093632C (en) 1996-04-23

Family

ID=24395368

Family Applications (1)

Application Number Title Priority Date Filing Date
CA002093632A Expired - Fee Related CA2093632C (en) 1990-10-16 1991-10-15 Coolant controlled ir (infrared) heat treat apparatus

Country Status (4)

Country Link
EP (1) EP0553303A1 (en)
JP (1) JPH06501059A (en)
CA (1) CA2093632C (en)
WO (1) WO1992006780A1 (en)

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3688422T2 (en) * 1985-08-07 1993-08-26 Samuel Strapping Systems Ltd HEATING A FLUID BED.
US4818849A (en) * 1987-07-13 1989-04-04 Matlen Abraham J Shielded lamp unit
DE3841448C1 (en) * 1988-12-09 1990-05-10 Heraeus Quarzschmelze Gmbh, 6450 Hanau, De

Also Published As

Publication number Publication date
EP0553303A1 (en) 1993-08-04
CA2093632A1 (en) 1992-04-17
JPH06501059A (en) 1994-01-27
WO1992006780A1 (en) 1992-04-30

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