IE43321B1 - Improvements in or relating to depositing metal on a surface of a metal workpiece - Google Patents
Improvements in or relating to depositing metal on a surface of a metal workpieceInfo
- Publication number
- IE43321B1 IE43321B1 IE229276A IE229276A IE43321B1 IE 43321 B1 IE43321 B1 IE 43321B1 IE 229276 A IE229276 A IE 229276A IE 229276 A IE229276 A IE 229276A IE 43321 B1 IE43321 B1 IE 43321B1
- Authority
- IE
- Ireland
- Prior art keywords
- metal
- light
- workpiece
- incipient fusion
- deposit
- Prior art date
Links
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 238000000151 deposition Methods 0.000 title claims abstract description 14
- 230000004927 fusion Effects 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000004044 response Effects 0.000 claims abstract description 13
- 238000001579 optical reflectometry Methods 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 16
- 238000002310 reflectometry Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims 2
- 238000002844 melting Methods 0.000 description 13
- 230000008018 melting Effects 0.000 description 13
- 230000005855 radiation Effects 0.000 description 6
- 238000009529 body temperature measurement Methods 0.000 description 3
- QFXZANXYUCUTQH-UHFFFAOYSA-N ethynol Chemical group OC#C QFXZANXYUCUTQH-UHFFFAOYSA-N 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000012255 powdered metal Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000012080 ambient air Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000031070 response to heat Effects 0.000 description 1
- 230000011664 signaling Effects 0.000 description 1
- 238000004861 thermometry Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
- C23C26/02—Coating not provided for in groups C23C2/00 - C23C24/00 applying molten material to the substrate
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Radiation Pyrometers (AREA)
- Coating By Spraying Or Casting (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Nozzles (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Physical Vapour Deposition (AREA)
- Investigating Or Analyzing Materials Using Thermal Means (AREA)
Abstract
In a method and an apparatus for depositing metal on a surface of an article, the surface of the article is heated to a state of incipient fusion. During the heating, a light beam is directed at the surface and the light reflectivity of the surface is detected. At the time of incipient fusion, an electrical control signal is created from the light reflections. Metal is deposited on the surface of the article after incipient fusion thereof and control of the deposit of the metal is effected in response to the electrical control signal.
Description
This invention relates to depositing metal on a surface of a metal workpiece.
Typical prior methods and. apparatus for depositing metal on a metal workpiece have relied upon the attainment of a particular temperature in the workpiece as an indication of the appropriate time for applying the metal material, or reliance was placed upon the visual judgement of the operator. In such prior art methods and apparatus, the workpiece is heated until the surface becomes molten and visually appears to be wet” and when the surface is judged to be uniformly 11 wet11 the metal material is applied. Due to variations in the composition of the material of the workpiece, melting temperature can fluctuate, and thus temperature measurement alone is not a reliable technique for determining surface melting. Further, relying on the judgement of the operator is not as efficient or reliable as automatic control.
It is an object of the present invontion to provide a better indication of the precise, point at which the metal material should be applied, namely, at incipient fusion of the base metal.
The invention includes a method of depositing metal on a surface of a metal workpiece comprising the steps of, heating at least the surface of the workpiece to a state of incipient fusion.
directing a light beam at the surface during heating, detecting the light reflectivity of the surface including reflectivity at the time of incipient fusion and creating an electrical control signal from the light reflections from the surface at the time of incipient fusion of the surface,
- 3 depositing the metal on the surface after incipient fusion thereof, and controlling deposit of metal on the surface in response to said electrical control signal.
The invention also includes apparatus for use in a method as defined in the last preceding paragraph, said apparatus comprising, means for heating at least the surface of the workpiece to a state of incipient fusion, means for directing a light beam at the surface during heating, means for detecting the light of reflectivity of the surface including reflectivity at the time of incipient fusion and for creating an electrical control signal from the
IS light reflections from the surface at the time of incipient fusion of the surface, means for effecting deposit of the metal on the surface after incipient fusion thereof, and means for controlling the deposit of metal on the 20 surface in response to said electrical control signal.
In a preferred embodiment of the present invention, which is described hereinafter, a light source and a means such as a rotating shutter for modulating the output of the light source produces a train of Light pulses, which are directed onto the surface being heated, and means arc provided for receiving the reflections of the train of light pulses from the surface. A photocell responsive to the reflected pulse train is used to generate an electrical control signal in response to the reflected pulses which it receives. The electrical control signal thus generated is visually observed as by means of a cathode ray oscilloscope or provides a controlling signal to a servomechanism, which controls the deposit of the material in a variety of ways by controlling a function or functions of metal depositing apparatus.
- 4 Interference from ambient or extraneous light sources is minimized by a suitable selection of the modulating frequency of the light source, and by employing a monochromatic source or, a color-limiting filter and a photocell which is responsive to the output of the filter.
Accordingly, a precise indication of the time of incipient fusion is provided and a control function is effected in response thereto. The deposit of the metal, on the surface is effected at the appropriate time and is not affected by the above-noted problem with regard to sensing of temperature of the workpiece. Further, obviously human error is avoided and eliminated, due to the fact that visual judgement is not utilized in the system to sense incipient fusion.
In order that the invention may be well understood the preferred embodiments referred to above, which is given by way of examply only, will now be described in more detail, reference being had to the accompanying drawings, in which:
Fig..1 is a somewhat schematic view of an assembly for depositing material on a surface of a workpiece;
Fig. 2 is a view partly in elevation and partly in cross section of a light modulating means and a detector which may be employed in the assembly of Fig 1;
Fig. 3 is a circuit diagram including a photocell of the detector of Fig 2.
Fig. 4 is a view of a cathode ray oscilloscope screen showing the type of indication presented when the surface of the workpiece to receive material has not yet reached fusion;
Fig. 5 is a view similar to Fig. 4 but showing the indication when the surface of the workpiece reaches incipient fusion;
- 5 Fig. 6 is a schematic view of an apparatus for depositing metal on a surface of a workpiece; and
Fig, 7 is a schematic view of a modification to the apparatus of Figure 6.
In Fig. 1 reference numeral 10 indicates generally a metal workpiece to which a metal (weld) deposit is to be applied. As indicated by an arrow, the workpiece 10 is mounted for rotation about its axis in a suitable support (not shown). An oxyacetylene torch 13 or other suitable heating means directs the flame at the portion of the workpiece 10 to which a deposit of weld material from a weld filler rod is to be applied. The plastic or non-plastic condition of the workpiece 10 is monitored by the combination of a light source identified generally at reference numeral which directs a modulated train of light pulses at the workpiece 10 and a detector generally indicated at numeral which picks up the reflections from the workpiece.
A suitable light source and detector structure are illustrated in Fig. 2 of the drawings. The light source may, for example, be an incandescent bulb 17 which emits polychromatic light. Monochromatic light sources, such as lasers, are, however, equally usable. The bulb 17 is mounted within a rotating shutter l8 in which a plurality of spaced windows 19 are formed. The shutter is driven at a suitably high velocity by means of a drive motor 20. The output of the light source is a train of essentially square wave light pulses which are directed by means of one or more lenses 21 at the surface to be observed. Alternatively, one may use a fiber optic bundle to direct the light at the surface.
The detector includes a housing 22 at one end of which there are one or more lenses 23 which focus the reflected light through a band-limiting filter 24 onto a photocell 25.
Advantage is taken of the phenomenon that a molten surface is much more reflective than a solid surface immediately prior to melting. Prior to surface melting, any
- 6 33321
LO reflection from the surface of the workpiece 10 is diffuse.
As the surface begins to melt, the reflection becomes specular so that more light goes into the lens system. The detector 16 focuses this reflected light through the filter 24 upon the photocell 25. The chromatic range of the filter and the photocell 25 are selected so as to minimize the response to heat-induced radiation from the heated surface and radiation froqi the heating torches 13, thus avoiding saturation of the photocell. The filter and photocell responses may be centred in the yellow-green range, thus blocking the light in the blue and red spectra, which are prevalent in the ambient.
The response to the photocell 25 in the reflectometer detector varies as a function of the light impinging upon the surface of the photosensitive material of the photocell.
The light emitted from the surface on which metal is to be deposited is composed of radiant energy due to its temperature, reflected ambient light, and reflected light from the modulated light source. The radiant portion is virtually steady state compared to the modulating frequency and is not a periodic function. The ambient light may be composed of time variable light, but when summed from the various sources, the time variations are minimized due to phase shifting, Supression of ambient light variations may be obtained by appropriate selection of the light source modulating frequency and the detector time response sensitivity so as to minimize the effects of ambient light variations, such as those resulting from the 50 to 60 Hertz power line frequency. Consequently, the majority of the light variations being detected by the photocell and associated circuitry is due to reflection of the modulated light source beam from the workpiece surface.
Referring to Fig. 3, the photocell 25 is connected in series with a direct current power source 26 and a load resistor 27. The voltage across the load resistor 27 varies inversely as a function of the photocell resistance.
An A.C. voltage measuring instrument provided with a blocking
49321
- Ί capacitor 29 is connected across the load resistor to measure only the time variable voltages and supresses the slowly varying and steady state voltages. Therefore, an increase in time variable voltage indicates an increase in reflectance of time variable light. Since the workpiece on which material is being deposited is virtually a diffuse reflector during heating and a specular reflector when the surface melts, a sudden increase in the time variable voltage signifies surface melting.
It should be recognized that the voltage measuring instrument 28 may take a variety of forms, such as a voltmeter, a cathode ray oscilloscope, or the signals may he used as shown in Figs. 6 and 7 to operate a servosystem or the like to control the deposit of the material when the voltage variation across the load resistor 27 signifies that the surface is sufficiently plastic.
In Fig. 4 there is shown a cathode ray oscilloscope screen 30 having a trace 31 thereon which is indicative of the absence of significant time variable voltage. Fig. 5 illustrates a trace 32 which is obtained when the detector circuit is receiving a considerable amount of reflected modulated light, indicative of surface melting. Comparison of these two figures shows the significant increase in reflectivity of the workpiece surface when fusion is achieved.
Unlike optical pyrometers or radiation thermometers tho illustrated detection apparatus does not detect surface melting by temperature measurement as such, but rather by sensing the phase change from solid to liquid. Determination of the surface temperature by radiation thermometry is limited in accuracy by the precision of the emissivity function for the material being measured, since the radiated energy from any object due to the temperature is a function of the temperature and the emissivity.
Using heating time as a method for signaling surface melting is unreliable due to fluctuations in the surrounding
3321
- 8 environment. Although the energy being released by an oxyacetylene torch or other heating means can be determined or calculated with appropriate apparatus, the energy being absorbed by the material being heated is influenced by many factors. The most significant factor is the presence of ambient air currents which tend to remove heat from both the oxyacetylene flame and the surface being heated. Also, the material composition and the surface conditions influence the rate at which heat is absorbed.
In addition, due to variations in the material composition, temperature measurement alone is not a reliable technique for determining surface melting. With each class or grade of various metals, the compositional ranges for the Constituent elements cause the melting point temperature to fluctuate. Therefore, melting is not a function solely of temperature, but also of metallurgical composition.
The illustrated apparatus and its use has numerous advantages over the types of systems previously used. The apparatus signals melting by optically measuring the surface reflectance as the material changes from the solid to the liquid phase, rather than by heating time, temperature or some less accurate indication of surface melting. Also, operator judgement and error is eliminated.
The fundamental frequency of the modulated light source is arbitary and can be adjusted so as to minimize the effects of other time variable light sources. Typically, the modulating frequency is not near a multiple of 5θ or 60
Hertz, but is high enough to allow several cycles to occur during the transition from diffuse to specular reflection.
The system does not respond to variation in temperature induced radiation because such radiation varies slowly compared to the modulating frequency of the light source.
j Moreover, energy peaks in the red and infrared light spectra which might saturate the photosensitive device can be
- 9 supressed by a suitable filter. Similarly, light from oxyactylene torches and most other heating devices can be eliminated, since the light is of an essentially steady state nature; here too, the sensitivity range of the filter and the photocell can be chosen to avoid its peaks.
As noted hereinabove, the illustrated apparatus provides for the control of the deposit of metal onto the surface of the workpiece when the surface has reached the point of incipient fusion. The control of tho deposit of metal can be effected by control, of a function or functions in automatic equipment in response to the detector 16 sensing incipient fusion. Specifically, when the detector 16 senses incipient fusion, an electrical control signal is provided which is applied to suitable servomechanism to control a function in the automatic equipment.
Fig. 6 illustrates apparatus for automatic control and application of metal to a surface 4-0 of a metal workpiece 10. The workpiece is mounted in a workholder 41 so that it can be rotatably driven by a driving motor 46 which has an output shaft 44 with a gear 43 which meshes with ring gear 42 on the workholder 41 so as to drive the workpiece 10 and holder 41. A motor control 47 is connected to motor 46 and has a control knob 48 for adjusting the application of power from the power supply 50, The motor control 47 receives an output from the voltage measuring instrument 28 and causes the motor 46 to drive the workpiece 10 at a speed such that the surface 40 is heated to a temperature by torch 13 at which it reaches the condition of incipient fusion as detected by detector 16.
Metal is added to the metal surface 40 when it is at a temperature of incipient fusion from metal rod 57 which terminates near the surface 40 and melts and coats such surface. Rod 57 is supplied by a reel 58 mounted on a supporting shaft 59 and is controlled by a feed mechanism 56 which has a drive wheel 54 which engages the rod 57 to drive it toward the surface 40. A second drive motor 53
- ίο drives wheel 54 and receives an input from a second motor control 51. Motor control 51 receives a power supply 50 and an input control signal from the voltage measuring instrument 28. A control knob 52 allows the gain of the motor control 51 to be manually set.
In operation, the motor controls 47 and 51 are set by knobs 48 and 52 such that the motor 46 turns the workpiece 10 such that the surface 4θ under the torch is at the point of incipient fusion. The motor 53 supplies rod to the surface 4θ in the region of incipient fusion at a rate such that the desired amount of metal is applied to surface 40.
Thus, the detector 16 in the embodiment of Fig. 6 controls both the speed of rotation of the workpiece and the rate of feed of rod 57. By adjusting motor controls 47 and 51j optimum results will be obtained.
For example, at initiation of operation, the torch is lighted and motor 46 preferably rotates the workpiece until the surface 40 reaches the condition of incipient fusion. At such condition, the detector 16 produces an output which controls motor 46 to control rotational speed of the workpiece 10. In addition, metal feed is initiated by energizing motor 53.
Fig. 7 illustrates a modified apparatus wherein powdered metal is sprayed onto surface 40 instead of using a rod as in Fig. 6.
The workpiece is rotated by motor 46 under control of detector 16, as in Fig.6 but such structure is not illustrated. Powdered metal is fed from reservoir 63 through valve 62 to nozzle 64 which sprays it onto metal surface 40 in the area under incipient fusion. A valve control 6l, which can be a solenoid, controls valve 62 and receives an input from voltage measuring instrument 28.
The output of detector 16 thus detects the condition of incipient fusion of surface 40 and drives the workpiece through motor 46 and controls valve 62 to apply the proper amount of material to surface 4θ·
Claims (15)
1. CLAIMS:1. A method of depositing metal on a surface of a metal workpiece comprising the steps of, heating at least the surface of the workpiece to a 5 state of incipient fusion, directing a light beam at the surface during heating, detecting the light reflectivity of the surface including reflectivity at the time of incipient fusion and creating an electrical control signal from the light 10 reflections from the surface at the time of incipient fusion of the surface, depositing the metal on the surface after incipient fusion thereof, and controlling deposit of metal on the surface in response 1.5 to said electrical control, signal.
2. A method as claimed in claim 1, further including feeding metal toward the surface, and the controlling of the deposit of metal is effected by initiating the feeding of the metal in response to said control signal. 20
3. A method as claimed in claim 1 or 2, in which said light beam is a time modulated polychromatic beam.
4. A method as claimed in any one of the preceding claims, in which the light reflections are filtered to produce a beam of substantially monochromatic light. 25
5. Apparatus for use in a method of depositing metal on a surface of a metal workpiece as claimed in claim 1, said apparatus comprising, means for heating at least the surface of the workpiece to a state of incipient fusion, 30 means for directing a light beam at the surface during heating, means for detecting the light of reflectivity of the - 12 surface including reflectivity at the time of incipient fusion and for creating an electrical control signal from the light reflections from the surface at the time of incipient fusion of the surface means for effecting deposit of the metal on the surface after incipient fusion thereof, and means for controlling the deposit of metal on the surface in response to said electrical control signal.
6. Apparatus as claimed in claim 5, in which said means for directing said light beam comprises means for producing and directing a light beam composed of time modulated polychromatic light.
7. Apparatus as claimed in claim 6, in which means for directing said light beam comprises a light bulb and a rotating shutter.
8. Apparatus as claimed in claim 5, 6 or 7, in which said means for detecting includes a photocell and a voltage generating means for generating a time varying voltage from the reflections.
9. Apparatus as claimed in claim 8, which includes a monochromatic filter positioned to deliver a monochromatic beam of reflected, light to said photocell.
10. Apparatus as claimed in any one of claims 5 to 9, wherein said means for effecting deposit of the metal includes means for feeding the metal to the workpiece and said means for controlling comprises means for initiating feed of the metal in response to said electrical control signal.
11. Apparatus as claimed in claim 10, wherein said material is contained in a weld rod and said feed means comprises drive means for moving said rod.
12. Apparatus as claimed in claim 10, wherein said metal is a powder flame spray mixture and said feed means comprises a valve for controlling feed of said powder mixture. -
13. 13· Apparatus as claimed in any one of claims 5 to 12, further including means for rotating the workpiece while material is deposited thereon.
14. · A method of depositing metal on a surface of a 5 metal workpiece substantially as herein described with reference to the accompanying drawings.
15. Apparatus for use in a method of depositing metal on a surface of a metal workpiece, which apparatus is substantially as herein described with reference to Figure 6 10 or Figure 6 modified as shown in Figure 7 of the accompanying drawings.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/623,647 US3995073A (en) | 1974-04-08 | 1975-10-20 | Method for thermal deposition of metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| IE43321L IE43321L (en) | 1977-04-20 |
| IE43321B1 true IE43321B1 (en) | 1981-01-28 |
Family
ID=24498887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IE229276A IE43321B1 (en) | 1975-10-20 | 1976-10-18 | Improvements in or relating to depositing metal on a surface of a metal workpiece |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS5843184B2 (en) |
| AU (1) | AU499025B2 (en) |
| BE (1) | BE847416A (en) |
| BR (1) | BR7606555A (en) |
| CA (1) | CA1060730A (en) |
| DE (1) | DE2645345C3 (en) |
| DK (1) | DK147603C (en) |
| FR (1) | FR2328780A1 (en) |
| GB (1) | GB1545532A (en) |
| IE (1) | IE43321B1 (en) |
| IT (1) | IT1068410B (en) |
| MX (1) | MX143802A (en) |
| NL (1) | NL7611609A (en) |
| SE (1) | SE7610470L (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5274553A (en) * | 1975-12-17 | 1977-06-22 | Kobe Steel Ltd | Hard facing oxygennacetylene gas welding process |
| DE19545005A1 (en) * | 1995-12-02 | 1997-06-05 | Abb Patent Gmbh | Monitoring coating of a disk of high conductivity with material of low conductivity |
| JP5331965B2 (en) * | 2008-03-12 | 2013-10-30 | 富山県 | Automatic overlay welding system |
-
1976
- 1976-09-17 CA CA261,432A patent/CA1060730A/en not_active Expired
- 1976-09-20 GB GB3893476A patent/GB1545532A/en not_active Expired
- 1976-09-21 SE SE7610470A patent/SE7610470L/en not_active Application Discontinuation
- 1976-09-22 AU AU18034/76A patent/AU499025B2/en not_active Expired
- 1976-09-30 BR BR7606555A patent/BR7606555A/en unknown
- 1976-10-01 MX MX16651876A patent/MX143802A/en unknown
- 1976-10-04 FR FR7629828A patent/FR2328780A1/en active Granted
- 1976-10-06 IT IT2804376A patent/IT1068410B/en active
- 1976-10-07 DE DE19762645345 patent/DE2645345C3/en not_active Expired
- 1976-10-18 IE IE229276A patent/IE43321B1/en unknown
- 1976-10-19 BE BE171615A patent/BE847416A/en unknown
- 1976-10-20 DK DK473576A patent/DK147603C/en not_active IP Right Cessation
- 1976-10-20 JP JP51126021A patent/JPS5843184B2/en not_active Expired
- 1976-10-20 NL NL7611609A patent/NL7611609A/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| IT1068410B (en) | 1985-03-21 |
| NL7611609A (en) | 1977-04-22 |
| DK147603C (en) | 1985-04-22 |
| IE43321L (en) | 1977-04-20 |
| JPS5250950A (en) | 1977-04-23 |
| BR7606555A (en) | 1977-05-24 |
| AU1803476A (en) | 1978-04-06 |
| FR2328780A1 (en) | 1977-05-20 |
| GB1545532A (en) | 1979-05-10 |
| MX143802A (en) | 1981-07-17 |
| DK473576A (en) | 1977-04-21 |
| DE2645345C3 (en) | 1980-12-11 |
| FR2328780B1 (en) | 1980-12-26 |
| SE7610470L (en) | 1977-04-21 |
| BE847416A (en) | 1977-02-14 |
| DK147603B (en) | 1984-10-15 |
| DE2645345B2 (en) | 1980-04-24 |
| JPS5843184B2 (en) | 1983-09-26 |
| DE2645345A1 (en) | 1977-04-28 |
| AU499025B2 (en) | 1979-04-05 |
| CA1060730A (en) | 1979-08-21 |
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