US3841894A - Minimizing crazing of hot-dip aluminum coatings - Google Patents
Minimizing crazing of hot-dip aluminum coatings Download PDFInfo
- Publication number
- US3841894A US3841894A US00290612A US29061272A US3841894A US 3841894 A US3841894 A US 3841894A US 00290612 A US00290612 A US 00290612A US 29061272 A US29061272 A US 29061272A US 3841894 A US3841894 A US 3841894A
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- 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
- C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
- C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
- C23C2/12—Aluminium or alloys based thereon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/2419—Fold at edge
- Y10T428/24215—Acute or reverse fold of exterior component
- Y10T428/24223—Embedded in body of web
Definitions
- this Sh samples (26 gage) e coated n' am nuh type coated h hot eashy formed due to the silicon alloy bath compositions containing a variety of formahoh of a hrhhe hohaihhhhum alloy layer at the Mn and Fe concentrations. (See Table 1) Prior to coatmterface between the coatmg and ferrous substrate.
- adherent coatings are q hf the led for four minutes in ten percent l-lCl solution, and generally p y from aholll 4 to l 1% the hath fluxed by immersion in a saturated aqueous solution of to retard the rate of hy g between the bath metal K2ZrF6. After fluxing, the samples were dried so as to and the ferrous substrate.
- each sample was bent taken conluhchhh wlth the appended Claims 30 again sothat the next bend was over one sheet thickg zf m ness (1T).
- Samples were then bent over increasing hlustratlhh of a behdtest Spec" sheet thicknesses (see the FIGURE) until the number 9; t edeva of cram? tehdehcy' l d h of sheet thicknesses was reached in which no crazing m t 6 causes 0 crahmg revea e a was observed.
- Results are reported in Table l for both the S k propagatgd through masswe nehdle'shapeh (a) the number of sheet thicknesses over which sampartlcles 1n the coating. Electron-probe microanalysis plegwele bent to obtain no crazing, anddfol. (b) the of these i revehled a h contalhe-d bend condition. For each composition, the ratings reh and m "i always ported are the average of from four to eight different present in aluminum-coating baths.
- the benefits of this invention may therefore be achieved by utilizing the following procedure.
- the cleaned strip is bright annealed under a controlled atmosphere, thereby obviating the need for fluxing.
- the annealed strip is cooled, preferably entering the coating bath at a temperature slightly above that of the bath.
- the strip is maintained in a controlled atmosphere between the annealing furnace and the coating bath, thus permittingthe strip surface to alloy readily with the molten bath metal and form a continuous protective coating.
- the coated strip is then passed through an appropriate device, e.g. an air knife, for final control of the coating weight.
- Typical coating weights or thicknesses for sheet product vary from about 0.20 to about 1.0 ounces per square foot of sheet (i.e., about 0.4 to 2.0 mils thick per side).
- the coating bath generally contains from about 7 to about 9 percent silicon and is maintained at temperatures ranging from about 1,180"! to about l,300F.
- a preferred practice employs a Mn content of about 0.4 to 0.8 percent, in a bath maintained at a temperature of l,200l ,250F, wherein iron content thereof will be less than about 1.5 percent. It has been found that manganese contents within the above preferred range reduces the maximum iron solubility from about 2.5 percent (manganese-free bath) to less than about 1.5 percent. Thus, the addition of manganese offers a further advantage in that the reduced iron solubility decreases the rate of attack on the rigging.
- the improvement which comprises, adding Mn to said molten bath in an amount sufficient to maintain a concentration of from about 0.2 to about 1.5 percent.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Coating With Molten Metal (AREA)
Abstract
The crazing resistance of hot dip Al coatings is substantially improved by adding from about 0.2 to 1.5 percent Mn to the molten Al bath.
Description
United States Patent [19] Leonard [451 Oct. 15,1974
MlNlMlZlNG CRAZING 0F HOT-DIP ALUMINUM COATINGS [75] Inventor: Ralph W. Leonard, Plum Borough,
[73] Assignee: United States Steel Corporation, Pittsburgh, Pa. [22] Filed: Sept. 20, 1972 [21] Appl. No; 290,612
[52] US. Cl. 117/50, 117/114 C [51] Int. Cl. C23c 1/08 [58] Field of Search 117/51, 114 C, 50,114 R [56] References Cited UNITED STATES PATENTS 2,731,362 H1956 Brondyke ll7/5l 3,639,107 2/l972 Thompson ll7/l l4 C OTHER PUBLICATIONS Handbook of Chemistry and Physics, Chemical Rubber Publishing Co., 1949, pages 1975-1976.
Primary Examiner-Ralph S. Kendall Assistant Examiner.lacqueline Ware Attorney, Agent, or FirmArthur J. Greif [5 7 ABSTRACT The crazing resistance of hot dip Al coatings is substantially improved by adding from about 0.2 to 1.5 percent Mn t0 the molten Al bath.
5 Claims, 1 Drawing Figure 37 Bend /7' Bend 07' (Flat) Bend PAIENTEunm 151924 41394 37' Bend 7' Bend /F/af) Bend 1 MINlMlZING CRAZING OF HOT-DIP ALUMINUM COATINGS This invention relates to a hot-dipped, aluminized ferrous product with decreased tendency to crazing and to a method for producing am weight Mn to the aluminum-silicon bath will produce The art commonly employs two basically different a more. desirable g pe p f ffohsthueht molten baths for hot-dip aluminizing of ferrous sub- (w i F M are m comblnatlonl m h strates (sheet, strip, wire). For the production of bright final f hh The beneficial effect of Such Mh addl coated articles, the Si content is kept to minimum or hohs evidenced in the fohowlhg eXamPleS- residual values, generally below 0.25%. However, this Sh samples (26 gage) e coated n' am nuh type coated h hot eashy formed due to the silicon alloy bath compositions containing a variety of formahoh of a hrhhe hohaihhhhum alloy layer at the Mn and Fe concentrations. (See Table 1) Prior to coatmterface between the coatmg and ferrous substrate. ing the sampks were cleaned in i hl h l i kwhen formable: adherent coatings are q hf the led for four minutes in ten percent l-lCl solution, and generally p y from aholll 4 to l 1% the hath fluxed by immersion in a saturated aqueous solution of to retard the rate of hy g between the bath metal K2ZrF6. After fluxing, the samples were dried so as to and the ferrous substrate. The Of this is generleave a residue of powdered flu The samples emh) Presehtasadlscrete Phase the coahhg- {Although ployed in the bend tests were coated using identical significantly more adherent, these latter coatings nevdi i i e a bath temperature of l300F and an ertheless tend to craze, i.e., form fine cracks on the teni r i time of 60 seconds. Excess coating metal h Side formefl article Duflhg ubsequeht P9- and oxide residue were removed from the coated sheets sure. a d etr1mental iron-rust stam quickly develops in b use f an aipknift G i resistance was d t the f y of these h mined in controlled bend tests as described in ASTM It is therefore an ob ect of this invention to provide 525 71 Severity f Grazing was evaluated b ahlethofl for hllmmlllhg the crazlhg tendency of examination of the tension side at x magnification, (hp h wherein severity was rated as follows: 0--no crazing, Other ob ects and advantages of the mvention will be I crazing, 2 medium Grazing and 3 heavy h apparhht m a h g of the fohowmg f crazing. After a flat bend (0T), each sample was bent taken conluhchhh wlth the appended Claims 30 again sothat the next bend was over one sheet thickg zf m ness (1T). Samples were then bent over increasing hlustratlhh of a behdtest Spec" sheet thicknesses (see the FIGURE) until the number 9; t edeva of cram? tehdehcy' l d h of sheet thicknesses was reached in which no crazing m t 6 causes 0 crahmg revea e a was observed. Results are reported in Table l for both the S k propagatgd through masswe nehdle'shapeh (a) the number of sheet thicknesses over which sampartlcles 1n the coating. Electron-probe microanalysis plegwele bent to obtain no crazing, anddfol. (b) the of these i revehled a h contalhe-d bend condition. For each composition, the ratings reh and m "i always ported are the average of from four to eight different present in aluminum-coating baths. lt accumulates to samples v an equilibrium concentration, up to about three perw cent, by dissolution from the rigging and incoming 40 The beneficial effect provided by the purposeful adstrip.) It is believed that these particles are the brittle, dition of Mn (baths D through 0) can readily be seen intermetallic compound Fe Si Al The crystal strucfrom the above results. Thus, while additions within the ture of this compound is triclinic, and because of the range of from about 0.2 to 0.80% Mn provided the unsymmetrical nature of this lattice type, it grows as maximum resistance, even higher amounts of Mn proplatelets when it is the primary phase to solidify. These vided some enhancement in crazing resistance over the characteristics of Fe Si Al explain why the particles baths containing essentially no Mn (baths A through exhibit cleavage fracture during forming or bending op- "C).
u Mm TABLE l h Comparison of Crazing Tendency Number of Sheet Coating-Bath Bath" Thicknesses to Rating for Designation Composition \Vt.% Obtain No Crazing 3T Bend M K A 7.3 1.4 a 0.01 2.5 6,6 8.8 2.5 C (Ni 2.67 7.5 7.5 L5 D 0.23 2.5 7,6 3.4 0.4 E 0.37. 2.5 7.4 3,5 (7.5
F 0.54 0.90 7.7 2.2 ,0 G 0.52 1.71 7.6 3.8 0.4 H 0.48 2.37 7.6 4.1 0.8 1 0.63 1.22 7.7 3.0 1 0.4 .I 0.73 0.32 7.9 3.0 0 K 0.73 1.47 7.8 2.8 0.2 L 0.76 2.31 7.8 4.0 0.5 M 0.87 1.26 7.5 5.7 1.6 N 0.99 1.04 8.0 5.6 1.5 0 1.41 0.93 7.8 5.4 1.0
2 erations. It would therefore appear that the crack propagation tendency of these particles could be diminished if their morphology could be altered. it has now been found that the addition of from about 0.2 to about 1.5
'" Balance Aluminum The benefits of this invention may therefore be achieved by utilizing the following procedure. The cleaned strip is bright annealed under a controlled atmosphere, thereby obviating the need for fluxing. The annealed strip is cooled, preferably entering the coating bath at a temperature slightly above that of the bath. To prevent oxidation, the strip is maintained in a controlled atmosphere between the annealing furnace and the coating bath, thus permittingthe strip surface to alloy readily with the molten bath metal and form a continuous protective coating. The coated strip is then passed through an appropriate device, e.g. an air knife, for final control of the coating weight. Typical coating weights or thicknesses for sheet product vary from about 0.20 to about 1.0 ounces per square foot of sheet (i.e., about 0.4 to 2.0 mils thick per side).
The coating bath generally contains from about 7 to about 9 percent silicon and is maintained at temperatures ranging from about 1,180"! to about l,300F. A preferred practice employs a Mn content of about 0.4 to 0.8 percent, in a bath maintained at a temperature of l,200l ,250F, wherein iron content thereof will be less than about 1.5 percent. It has been found that manganese contents within the above preferred range reduces the maximum iron solubility from about 2.5 percent (manganese-free bath) to less than about 1.5 percent. Thus, the addition of manganese offers a further advantage in that the reduced iron solubility decreases the rate of attack on the rigging.
I claim:
l. in the method for hot-dip aluminizing of ferrous substrates to produce a protective coating thereon. which comprises; cleaning said substrate and thereafter passing said substrate through a bath of molten aluminum consisting essentially of from about 4 to 11% Si, from about 0.1 to about 3.0% Fe,
the improvement which comprises, adding Mn to said molten bath in an amount sufficient to maintain a concentration of from about 0.2 to about 1.5 percent.
2. The method of claim 1, wherein the bath is maintained at a temperature of from about 1,1 F to 1,300F and the Mn content of the bath is within the range of from about 0.4 to 0.8 percent.
3. The method of claim 2, wherein said bath temperature is about 1,200F to 1,250F and the Fe content is less than about 1.5 percent.
4. The method of claim 2, wherein the Si content of said bath ranges from about 7 to about 9 percent.
. 5. The method of claim 4, wherein the final thickness of said protective coating ranges from about 0.4 to about 2.0 mils; said bath is maintained at a temperature of about 1,200F to 1,250F and the Fe content is less than about l.5 percent.
a; i a:
Claims (5)
1. IN THE METHOD FOR HOT-DIP ALUMINIZING OF FERROUS SUBSTRATES TO PRODUCE A PROTECTIVE COATING THEREON, WHICH COMPRIES, CLEANING SAID SUBSTRATE AND THEREAFTER PASSING SAID SUBSTRATE THROUGH A BATH OF MOLTEN ALUMINUM CONSISTING ESSENTIALLY OF FROM ABOUT 4 TO 11% SI, FROM ABOUT 0.1 TO ABOUT 3.0% FE, THE IMPROVEMENT WHICH COMPRISES, ADDING MN TO SAID MOLTEN BATH IN AN AMOUNT SUFFICIENT TO MAINTAIN A CONCENTRATION OF FROM ABOUT 0.2 TO ABOUT 1.5 PERCENT.
2. The method of claim 1, wherein the bath is maintained at a temperature of from about 1,180*F to 1,300*F and the Mn content of the bath is within the range of from about 0.4 to 0.8 percent.
3. The method of claim 2, wherein said bath temperature is about 1,200*F to 1,250*F and the Fe content is less than about 1.5 percent.
4. The method of claim 2, wherein the Si content of said bath ranges from about 7 to about 9 percent.
5. The method of claim 4, wherein the final thickness of said protective coating ranges from about 0.4 to about 2.0 mils; said bath is maintained at a temperature of about 1,200*F to 1,250*F and the Fe content is less than about 1.5 percent.
Priority Applications (16)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00290612A US3841894A (en) | 1972-09-20 | 1972-09-20 | Minimizing crazing of hot-dip aluminum coatings |
ZA737248*A ZA737248B (en) | 1972-09-20 | 1973-09-11 | Minimizing crazing of hot-dip aluminum coatings |
AU60244/73A AU476750B2 (en) | 1972-09-20 | 1973-09-12 | Minimizing crazing of hot-drip aluminum coatings |
BR7215/73A BR7307215D0 (en) | 1972-09-20 | 1973-09-18 | PROCESS FOR COVERING ALUMINUM IRON SUBSTRATES, AND THE COATED FERROUS SUBSTRATE |
GB4374773A GB1445693A (en) | 1972-09-20 | 1973-09-18 | Reducing crazing of hot-dip aluminum coatings |
JP48105827A JPS4993232A (en) | 1972-09-20 | 1973-09-19 | |
ES418900A ES418900A1 (en) | 1972-09-20 | 1973-09-19 | Minimizing crazing of hot-dip aluminum coatings |
AR250159A AR197633A1 (en) | 1972-09-20 | 1973-09-19 | METHOD OF ALUMINIZING FERROUS SUBSTRATES BY HOT DIPPING |
CA181,459A CA1003711A (en) | 1972-09-20 | 1973-09-19 | Minimizing crazing of hot-dip aluminum coatings |
DE19732347206 DE2347206A1 (en) | 1972-09-20 | 1973-09-19 | PROCESS FOR APPLYING ALUMINUM PROTECTIVE COATING TO IRON SUBSTRATES AND SUBSTRATES COATED WITH SUCH |
AT806773A AT327635B (en) | 1972-09-20 | 1973-09-19 | PROCESS FOR COATING AN IRON SUBSIDY WITH AN ALUMINUM TOP LAYER |
IT7369772A IT999572B (en) | 1972-09-20 | 1973-09-19 | PROCEDURE FOR ALUMINIZING LOST SUBSTRATES BY IMMERSION IN MOLTEN BATH |
PL1973165326A PL94432B1 (en) | 1972-09-20 | 1973-09-20 | METHOD OF SUBMERSIBLE ALUMINUM IRON SURFACE |
RO7300076128A RO63004A (en) | 1972-09-20 | 1973-09-20 | PROCESS FOR COATING ALUMINUM METAL TAPES |
FR7333824A FR2200373B1 (en) | 1972-09-20 | 1973-09-20 | |
BE135876A BE805116A (en) | 1972-09-20 | 1973-09-20 | MINIMUM REDUCTION OF SURFACE CRACKS IN ALUMINUM COATINGS APPLIED BY HOT IMMERSION |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00290612A US3841894A (en) | 1972-09-20 | 1972-09-20 | Minimizing crazing of hot-dip aluminum coatings |
Publications (1)
Publication Number | Publication Date |
---|---|
US3841894A true US3841894A (en) | 1974-10-15 |
Family
ID=23116791
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00290612A Expired - Lifetime US3841894A (en) | 1972-09-20 | 1972-09-20 | Minimizing crazing of hot-dip aluminum coatings |
Country Status (16)
Country | Link |
---|---|
US (1) | US3841894A (en) |
JP (1) | JPS4993232A (en) |
AR (1) | AR197633A1 (en) |
AT (1) | AT327635B (en) |
AU (1) | AU476750B2 (en) |
BE (1) | BE805116A (en) |
BR (1) | BR7307215D0 (en) |
CA (1) | CA1003711A (en) |
DE (1) | DE2347206A1 (en) |
ES (1) | ES418900A1 (en) |
FR (1) | FR2200373B1 (en) |
GB (1) | GB1445693A (en) |
IT (1) | IT999572B (en) |
PL (1) | PL94432B1 (en) |
RO (1) | RO63004A (en) |
ZA (1) | ZA737248B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5789089A (en) * | 1995-05-18 | 1998-08-04 | Nippon Steel Corporation | Hot-dipped aluminum coated steel sheet having excellent corrosion resistance and heat resistance, and production method thereof |
CN108774709A (en) * | 2018-05-31 | 2018-11-09 | 马鞍山钢铁股份有限公司 | It is a kind of that there is the reflexive hot-dip coated steel sheet of excellent thermal insulation and preparation method to light and heat |
US10287440B2 (en) | 2014-07-16 | 2019-05-14 | Thyssenkrupp Steel Europe Ag | Steel product with an anticorrosive coating of aluminum alloy and method for the production thereof |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3212181A1 (en) * | 1982-04-01 | 1983-10-06 | Nisshin Steel Co Ltd | Steel support for a lithographic printing plate, and method of producing it |
JPH0715964Y2 (en) * | 1988-06-25 | 1995-04-12 | 段谷産業株式会社 | Construction skirting |
IT1254402B (en) * | 1992-06-23 | 1995-09-14 | Sviluppo Materiali Spa | ALUMINUM-BASED COVERING FOR METALLIC PRODUCTS. |
CN107287543A (en) * | 2017-06-06 | 2017-10-24 | 上海大学 | Al Si systems alloy layer material, its preparation method and application |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2731362A (en) * | 1953-01-02 | 1956-01-17 | Aluminum Co Of America | Aluminum coating of ferrous metal articles |
US3639107A (en) * | 1969-07-22 | 1972-02-01 | Aluminum Co Of America | Hot-dip-aluminizing alloy |
-
1972
- 1972-09-20 US US00290612A patent/US3841894A/en not_active Expired - Lifetime
-
1973
- 1973-09-11 ZA ZA737248*A patent/ZA737248B/en unknown
- 1973-09-12 AU AU60244/73A patent/AU476750B2/en not_active Expired
- 1973-09-18 BR BR7215/73A patent/BR7307215D0/en unknown
- 1973-09-18 GB GB4374773A patent/GB1445693A/en not_active Expired
- 1973-09-19 AR AR250159A patent/AR197633A1/en active
- 1973-09-19 AT AT806773A patent/AT327635B/en not_active IP Right Cessation
- 1973-09-19 CA CA181,459A patent/CA1003711A/en not_active Expired
- 1973-09-19 IT IT7369772A patent/IT999572B/en active
- 1973-09-19 JP JP48105827A patent/JPS4993232A/ja active Pending
- 1973-09-19 DE DE19732347206 patent/DE2347206A1/en not_active Ceased
- 1973-09-19 ES ES418900A patent/ES418900A1/en not_active Expired
- 1973-09-20 PL PL1973165326A patent/PL94432B1/en unknown
- 1973-09-20 BE BE135876A patent/BE805116A/en unknown
- 1973-09-20 RO RO7300076128A patent/RO63004A/en unknown
- 1973-09-20 FR FR7333824A patent/FR2200373B1/fr not_active Expired
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2731362A (en) * | 1953-01-02 | 1956-01-17 | Aluminum Co Of America | Aluminum coating of ferrous metal articles |
US3639107A (en) * | 1969-07-22 | 1972-02-01 | Aluminum Co Of America | Hot-dip-aluminizing alloy |
Non-Patent Citations (1)
Title |
---|
Handbook of Chemistry and Physics, Chemical Rubber Publishing Co., 1949, pages 1975 1976. * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5789089A (en) * | 1995-05-18 | 1998-08-04 | Nippon Steel Corporation | Hot-dipped aluminum coated steel sheet having excellent corrosion resistance and heat resistance, and production method thereof |
US10287440B2 (en) | 2014-07-16 | 2019-05-14 | Thyssenkrupp Steel Europe Ag | Steel product with an anticorrosive coating of aluminum alloy and method for the production thereof |
CN108774709A (en) * | 2018-05-31 | 2018-11-09 | 马鞍山钢铁股份有限公司 | It is a kind of that there is the reflexive hot-dip coated steel sheet of excellent thermal insulation and preparation method to light and heat |
Also Published As
Publication number | Publication date |
---|---|
PL94432B1 (en) | 1977-08-31 |
CA1003711A (en) | 1977-01-18 |
FR2200373B1 (en) | 1976-10-01 |
RO63004A (en) | 1978-01-15 |
BR7307215D0 (en) | 1974-06-27 |
ES418900A1 (en) | 1976-03-01 |
ATA806773A (en) | 1975-04-15 |
GB1445693A (en) | 1976-08-11 |
JPS4993232A (en) | 1974-09-05 |
BE805116A (en) | 1974-03-20 |
AU6024473A (en) | 1975-03-13 |
ZA737248B (en) | 1974-08-28 |
AT327635B (en) | 1976-02-10 |
IT999572B (en) | 1976-03-10 |
DE2347206A1 (en) | 1974-03-28 |
AR197633A1 (en) | 1974-04-23 |
FR2200373A1 (en) | 1974-04-19 |
AU476750B2 (en) | 1976-09-30 |
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