CA1043673A - Organic coating characteristics of cold rolled steel - Google Patents
Organic coating characteristics of cold rolled steelInfo
- Publication number
- CA1043673A CA1043673A CA209,055A CA209055A CA1043673A CA 1043673 A CA1043673 A CA 1043673A CA 209055 A CA209055 A CA 209055A CA 1043673 A CA1043673 A CA 1043673A
- Authority
- CA
- Canada
- Prior art keywords
- heat treated
- steel
- rolling oil
- cold rolled
- rolled steel
- 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
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
Abstract
Abstract of the Disclosure The invention provides a novel method of increasing the corrosion resistance and improving the organic coating character-istics of cold rolled steel. In practicing the method, cold rolled steel in the as rolled condition having iron oxide and thermally degradable rolling oil on the surface thereof is heat treated at a temperature sufficiently elevated to thermally degrade the rolling oil. The surface of the cold rolled steel has a relatively low corrosion resistance and relatively poor organic coating character-istics initially, and the heat treatment is continued until the corrosion resistance and the organic coating characteristics of the resulting heat treated steel are improved. Thereafter the heat treated steel is cooled to a temperature sufficiently low to pre-vent further thermal degradation of the rolling oil and produce a residual film on the heat treated steel surface which imparts corrosion resistance and improved organic coating characteristics.
In a further variant of the invention, as rolled cold rolled steel of container stock gage is heat treated as described above, a hardenable fluid organic protective coating composition is applied to the resulting cooled heat treated steel, and thereafter the coating composition is hardened to produce contains: ?ock having a hardened coating of an organic protective coating thereon. The invention further provides the various products produced by the method of the invention.
In a further variant of the invention, as rolled cold rolled steel of container stock gage is heat treated as described above, a hardenable fluid organic protective coating composition is applied to the resulting cooled heat treated steel, and thereafter the coating composition is hardened to produce contains: ?ock having a hardened coating of an organic protective coating thereon. The invention further provides the various products produced by the method of the invention.
Description
. . , SPECIFICATION
The present invention is concerned with a novel method of increasing the corrosion resistance and improving the organic protective coating characteristics of cold rolled steel. In one of its more specific variants, the invention is further concerned ~ -with a novel process for preparing container stock having a harden-ed coating of an organic protective coating thereon from cold rolled steel in the as rolled condition. The invention is also concerned with the various products produced by the method of the , 10 invention.
Cold reduced flat rolled mild steel products having ~ ;
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;~, thicknesses not greater than about 0.065 inch are usually produced by cold rolling hot rolled strip in coil form from a con-tinuous hot strip mill. The sequence of operations involves uncoiling the ;~ hot rolled strip, passing the strip through a continuous picker, rinsing, drying, oiling with a cold reduction lubricant which also ^:
protects against rusting, and recoiling. The resulting hot rolled . ~ : :
~ strlp is subsequently uncoiled and passed through a continuous cold .~ ~
reduction~mill which has a plurality of stands with driven rolls.
; 20 Modern continuous cold reduction mills operate at high strip speeds ~ and often with heavy reductions in each stage and a large amount `~ of heat i9 generated by frictional contact between the roll sur-faces and the steel. The heat thus generated is removed by a system of~flood lubrication in which streams or jets of an aqueous dispension of cold rolling oil are directed against the roll bodies and~ the~surface of the steel. Following cold reduction to the desired gage, the cold rolled strip is coiled without removing the , ~ residual cold rolling oiI and other surface contaminants such as .. : i~
; iron oxide and dirt. Thereafter the strip may be side trimmed and ~,,; ~.
' given any further treatments that are necessary or desirable for a ~;
given end use. Inasmuch as the freshly cold rolled steel surface is very susceptible to rusting, often a protective coating is ~`~
applied. The protective coating may be metallic in nature such as in the production of tin plate, or an organic protective coat-~ ing may be applied such as in the production of lacquer or enamel g~ coated blackplate.
3 The preparation of cold rolled steel having an organic protective coating thereon from cold rolled steel in the as rolled condition presents a number of problems. One serious problem is ;
the above mentioned pronounced suaceptibility to rusting while in `-transit to the customer and during storage awaiting use. Unless the as rolled steel is given a temporary protective coating, often i: , rusting cannot be controlled at an acceptable level while awaiting application of the final organic protective coating. The temporary protective coating increases the production C09tS substantially ~-and usually adds very llttle, if any*hing, to the corrosion resis~
tance of the~final product. Thus, it would be possible to eIiminate the temporary protective coating and reduce costs provided suffi-;;2~0 ~ cient~corrosion resistance to provide an adequate floor life could bé imparted directly to the as rolled steel.
; Another important disadvantage of the cold rolled steel lies in the organic coating chàracteristics of the initial as rolled surface~ The residual~ cold rolling oil and perhaps other surface - -, ~ ;contamlnanta such as iron oxlde and dirt cause the as rolled steel surface~to have extremely~poor organic coating characteristics. As a result, the as rolled steel surface cannot be uniformly coated with a tlghtly adherent organic coating. The prior art has always taught that the organic coating characteristics can be improved
The present invention is concerned with a novel method of increasing the corrosion resistance and improving the organic protective coating characteristics of cold rolled steel. In one of its more specific variants, the invention is further concerned ~ -with a novel process for preparing container stock having a harden-ed coating of an organic protective coating thereon from cold rolled steel in the as rolled condition. The invention is also concerned with the various products produced by the method of the , 10 invention.
Cold reduced flat rolled mild steel products having ~ ;
.. . ...
;~, thicknesses not greater than about 0.065 inch are usually produced by cold rolling hot rolled strip in coil form from a con-tinuous hot strip mill. The sequence of operations involves uncoiling the ;~ hot rolled strip, passing the strip through a continuous picker, rinsing, drying, oiling with a cold reduction lubricant which also ^:
protects against rusting, and recoiling. The resulting hot rolled . ~ : :
~ strlp is subsequently uncoiled and passed through a continuous cold .~ ~
reduction~mill which has a plurality of stands with driven rolls.
; 20 Modern continuous cold reduction mills operate at high strip speeds ~ and often with heavy reductions in each stage and a large amount `~ of heat i9 generated by frictional contact between the roll sur-faces and the steel. The heat thus generated is removed by a system of~flood lubrication in which streams or jets of an aqueous dispension of cold rolling oil are directed against the roll bodies and~ the~surface of the steel. Following cold reduction to the desired gage, the cold rolled strip is coiled without removing the , ~ residual cold rolling oiI and other surface contaminants such as .. : i~
; iron oxide and dirt. Thereafter the strip may be side trimmed and ~,,; ~.
' given any further treatments that are necessary or desirable for a ~;
given end use. Inasmuch as the freshly cold rolled steel surface is very susceptible to rusting, often a protective coating is ~`~
applied. The protective coating may be metallic in nature such as in the production of tin plate, or an organic protective coat-~ ing may be applied such as in the production of lacquer or enamel g~ coated blackplate.
3 The preparation of cold rolled steel having an organic protective coating thereon from cold rolled steel in the as rolled condition presents a number of problems. One serious problem is ;
the above mentioned pronounced suaceptibility to rusting while in `-transit to the customer and during storage awaiting use. Unless the as rolled steel is given a temporary protective coating, often i: , rusting cannot be controlled at an acceptable level while awaiting application of the final organic protective coating. The temporary protective coating increases the production C09tS substantially ~-and usually adds very llttle, if any*hing, to the corrosion resis~
tance of the~final product. Thus, it would be possible to eIiminate the temporary protective coating and reduce costs provided suffi-;;2~0 ~ cient~corrosion resistance to provide an adequate floor life could bé imparted directly to the as rolled steel.
; Another important disadvantage of the cold rolled steel lies in the organic coating chàracteristics of the initial as rolled surface~ The residual~ cold rolling oil and perhaps other surface - -, ~ ;contamlnanta such as iron oxlde and dirt cause the as rolled steel surface~to have extremely~poor organic coating characteristics. As a result, the as rolled steel surface cannot be uniformly coated with a tlghtly adherent organic coating. The prior art has always taught that the organic coating characteristics can be improved
- 2 -only by carrying out a very efficient cleaning step. Usually the as ro~led steel is passed through a strip cleaning line which employs a strong alkaline detergent solution to remove the rolling oil and other surface contaminants, and often the strip must be given an electrolytic treatment. The prior art has further taught that the cleaning step must be practiced prior to heating the cold reduced strip to a sufficiently elevated temperature to decompose the cold rolling lubricant as the carbonaceous residue left on the strip surface was thought to be detrimental. The cleaning step adds substantially to the overall cost of processing the as rolled cold reduced strip and it would be desirable to eliminate this expense.
Prior to the present invention, an entirely satisfactory process was not available to the industry for overcoming the above mentioned difficulties with as rolled cold rolled steel to be given .~
an organic protective coating. As a result, up until the present invention the art has followed the traditional practices of apply-ing a temporary protective coating designed to increase floor life, and/or carrying out an expensive cleaning step to remove residual , rolling oil and other surface contaminants prior to applying the ;1 final organic protective coating.
~ It is an object of the present invention to provide a ;' method of increasing the corrosion resistance of cold rolled steel in the as rolled condition.
, It is a further object to provide a method of improving ;~ the protective organic coating characteristics of cold rolled steel in the as rolled condition which has iron oxide and a ther-mally degradable rolling oil on the surface thereof.
Prior to the present invention, an entirely satisfactory process was not available to the industry for overcoming the above mentioned difficulties with as rolled cold rolled steel to be given .~
an organic protective coating. As a result, up until the present invention the art has followed the traditional practices of apply-ing a temporary protective coating designed to increase floor life, and/or carrying out an expensive cleaning step to remove residual , rolling oil and other surface contaminants prior to applying the ;1 final organic protective coating.
~ It is an object of the present invention to provide a ;' method of increasing the corrosion resistance of cold rolled steel in the as rolled condition.
, It is a further object to provide a method of improving ;~ the protective organic coating characteristics of cold rolled steel in the as rolled condition which has iron oxide and a ther-mally degradable rolling oil on the surface thereof.
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~043673 ,s ~'~ It is still a further object to provide a method of -is preparing container stock coated with a protective organic coating :! from cold rolled steel in the as rolled condition.
It is still a further object to provide the products prepared in accordance with the method of the invention.
.,1, ~ .
Still other objects and advantages of the invention will be apparent to those skilled in the art upon reference to the following detailed description and the Examples.
In accordance with the invention, the corrosion resistance of cold rolled steel having iron oxide and thermally degradable rolling oil on the surface thereof is increased and the protective organic coating characteristics of the surface thereof are improved by heat treating the steel under controlled conditions of tempera-ture and time. The steel is heat treated at a temperature suffi-ciently elevated to thermally degrade the rolling oil and the heat treatment is continued until the corrosion resistance and the organic protective coating characteristics of the resulting heat treated steel are improved. Thereafter, the heat treated steel i9 cooled to a temperature sufficiently low to prevent further thermal ~20 degradatlon of the rolling oil.
The surface of the resulting cooled heat treated steel has a residual film thereon containing iron oxide and thermally ~ degraded rolling oil which imparts increased corrosion resistance r, ~ and improved organic coating characteristics. If stlll additional corroslon resistance is desired, a coating of a hardenable fluid -organic protective coating composition for container stocks may be .
applied and thereafter hardened or cured to produce a hardened organic protective coating on the surface of the cooled heat treated ~il steel.
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1~4 36 L 3 The cold rolled steel to be heat treated may be pro-duced by prior art practices such as those disclosed in the text The Making, Shaping and Treating of Steel, Seventh Edition, pub--- . .
lished by The United States Steel Corporation. Chapter 34 on the manufacture of cold reduced flat rolled steel products and Chap-ter 37 on the manufacture of coated container stocks such as tin plate are especially pertinent. As is discussed therein, the re-~ sulting cold rolled steel strip is coiled in the as rolled condi-3 tion without first removing the residual rolling oil or surface contaminants such as iron oxide, dirt and the like from the steel ~J
;1 surface. Thereafter the cold rolled steel strip may be uncoiled, trimmed, sheared, or given any other desired treatment. The cold rolled steel may be produced by a process including one or more cold rolling steps or stages, and in instances where a plurality of cold rolling steps or stages are used, with or without one or , more intermediate annealing steps. The cold rolled steel may be produced, for example, by cold rolling directly to the desired thickness in a prior art tandem mill, or it may be produced by a prior art double reduction process wherein an initial tandem mill ' 20 cold rolled product is annealed and then further reduced in thick-ness in a double reduction mill. It is understood that the cold rolled steel to be heat treated in accordance with the invention ~ -is in the "as rolled" condltion following the last cold rolling step insofar as the residual rolling oil and the iron oxide sur-face contaminants on the strip surface are concerned, and the -j. . . .
term "as rolled" is so used herein.
The surface of the as rolled steel has a relatively low corrosion resistance which is not normally considered to be suffi-~1 cient for adequate floor life, and also relatively poor organic 'J
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protective coating characteristics which normally prevent organic protective coatings from being applied directly thereto. The as rolled steel has not received a cleaning treatment for the purpose of removing residual rolling oil and iron oxide at the time of ~ heat treating in accordance with the invention. The cold rolled ;~ steel usually has a thickness not greater than about 0.065 inch, . .~ .
j and often about 0.025-0.065 inch when it is used for the manufac-h ture of articles such as automotive bodies, furniture, household . ~ ~
equipment and the like. In instances where the steel is used for the manufacture of containers, blackplate of gage 29 and lighter (0.0141 inch or less in thickness) is preferred. Cold rolled steel of a thickness suitable for the manufacture of containers is some-times referred to herein as container stock, as this term is widely ~, used and has a well recognized meaning in this art.
Cold rolled steel in the as rolled condition to be heat treated has at least one gram per base box of residual rolling oil -thereon and varying amounts of iron oxide and other surface contami-nants. For better results, the surface has about 2-50 grams per base box of residual rolling oil and preferably about 5-25 grams per base box. Optimum results are often achieved when the surface has about 10-15 grams per base box of residual rolling oil. Resi-dual rolling oil in the foregoing quantities is normally present ~ on as rolled steel strip produced in modern continuous multi-stand "~; cold rolling mills. It is not necessary to wash or scrub residual r~ ~
rolling oil from the strip surface, or treat the strip surface for the purpose of removing iron oxide and other impurities and contami-nants prior to the heat treatment and such cleaning steps should be avoided. The term "base box" is widely used in this art and I
~, - 6 -~04~ 3 refers to a surface area of 31,360 square inches or 217.78 square feet.
The cold rolling oil should be thermally degradable at the temperature of the heat treatment. As a general rule, mineral oil based rolling oils are not preferred and especially the satu-rated mineral oils which do not thermally degrade readily. Good results may be achieved in most instances when the rolling oil contains a substantial percentage of mineral oil, such as up to 20% by volume and preferably up to 10% by volume. Cold rolling oils based upon animal oils or fats and vegetable oils are very satisfactory as they thermally degrade easily. Rolling oils of this type usually contain fatty acids and/or fatty acid mono-, di-, and tri-glycerides having about 14-22 carbon atoms and preferably about 16-18 carbon atoms. Varying amounts of unsaturation may be ~ -present and at least some unsaturation is preferred as often highly ' saturated or hydrogenated oils do not give as good results. Examples of animal oils and fats which may be used as cold rolling lubricants i include tallow, lard, fish oils and the like. Examples of vegetable 'J' oils include corn oil, cotton seed oil, peanut oil, poppy seed oil, safflower seed oil, sunflower seed oil, soybean oil, rape seed oil, palm oil and the like. Mixtures of animal and vegetable fats and ~ oils may be used when desired, and mineral oils also may be added ;~ thereto in the quantities stated. Additionally, synthetic ester rolling oils of the prior art may be used such as dioctyl sebacate, dioctyl phthalate, butyl stearate, butyl palmitate and the like.
~, The synthetic ester rolling oils may be used alone, or used in `i admixtures with one or more of the aforementioned oils and fats.
One type of fatty oil which has been found to produce very satis-factory results contains a preponderance of fatty aclds and/or fatty i`
)43~ 3 ~`~r;'~ acid gl~cerides having 16-18 carbon atoms in the acidic ~ ,.;
~ residua thereof, of which palmitic, stearic, oleic and 3~ linoleic acids are preferred. An oil of this type is palm ; ,., ~ oil, or an admixture of corn oil and cotton seed oil.
,~ "... .
The temperature of the heat treatment and the , ;i~ period of heat treatment are critical insofar as the higher ,.,~., . :
~ temperatures of treatment are concerned and must be main-.~h'.', tained within the limits defined herein if entirely satis-factory results are to be achieved. As far as the lower temperatures of treatment are concerned, the as rolled :;~.,.; j steel must be heat treated at a temperature sufficiently ,r~,, elevated to thermally degrade the rolling oil over a period of time compatible with commercial treating line operating speed8. Usually the temperature of heat treatment is about 400-800F., and about 600F. for best result~. As a general rule, the period of the heat treatment ~hould not ex¢eed~10 8econd8, and for better results should not be more than 5 seconds. The best results are achi-ved when the~heat treatm-nt is not long r than 1 second. Usually 20~ there is no minimum period of heat treatment with the ; higher temperatures~of treatment as the rolling oil therm-!~, '""~ ; ;ally~degrades~upon heating to proper temperatur to an extent sufficient for the purposes of the present invention.
Thus,~periods of heat treatment of 0.1-10, 0.1-5 and 0.0-1 econds are satisfactory depending on the temperature of ~ treatm~nt. As a general rule, lower temperatures and ; ~ horter~periods 0f heat treatment are preferred within the foregoing range~;and~ n uch cases it is only necessary i~ ;that the heat treatment be continued until the corrosion 30`~ reoistan oe and the organic coating charact rist~cs of the ~ resulting heat treat-d`steel are improved~ Thus whether ;~ ~
. ~
~ -8-~043ti~3 the tempe~ature of treatm~nt i~ on the high side and the time short or the temperature of treatment is on the low side and time long, the time of treatment is until the corrosion resistance and the organic coating charact-eristics of the resulting heat treated steel are improved -. regardless of the extent and character of degradation of the oil.
The heat treated steel is quenched to a temperature sufficiently low to prevent further thermal - 10 degradation of the rolling oil. Preferably, the heat J treated steel is quenched immediately following the heat treatment for the above mentioned period of time to a temperature not greater than 200F. and for best ~ :
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3L0~3673 results to a temperature not greater than 100F. The heat treated steel may be quenched in water, cool or cold air streams, or by other suitable means. Thereafter, the heat treating strip may be dried and coiled if quenched in water, or merely coiled if quenched in cool or cold air. If desired, an organic coating may be applied thereto before or following coiling as will be described hereinafter.
In a preferred variant, the as rolled steel is rapidly heated to the heat treating temperature, and then rapidly cooled to a temperature below the thermal degradation temperature. This procedure prevents warpage of the strip, and also discoloration of the coating that is formed on the strip. Additionally, adverse physical and metallurgical effects on the heat treated strip are prevented. Heat treatment at temperatures of 500-700F. for not more than 5 seconds, and preferably at about 600F. for not more than 1 second, avoids the aforementioned problems.
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The as rolled steel strip is preferably heat treated at high strip speeds employing high frequency induction heating.
Strip speeds of 1,000, 2,000 or 3,000 feet per minute or higher may be used. The heat treatment may be performed along with other operations such as side trimming by placing a high frequency induc-tion heater in the line at a convenient point. It is not necessary to wash the heat treated strip or perform any other operation thereon following the heat treatment with the exception of the quenching step. If desired, the heat treated steel may be oiled ~ with a lubricant in the same manner as in the manufacture of tin `i plate following the flow brightening step. High frequency induc-tion heating is the only practical way to heat the strip sufficient-ly fast to reach the proper temperature without inducing the adverse physical and metallurgical properties noted above in instances ; _ 9 _ ,::
!
where strip speeds of 1,000 feet per minute and higher are employed.
Infrared heating is not fast enough to raise the temperature of the strip to the proper heat treating level within the required period of time at high strip speeds. Infrared heating and other methods of heating may be employed when the period of time avail-able therefor permits.
The residual film produced on the surface of the heat ~- treated steel usually contains thermally degraded rolling oil in an amount of about 0.05-2 grams per base box, and preferably about 0.1-1 gram per base box. setter results are achieved when the resi-1 6.~
B dual film contains about e~e~-0.5 gram per base box of thermally ~' degraded rolling oil, and best results at about 0.3 gram per base box.
Thr residual film of iron oxide and thermally degraded , rolling oil markedly increases the corrosion resistance of the ~ heat treated steel surface. Normally, the as rolled steel surface ;~ rusts very rapidly and the floor life is too short for practical i operating conditions. The corrosion resistance of the heat treated steel product approaches that of one quarter pound electrolytic tin plate. This degree of corrosion resistance is remarkable in view of the fact that no additional substance is applied to the steel , surface prior to heat treating.
The residual film is tightly adherent and forms an excel-¦ lent base for organic protective coatings. It is compatible with ... ..
the various types of organic protective coatings applied to container 1 stocks in general, and to tin plate or blackplate in particular.
- The prior art organic coatings may be applied directly to the cooled -heat treated steel surface, immediately after quenching, and prior to coiling, or in a separate coating step at any time following "'' " -- 1 0 1(~43~73 coiling. The organic protective coatings may be applied by prior art techniques such as by spraying, brushing, roller coating and -~
electrostatic deposition. High speed organic protective coating - lines of the type employed in the manufacture of coated container stock may be employed. The heat treated steel may be in the form of sheet or strip at the time of applying the organic protective coating.
In practicing the organic coating method of the invention, any suitable prior aLt fluid organic protective coating material that is subsequently hardenable or curable may be used, including varnishes, lacquers and enamels for metallic container stocks.
;1 Specific examples of organic coating materials include epoxy, modi-fied epoxy, phenolic, modified phenolic, acrylic, modified acrylic, vinyl, modified vinyl, alkyd and polyurethane varnishes, lacquers and/or enamels. Prior art lithographing or printing inks which are suitable for use on metallic container stocks for labeling and decorative purposes are considered to be organic coatings for the purpose of the present invention. The organic coating materials . ..
:
should be fluid initially, i.e., sufficiently fluid to be applied by metering rolls, spraying, brushing, and direct or indirect printing or lithographing, and may vary from soft pastes to fluid ;
liquids depending upon the selected method of application. The , ; initially fluid organic coatlng material is hardened or cured ~; following application by, for example, evaporating solvent or bak-ing to produce the final organic coating. The method of applying the initially fluid organic coating material and then hardening the same to produce the final organic coating may be in accordance with prior art practice.
1. ~ - 11 - -~: :
~a43673 The foregoing detailed description and the following specific examples are for purposes of illustration only, and are not intended as being limiting to the spirit or scope of the ~ `
appended claims.
EXAMPLE I
This Example illustrates the improved corrosion resistance that is obtained upon heat treating as rolled blackplate in accord-ance with the invention.
' Two coils of blackplate in the as rolled condition are j 10 produced in a prior art four stand continuous cold reduction line ' employing a 50-50 mixture of corn oil and cotton seed oil as a rolling lubricant in the form of an aqueous emulsion. The two coils are produced under identical operating conditions and have 10 grams per base box of residual rolling oil on the steel surfaces.
~, The steel surfaces also have varying amounts of iron oxide, dirt and other contaminants in the usual quantities. No rolling oil or ~,~
other contaminants are removed.
~. One coil of the as rolled blackplate is reserved for use 3 as a control. The other coil of blackplate is passed through a i? 20 side trimmer line at a strip speed of about 2,000 feet per minute and is heat treated by induction heating at a temperature of 600F.
for a period of 1 second. The heat treated blackplate is quenched ; immediately with water to a temperature below 100F., dried, and -coiled. ~
. -ii: ~ .
.~
~ The heat treated coil of blackplate and the as rolled . ~
coil of blackplate are stored for 12 months in a warehouse under ,~ identical conditions. At the end of the 12 months test period, the coil of as rolled blackplate has sufficient rusting to adversely affect the quality of a coated product prepared therefrom. The -~, ' ' ~ ' .':: '`,.. . ` ! ' . , ` - . . , ... , . : . . ` . !
~ 0~3ti73 heat treated coil of blackplate is substantially free of rust and is entirely satisfactory for coating with an organic protective coating without further cleaning or pretreatment. Thus, the heat treatment of the present invention greatly extends the floor life of cold reduced steel.
EXAMPLE_II
; This Example illustrates the improvement in the organic ~ , coating characteristics of as rolled blackplate following heat , treatment in accordance with the invention.
Two additional coils of as rolled blackplate are prepared in accordance with Example I. The first coil is not heat treated -and is reserved as a control. The second coil is given a heat ~¦ treatment in accordance with the general procedure of Example I.
The heat treated coil is passed through a high speed line for lacquering and lithographing container stock. The organic coating is an epoxy lacquer which exhibits a tendency toward poor wetting, eyeholing and poor adherence.
No problems are experienced with respect to eyeholing or ~3~ nonuniform wetting of the heat treated blackplate. The coating was tightly adherent and an entirely satisfactory epoxy lacquer coated blackplate was produced.
~; Entirely unsatisfactory results are obtained when an effort is made to pass the as rolled blackplate coil through the lacquering and lithographing line. The hardened film of epoxy lacquer is not adherent and eyeholing is apparent. Thus, the as rolled blackplate cannot be satisfactorily lacquered and litho-graphed in the absence of the heat treatment of the invention.
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.. . .. ...... . _ . _ . . _ _ . .. . .
~043673 ,s ~'~ It is still a further object to provide a method of -is preparing container stock coated with a protective organic coating :! from cold rolled steel in the as rolled condition.
It is still a further object to provide the products prepared in accordance with the method of the invention.
.,1, ~ .
Still other objects and advantages of the invention will be apparent to those skilled in the art upon reference to the following detailed description and the Examples.
In accordance with the invention, the corrosion resistance of cold rolled steel having iron oxide and thermally degradable rolling oil on the surface thereof is increased and the protective organic coating characteristics of the surface thereof are improved by heat treating the steel under controlled conditions of tempera-ture and time. The steel is heat treated at a temperature suffi-ciently elevated to thermally degrade the rolling oil and the heat treatment is continued until the corrosion resistance and the organic protective coating characteristics of the resulting heat treated steel are improved. Thereafter, the heat treated steel i9 cooled to a temperature sufficiently low to prevent further thermal ~20 degradatlon of the rolling oil.
The surface of the resulting cooled heat treated steel has a residual film thereon containing iron oxide and thermally ~ degraded rolling oil which imparts increased corrosion resistance r, ~ and improved organic coating characteristics. If stlll additional corroslon resistance is desired, a coating of a hardenable fluid -organic protective coating composition for container stocks may be .
applied and thereafter hardened or cured to produce a hardened organic protective coating on the surface of the cooled heat treated ~il steel.
' - 4 -, ......................................................................... .
1~4 36 L 3 The cold rolled steel to be heat treated may be pro-duced by prior art practices such as those disclosed in the text The Making, Shaping and Treating of Steel, Seventh Edition, pub--- . .
lished by The United States Steel Corporation. Chapter 34 on the manufacture of cold reduced flat rolled steel products and Chap-ter 37 on the manufacture of coated container stocks such as tin plate are especially pertinent. As is discussed therein, the re-~ sulting cold rolled steel strip is coiled in the as rolled condi-3 tion without first removing the residual rolling oil or surface contaminants such as iron oxide, dirt and the like from the steel ~J
;1 surface. Thereafter the cold rolled steel strip may be uncoiled, trimmed, sheared, or given any other desired treatment. The cold rolled steel may be produced by a process including one or more cold rolling steps or stages, and in instances where a plurality of cold rolling steps or stages are used, with or without one or , more intermediate annealing steps. The cold rolled steel may be produced, for example, by cold rolling directly to the desired thickness in a prior art tandem mill, or it may be produced by a prior art double reduction process wherein an initial tandem mill ' 20 cold rolled product is annealed and then further reduced in thick-ness in a double reduction mill. It is understood that the cold rolled steel to be heat treated in accordance with the invention ~ -is in the "as rolled" condltion following the last cold rolling step insofar as the residual rolling oil and the iron oxide sur-face contaminants on the strip surface are concerned, and the -j. . . .
term "as rolled" is so used herein.
The surface of the as rolled steel has a relatively low corrosion resistance which is not normally considered to be suffi-~1 cient for adequate floor life, and also relatively poor organic 'J
... .
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....... . . . . . . . .. .
protective coating characteristics which normally prevent organic protective coatings from being applied directly thereto. The as rolled steel has not received a cleaning treatment for the purpose of removing residual rolling oil and iron oxide at the time of ~ heat treating in accordance with the invention. The cold rolled ;~ steel usually has a thickness not greater than about 0.065 inch, . .~ .
j and often about 0.025-0.065 inch when it is used for the manufac-h ture of articles such as automotive bodies, furniture, household . ~ ~
equipment and the like. In instances where the steel is used for the manufacture of containers, blackplate of gage 29 and lighter (0.0141 inch or less in thickness) is preferred. Cold rolled steel of a thickness suitable for the manufacture of containers is some-times referred to herein as container stock, as this term is widely ~, used and has a well recognized meaning in this art.
Cold rolled steel in the as rolled condition to be heat treated has at least one gram per base box of residual rolling oil -thereon and varying amounts of iron oxide and other surface contami-nants. For better results, the surface has about 2-50 grams per base box of residual rolling oil and preferably about 5-25 grams per base box. Optimum results are often achieved when the surface has about 10-15 grams per base box of residual rolling oil. Resi-dual rolling oil in the foregoing quantities is normally present ~ on as rolled steel strip produced in modern continuous multi-stand "~; cold rolling mills. It is not necessary to wash or scrub residual r~ ~
rolling oil from the strip surface, or treat the strip surface for the purpose of removing iron oxide and other impurities and contami-nants prior to the heat treatment and such cleaning steps should be avoided. The term "base box" is widely used in this art and I
~, - 6 -~04~ 3 refers to a surface area of 31,360 square inches or 217.78 square feet.
The cold rolling oil should be thermally degradable at the temperature of the heat treatment. As a general rule, mineral oil based rolling oils are not preferred and especially the satu-rated mineral oils which do not thermally degrade readily. Good results may be achieved in most instances when the rolling oil contains a substantial percentage of mineral oil, such as up to 20% by volume and preferably up to 10% by volume. Cold rolling oils based upon animal oils or fats and vegetable oils are very satisfactory as they thermally degrade easily. Rolling oils of this type usually contain fatty acids and/or fatty acid mono-, di-, and tri-glycerides having about 14-22 carbon atoms and preferably about 16-18 carbon atoms. Varying amounts of unsaturation may be ~ -present and at least some unsaturation is preferred as often highly ' saturated or hydrogenated oils do not give as good results. Examples of animal oils and fats which may be used as cold rolling lubricants i include tallow, lard, fish oils and the like. Examples of vegetable 'J' oils include corn oil, cotton seed oil, peanut oil, poppy seed oil, safflower seed oil, sunflower seed oil, soybean oil, rape seed oil, palm oil and the like. Mixtures of animal and vegetable fats and ~ oils may be used when desired, and mineral oils also may be added ;~ thereto in the quantities stated. Additionally, synthetic ester rolling oils of the prior art may be used such as dioctyl sebacate, dioctyl phthalate, butyl stearate, butyl palmitate and the like.
~, The synthetic ester rolling oils may be used alone, or used in `i admixtures with one or more of the aforementioned oils and fats.
One type of fatty oil which has been found to produce very satis-factory results contains a preponderance of fatty aclds and/or fatty i`
)43~ 3 ~`~r;'~ acid gl~cerides having 16-18 carbon atoms in the acidic ~ ,.;
~ residua thereof, of which palmitic, stearic, oleic and 3~ linoleic acids are preferred. An oil of this type is palm ; ,., ~ oil, or an admixture of corn oil and cotton seed oil.
,~ "... .
The temperature of the heat treatment and the , ;i~ period of heat treatment are critical insofar as the higher ,.,~., . :
~ temperatures of treatment are concerned and must be main-.~h'.', tained within the limits defined herein if entirely satis-factory results are to be achieved. As far as the lower temperatures of treatment are concerned, the as rolled :;~.,.; j steel must be heat treated at a temperature sufficiently ,r~,, elevated to thermally degrade the rolling oil over a period of time compatible with commercial treating line operating speed8. Usually the temperature of heat treatment is about 400-800F., and about 600F. for best result~. As a general rule, the period of the heat treatment ~hould not ex¢eed~10 8econd8, and for better results should not be more than 5 seconds. The best results are achi-ved when the~heat treatm-nt is not long r than 1 second. Usually 20~ there is no minimum period of heat treatment with the ; higher temperatures~of treatment as the rolling oil therm-!~, '""~ ; ;ally~degrades~upon heating to proper temperatur to an extent sufficient for the purposes of the present invention.
Thus,~periods of heat treatment of 0.1-10, 0.1-5 and 0.0-1 econds are satisfactory depending on the temperature of ~ treatm~nt. As a general rule, lower temperatures and ; ~ horter~periods 0f heat treatment are preferred within the foregoing range~;and~ n uch cases it is only necessary i~ ;that the heat treatment be continued until the corrosion 30`~ reoistan oe and the organic coating charact rist~cs of the ~ resulting heat treat-d`steel are improved~ Thus whether ;~ ~
. ~
~ -8-~043ti~3 the tempe~ature of treatm~nt i~ on the high side and the time short or the temperature of treatment is on the low side and time long, the time of treatment is until the corrosion resistance and the organic coating charact-eristics of the resulting heat treated steel are improved -. regardless of the extent and character of degradation of the oil.
The heat treated steel is quenched to a temperature sufficiently low to prevent further thermal - 10 degradation of the rolling oil. Preferably, the heat J treated steel is quenched immediately following the heat treatment for the above mentioned period of time to a temperature not greater than 200F. and for best ~ :
, 1, .1 :
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A -8a-., :
3L0~3673 results to a temperature not greater than 100F. The heat treated steel may be quenched in water, cool or cold air streams, or by other suitable means. Thereafter, the heat treating strip may be dried and coiled if quenched in water, or merely coiled if quenched in cool or cold air. If desired, an organic coating may be applied thereto before or following coiling as will be described hereinafter.
In a preferred variant, the as rolled steel is rapidly heated to the heat treating temperature, and then rapidly cooled to a temperature below the thermal degradation temperature. This procedure prevents warpage of the strip, and also discoloration of the coating that is formed on the strip. Additionally, adverse physical and metallurgical effects on the heat treated strip are prevented. Heat treatment at temperatures of 500-700F. for not more than 5 seconds, and preferably at about 600F. for not more than 1 second, avoids the aforementioned problems.
.... .
The as rolled steel strip is preferably heat treated at high strip speeds employing high frequency induction heating.
Strip speeds of 1,000, 2,000 or 3,000 feet per minute or higher may be used. The heat treatment may be performed along with other operations such as side trimming by placing a high frequency induc-tion heater in the line at a convenient point. It is not necessary to wash the heat treated strip or perform any other operation thereon following the heat treatment with the exception of the quenching step. If desired, the heat treated steel may be oiled ~ with a lubricant in the same manner as in the manufacture of tin `i plate following the flow brightening step. High frequency induc-tion heating is the only practical way to heat the strip sufficient-ly fast to reach the proper temperature without inducing the adverse physical and metallurgical properties noted above in instances ; _ 9 _ ,::
!
where strip speeds of 1,000 feet per minute and higher are employed.
Infrared heating is not fast enough to raise the temperature of the strip to the proper heat treating level within the required period of time at high strip speeds. Infrared heating and other methods of heating may be employed when the period of time avail-able therefor permits.
The residual film produced on the surface of the heat ~- treated steel usually contains thermally degraded rolling oil in an amount of about 0.05-2 grams per base box, and preferably about 0.1-1 gram per base box. setter results are achieved when the resi-1 6.~
B dual film contains about e~e~-0.5 gram per base box of thermally ~' degraded rolling oil, and best results at about 0.3 gram per base box.
Thr residual film of iron oxide and thermally degraded , rolling oil markedly increases the corrosion resistance of the ~ heat treated steel surface. Normally, the as rolled steel surface ;~ rusts very rapidly and the floor life is too short for practical i operating conditions. The corrosion resistance of the heat treated steel product approaches that of one quarter pound electrolytic tin plate. This degree of corrosion resistance is remarkable in view of the fact that no additional substance is applied to the steel , surface prior to heat treating.
The residual film is tightly adherent and forms an excel-¦ lent base for organic protective coatings. It is compatible with ... ..
the various types of organic protective coatings applied to container 1 stocks in general, and to tin plate or blackplate in particular.
- The prior art organic coatings may be applied directly to the cooled -heat treated steel surface, immediately after quenching, and prior to coiling, or in a separate coating step at any time following "'' " -- 1 0 1(~43~73 coiling. The organic protective coatings may be applied by prior art techniques such as by spraying, brushing, roller coating and -~
electrostatic deposition. High speed organic protective coating - lines of the type employed in the manufacture of coated container stock may be employed. The heat treated steel may be in the form of sheet or strip at the time of applying the organic protective coating.
In practicing the organic coating method of the invention, any suitable prior aLt fluid organic protective coating material that is subsequently hardenable or curable may be used, including varnishes, lacquers and enamels for metallic container stocks.
;1 Specific examples of organic coating materials include epoxy, modi-fied epoxy, phenolic, modified phenolic, acrylic, modified acrylic, vinyl, modified vinyl, alkyd and polyurethane varnishes, lacquers and/or enamels. Prior art lithographing or printing inks which are suitable for use on metallic container stocks for labeling and decorative purposes are considered to be organic coatings for the purpose of the present invention. The organic coating materials . ..
:
should be fluid initially, i.e., sufficiently fluid to be applied by metering rolls, spraying, brushing, and direct or indirect printing or lithographing, and may vary from soft pastes to fluid ;
liquids depending upon the selected method of application. The , ; initially fluid organic coatlng material is hardened or cured ~; following application by, for example, evaporating solvent or bak-ing to produce the final organic coating. The method of applying the initially fluid organic coating material and then hardening the same to produce the final organic coating may be in accordance with prior art practice.
1. ~ - 11 - -~: :
~a43673 The foregoing detailed description and the following specific examples are for purposes of illustration only, and are not intended as being limiting to the spirit or scope of the ~ `
appended claims.
EXAMPLE I
This Example illustrates the improved corrosion resistance that is obtained upon heat treating as rolled blackplate in accord-ance with the invention.
' Two coils of blackplate in the as rolled condition are j 10 produced in a prior art four stand continuous cold reduction line ' employing a 50-50 mixture of corn oil and cotton seed oil as a rolling lubricant in the form of an aqueous emulsion. The two coils are produced under identical operating conditions and have 10 grams per base box of residual rolling oil on the steel surfaces.
~, The steel surfaces also have varying amounts of iron oxide, dirt and other contaminants in the usual quantities. No rolling oil or ~,~
other contaminants are removed.
~. One coil of the as rolled blackplate is reserved for use 3 as a control. The other coil of blackplate is passed through a i? 20 side trimmer line at a strip speed of about 2,000 feet per minute and is heat treated by induction heating at a temperature of 600F.
for a period of 1 second. The heat treated blackplate is quenched ; immediately with water to a temperature below 100F., dried, and -coiled. ~
. -ii: ~ .
.~
~ The heat treated coil of blackplate and the as rolled . ~
coil of blackplate are stored for 12 months in a warehouse under ,~ identical conditions. At the end of the 12 months test period, the coil of as rolled blackplate has sufficient rusting to adversely affect the quality of a coated product prepared therefrom. The -~, ' ' ~ ' .':: '`,.. . ` ! ' . , ` - . . , ... , . : . . ` . !
~ 0~3ti73 heat treated coil of blackplate is substantially free of rust and is entirely satisfactory for coating with an organic protective coating without further cleaning or pretreatment. Thus, the heat treatment of the present invention greatly extends the floor life of cold reduced steel.
EXAMPLE_II
; This Example illustrates the improvement in the organic ~ , coating characteristics of as rolled blackplate following heat , treatment in accordance with the invention.
Two additional coils of as rolled blackplate are prepared in accordance with Example I. The first coil is not heat treated -and is reserved as a control. The second coil is given a heat ~¦ treatment in accordance with the general procedure of Example I.
The heat treated coil is passed through a high speed line for lacquering and lithographing container stock. The organic coating is an epoxy lacquer which exhibits a tendency toward poor wetting, eyeholing and poor adherence.
No problems are experienced with respect to eyeholing or ~3~ nonuniform wetting of the heat treated blackplate. The coating was tightly adherent and an entirely satisfactory epoxy lacquer coated blackplate was produced.
~; Entirely unsatisfactory results are obtained when an effort is made to pass the as rolled blackplate coil through the lacquering and lithographing line. The hardened film of epoxy lacquer is not adherent and eyeholing is apparent. Thus, the as rolled blackplate cannot be satisfactorily lacquered and litho-graphed in the absence of the heat treatment of the invention.
.,, , - .
:~ .
' ~- - 13 - ~
Claims (25)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of increasing the corrosion resistance of cold rolled steel and improving the organic coating characteristics of the surface thereof comprising:
heat treating as rolled cold rolled steel having iron oxide and thermally degradable rolling oil on the surface thereof at a temperature sufficiently elevated to thermally degrade the rolling oil, the surface of the cold rolled steel having relatively low corrosion resistance and relatively poor organic coating characteristics initially and the heat treatment being continued until the corrosion resistance and the organic coating characteristics of the resulting heat treated steel are improved, and cooling the said heat treated steel to a temperature sufficiently low to prevent further thermal degradation of the rolling oil, the surface of the resulting cooled heat treated steel having a residual film thereon containing iron oxide and thermally degraded rolling oil which imparts corrosion resistance and improved organic coating characteristics thereto.
heat treating as rolled cold rolled steel having iron oxide and thermally degradable rolling oil on the surface thereof at a temperature sufficiently elevated to thermally degrade the rolling oil, the surface of the cold rolled steel having relatively low corrosion resistance and relatively poor organic coating characteristics initially and the heat treatment being continued until the corrosion resistance and the organic coating characteristics of the resulting heat treated steel are improved, and cooling the said heat treated steel to a temperature sufficiently low to prevent further thermal degradation of the rolling oil, the surface of the resulting cooled heat treated steel having a residual film thereon containing iron oxide and thermally degraded rolling oil which imparts corrosion resistance and improved organic coating characteristics thereto.
2. The method of claim 1 wherein the colt rolled steel is heat treated for not more than 10 seconds.
3. The method of claim 1 wherein the colt rolled steel is heat treated for not more than 10 seconds by induction heating.
4. The heat treated cold rolled steel prepared by the method of claim 1, 2 or 3.
5. The method of claim 1 wherein the cold rolled steel is heat treated at a temperature of about 400-800°F.
6. The method of claim 5 wherein the said heat treated steel is cooled to a temperature less than 200°F following heat treatment.
7. The method of claim 1 wherein at least one gram per base box of thermally degradable rolling oil is on the cold rolled steel surface to be heat treated.
8. The heat treated cold rolled steel prepared by the method of claim 5, 6 or 7.
9. The method of claim 1 wherein the said residual film on the heat treated steel surface contains at least 0.05 gram per base box of thermally degraded rolling oil.
10. The method of claim 1 wherein the cold rolled steel is heat treated at a temperature of 500-700°F for a period of not more than 5 seconds.
11. The method of claim 1 wherein about 2-25 grams per base box of rolling oil is on the cold rolled steel surface to be heat treated and the said residual film on the heat treated steel surface contains about 0.1-1 gram per base box of thermally degraded rolling oil.
12. The heat treated cold rolled steel prepared by the method of claim 9, 10 or 11.
13. The method of claim 1 wherein about 10-15 grams per base box of rolling oil is on the cold rolled steel surface to be heat treated, the steel is heat treated at a temperature of about 500-700°F for not more than 5 seconds, the said heat treated steel is cooled to a temperature less than 200°F following the heat treatment and the said residual film on the heat treated steel surface contains about 0.2-0.5 gram per base box of thermally degraded rolling oil.
14. The method of claim 1 wherein about 10 grams per base box of rolling oil is on the cold rolled steel surface to be heat treated, the steel is heat treated by induction heating at a temperature of about 600°F
for not more than one second, the said heat treated steel is cooled to a temperature less than 100°F immediately following the heat treatment, and the said residual film on the heat treated steel surface contains about 0.3 gram per base box of thermally degraded rolling oil.
for not more than one second, the said heat treated steel is cooled to a temperature less than 100°F immediately following the heat treatment, and the said residual film on the heat treated steel surface contains about 0.3 gram per base box of thermally degraded rolling oil.
15. The heat treated cold rolled steel prepared by the method of claim 13 or 14.
16. A method of preparing container stock coated with an organic protective coating comprising:
heat treating as rolled cold rolled steel of container stock gage having iron oxide and thermally degradable rolling oil on the surface thereof at a temperature sufficiently elevated to thermally degrade the rolling oil, the surface of the cold rolled steel having relatively low corrosion resistance and relatively poor organic coating characteristics initially and the heat treatment being continued until the corrosion resistance and the organic coating characteristics of the resulting heat treated steel are improved, cooling the said heat treated steel to a temperature sufficiently low to prevent further thermal degradation of the rolling oil, the surface of the resulting cooled heat treated steel having a residual film thereon containing iron oxide and thermally degraded rolling oil which imparts corrosion resistance and improved organic coating characteristics thereto, applying a coating of a hardenable fluid organic protective coating composition for container stock on the surface of the cooled heat treated steel, and thereafter hardening the said fluid organic coating composition to produce container stock having a hardened organic protective coating thereon.
heat treating as rolled cold rolled steel of container stock gage having iron oxide and thermally degradable rolling oil on the surface thereof at a temperature sufficiently elevated to thermally degrade the rolling oil, the surface of the cold rolled steel having relatively low corrosion resistance and relatively poor organic coating characteristics initially and the heat treatment being continued until the corrosion resistance and the organic coating characteristics of the resulting heat treated steel are improved, cooling the said heat treated steel to a temperature sufficiently low to prevent further thermal degradation of the rolling oil, the surface of the resulting cooled heat treated steel having a residual film thereon containing iron oxide and thermally degraded rolling oil which imparts corrosion resistance and improved organic coating characteristics thereto, applying a coating of a hardenable fluid organic protective coating composition for container stock on the surface of the cooled heat treated steel, and thereafter hardening the said fluid organic coating composition to produce container stock having a hardened organic protective coating thereon.
17. The method of claim 16 wherein the cold rolled steel is heat treated at a temperature of about 400-800°F for not more than 10 seconds by induction heating.
18. The method of claim 17 wherein at least one gram per base box of thermally degradable rolling oil is on the cold rolled steel surface to be heat treated and the said residual film on the heat treated steel surface contains at least 0.05 gram per base box of thermally degraded rolling oil.
19. The container stock coated with an organic protective coating prepared by the method of claim 16, 17 or 18.
20. The method of claim 18 wherein the said heat treated steel is cooled to a temperature less than 200°F following the heat treatment.
21. The method of claim 16 wherein about 2-25 grams per base box of rolling oil is on the cold rolled steel surface to be heat treated, the cold rolled steel is heat treated at a temperature of about 500-700°F for a period of not more than 5 seconds, and the said residual film on the heat treated steel surface contains about 0.1 1 gram per base box of thermally degraded rolling oil.
22. The method of claim 16 wherein about 10-15 grams per base box of rolling oil is on the cold rolled steel surface to be heat treated, the steel is heat treated at a temperature of about 500-700°F for not more than 5 seconds, the said heat treated steel is cooled to a temperature less than 200°F
following the heat treatment, and the said residual film on the heat treated steel surface contains about 0.2-0.5 gram per base box of thermally degraded rolling oil.
following the heat treatment, and the said residual film on the heat treated steel surface contains about 0.2-0.5 gram per base box of thermally degraded rolling oil.
23. The container stock coated with an organic protective coating prepared by the method of claim 20, 21 or 22.
24. The method of claim 16 wherein about 10 grams per base box of rolling oil is on the cold rolled steel surface to be heat treated, the steel is heat treated by induction heating at a temperature of about 600°F
for not more than one second, the said heat treated steel is cooled to a temperature less than 100°F immediately following the heat treatment, and the said residual film on the heat treated steel surface contains about 0.3 gram per base box of thermally degraded rolling oil.
for not more than one second, the said heat treated steel is cooled to a temperature less than 100°F immediately following the heat treatment, and the said residual film on the heat treated steel surface contains about 0.3 gram per base box of thermally degraded rolling oil.
25. The container stock coated with an organic protective coating prepared by the method of claim 24.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US39830873A | 1973-09-18 | 1973-09-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1043673A true CA1043673A (en) | 1978-12-05 |
Family
ID=23574887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA209,055A Expired CA1043673A (en) | 1973-09-18 | 1974-09-12 | Organic coating characteristics of cold rolled steel |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5064131A (en) |
| BR (1) | BR7407727D0 (en) |
| CA (1) | CA1043673A (en) |
| DE (1) | DE2444216A1 (en) |
| FR (1) | FR2244015B1 (en) |
| GB (1) | GB1485781A (en) |
| IT (1) | IT1021645B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113817904A (en) * | 2021-08-11 | 2021-12-21 | 富兰克润滑科技（太仓）有限公司 | Low-carbon environment-friendly biodegradable quenching oil and preparation method thereof |
-
1974
- 1974-09-12 CA CA209,055A patent/CA1043673A/en not_active Expired
- 1974-09-16 IT IT5302774A patent/IT1021645B/en active
- 1974-09-16 DE DE19742444216 patent/DE2444216A1/en active Pending
- 1974-09-17 GB GB4037174A patent/GB1485781A/en not_active Expired
- 1974-09-17 FR FR7431361A patent/FR2244015B1/fr not_active Expired
- 1974-09-17 JP JP10613174A patent/JPS5064131A/ja active Pending
- 1974-09-17 BR BR772774A patent/BR7407727D0/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR7407727D0 (en) | 1975-07-29 |
| DE2444216A1 (en) | 1975-03-20 |
| AU7336574A (en) | 1976-03-25 |
| GB1485781A (en) | 1977-09-14 |
| FR2244015B1 (en) | 1978-03-24 |
| IT1021645B (en) | 1978-02-20 |
| JPS5064131A (en) | 1975-05-31 |
| FR2244015A1 (en) | 1975-04-11 |
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