PL83640B1 - - Google Patents

Description

METHOD OF PRE-TREATING METAL SURFACES The present invention relates to a method for pretreating metal surfaces by applying a phosphate protective layer to them in order to increase the performance of the organic coatings and / or to prevent premature corrosion. The metal subjected to this pretreatment is, in particular, steel. A serious problem in the production of steel drums is the fact that the surface of the steel coils or sheets obtained from the steel mill is often contaminated, especially in the form of rust spots, often very numerous. A special treatment is therefore required to bring the surface of the steel into a coatable condition without introducing adverse effects, for example, water sensitivity. Additional economic benefits would be obtained if steel mills could provide steel substantially free of rust and other undesirable contaminants to the steel, which would have a temporary corrosion resistance and provide a suitable substrate for coating without additional treatment. steel finishes by applying oily substances to the surface or by phosphating the surface, and also that phosphating seals the phosphate film, for example with oil. As for protecting the steel against corrosion, this method is satisfactory, but a common disadvantage is that steel protected with such oil or oil-sealed phosphate, a; 3 can be coated without degreasing as the performance of many such coatings would deteriorate, and the protection by phosphating alone to an extent that would be possible. corrosion resistance and effective coating is uneconomical and impractical for widespread use . This inconvenience causes a serious problem in the production of steel drums, which are to be painted on the outside and often varnished on the inside. Corrosion-resistant steel by known methods can seldom be satisfactorily coated without removal of said oil, if used. Consequently, the manufacturer of steel drums must degrease the surfaces of the steel with organic solvents such as trichlorethylene, or wash the surfaces with aqueous alkaline solutions, for example aqueous sodium hydroxide, sodium carbonate, alkali metal silicates or condensed phosphate. especially pyrophosphates, or aqueous acidic solutions, for example aqueous solutions of monometallic phosphate. According to British Patent Specification No. 625297, the properties of metallic surfaces such as abrasion resistance and storage stability can be improved by applying a stabilized solution , pastes or emulsions containing orthophosphoric acid and water-insoluble and non-drying polar oil or fat in a weight ratio of 1: 100 to 15: 100. Whilst the amount of safener per m2 is not fixed, it seems that such an amount of 'polar oil or fat, especially "degras", should be used so that the finish coat can only be applied after the removal of said oily material without removing the phosphate layer. U.S. Patent No. 3,525,651 describes a one-step coating process with an aqueous solution of zinc phosphate containing a special solid steel mixture of fatty grease and a water-soluble surfactant. this coating will provide sufficient lubrication, but if the deformation operation is to be severe, a layer of grease should be applied to the metal surface covered with it. which were used to protect the steel do not, as such, provide adequate protection against wear and tear lightening caused by the action of weather conditions. Phosphate coatings, much lighter than those used as a pretreatment for painting, also do not provide sufficient corrosion protection. Surprisingly, what is the subject of the invention, that sufficient corrosion resistance and an efficient coating are obtained in a more perfect manner. by the use of a phosphating agent and an oily material, either simultaneously or separately, but with the exception of a system in which more than 50 mg / m2 of the phosphating agent is deposited in a separate stage directly onto the metal in combination with more than 150 mg / m2. m2 of oily material It has also been found that the process of the invention achieves an unexpectedly high degree of lubricity (slipperiness) together with improved corrosion resistance and even with the benefit of at least without detriment to the coatings, which are possibly subsequently applied without prior re-application. In this description the expression "oily material" means oils which are insoluble in water and of which small amounts are they dissolve easily in solvents commonly used for paints and adhesives. These oils are mineral, vegetable, animal and other fatty oils, synthetic oils, modified oils and plasticizing oils. \ The choice of the right material depends on the type of application. The ingredients can be used in the form of a mixture of an oily material with the agent. or separately, for example by treating the steel surface with an oily material and stepwise treatment with a phosphating agent. The oily material and the phosphating agent may be used in the form of an emulsion or in the form of a solution (a considerable amount of water is needed during treatment to facilitate ionization of the phosphate agent). It is best to use an oily material and an emulsion as a phosphating agent. Such emulsions are prepared, for example, from dilute phosphoric acid, a surfactant and octyl sebacate. Octyl sebacate, often used in the manufacture of tinplate, is the best oily material. The best phosphating agent is orthophosphoric acid, but other phosphoric acids, phosphorous acid or acidic phosphates (possibly in combination with detergents) are not excluded. substrate, processing time and temperature, coating method, and finish required, but the most common is 0.01-1% (by volume) in water. The amount of phosphate used per m2 may be much lower than the amount of phosphate commonly used in the prior art methods. The present invention produces a preferred phosphate layer with a thickness of 0.01-50 mg per m2. If the phosphating agent contains an accelerator, for example, sodium nitrate, sodium nitrite, sodium chloride, copper or nickel salts, it is possible to obtain a better phosphate layer, the temperature and time required for its formation being reduced. The same result can be obtained if the phosphatizing accelerator is on the surface of the treated steel. The best accelerator is the combination of sodium nitrite with sodium nitrate. Although the amount of the oily material used is not limited, it is preferably 5-100 mg per m2, depending on the above-mentioned parameters. It is also possible to use an excess of a protective agent, for example an aqueous emulsion of an oily material, and a phosphating agent to neutralize the harmful effects of contaminants, if present. In this way, the usual cleaning treatment that the steel is subjected to before painting can be partially or completely omitted. It is desirable to create a surface condition, especially with controlled slippery, that allows subsequent metal treatments such as stretching (dragging) to be carried out. ¬many steel sheets. This state is achieved in the method according to the invention by selecting a suitable oily material. The components of the emulsion or solution, both collectively and separately, can be applied to the steel by various methods, such as rolling, dipping, brushing, spraying. Only a short contact time of the metal with the solution or the emulsion to be processed is required, but this is not a limiting feature. Preferably, a contact time of less than 3 minutes, especially less than 30 seconds, is used. A short drying time after this treatment is recommended. The method according to the invention can be applied to both cold-reduced and pickled hot-rolled steel. This treatment can be carried out during the production of cold-rolled or cold-rolled steel. hot during each stage of the process following annealing or etching. The process of the invention has a special significance in the protection of steel strips used in particular in the manufacture of steel drums. The steel treated according to the invention is packaged in the usual manner. Most often, the steel coils are wrapped with a laminate of paper and polyethylene and, in turn, covered with the outer casing made of steel sheets, possibly supported by wooden strips, which protect against direct contact with the weather. By treating the steel surface with the method according to the invention, a state of its surface is obtained (1) with a greater degree of corrosion resistance, (2) with an excellent appearance for a considerable period of time, (3) with greater efficiency of the subsequent coatings and (4) with a favorable degree of slipperiness. The examples are given to illustrate the invention without limiting its scope. The tests in Examples 1-18 were used. Paintability was assessed as follows. Generally - steel plates 150 × 300 mm or 150 × 100 mm held in an upright position are sprayed with paint in front of a cascade-type spray booth. Bright green pigmented inks are used in all cases, except where otherwise noted. Conventional spray equipment is used, ie a hand-held spray gun, and the paint is applied. it is possible to a thickness of 20-30 mm in one layer (paint coat). A 5-minute flash off period in a dust-free atmosphere is allowed prior to heating. After removing the plates from the oven and allowing them to cool down, the thickness of the coating is determined using an electromagnetic induction indicator. The number of plates is sufficient to obtain 18 test specimens in the form of 55 mm discs for the series of measurements described below. The specimens are brought to the desired state by leaving them under the following conditions: temperature and humidity of the surrounding atmosphere , soaking in a water bath heated to a temperature of 40 ± 0.2 ° C thermostatically controlled and stirred for an appropriate period of time. E3: 1966, the apparatus corresponds to the description, and the method of evaluating the results is slightly modified. The evaluation of the result using a 2.5 mm indentation on a sample is carried out as follows. A piece of transparent tape 25 mm wide, sensitive to iria, pressure is applied to the dented painted surface and pressed to adhere to the painted surface. The tape is then pulled off to remove all non-adhered paint. This piece of tape is in turn overlaid on the millimeter squared paper in order to permanently record the result and measure the stripped paint. The measurement is obtained by marking the diameter of the strip of paint stripped. Where the disc is not completely painted but consists of fine flakes, the area of the paint removed is considered to be that of the disc. An evaluation of 3 samples is made for each 10 25 30 35 substrate, coating and conditions and the average area of the paint removed is recorded. As the test program includes a surface control treatment, the value of the reference line is obtained for the efficiency of each coating / surface combination. The areas are expressed in square millimeters, and variations of 20-30 mm 2, representing ± 2 mm in diameter, are considered to be within the experimental variation and do not represent a major change in performance. Larger differences between the reference line and each modification indicate a change in performance for better or worse. In the event that by pulling the tape, the paint coating is removed from the insulated surface of the non-deformed part of the test sample as well as from the dented surface, the result is noted as a sharp loss of adhesion. (SLA). IN; In the extreme case, when the paint is removed from all or almost all of the test specimen, the result is recorded as the total loss of adhesion (CLA. The results of the CLA or SLA indicate far more serious deficiencies than the results expressed numerically as the surface removed because there was a loss of adhesion on the undeformed surface Pressure test according to Erichsen: German industry standard DIN 53156; British standard: BS 3900 Part E4, 1969 Method and apparatus are based on British standard BS 3900 Part E4, 1969 for single depth with a modified interpretation of the results, with the use of a thin table. Table 1 Characteristics of the reference Erichsen pressure test results. 50 55 66 Grade 0 1 2 3 4! 5 SLA "CLA Model Description no visible loss of adhesion or barely discernible cracking Fig. 1 Fig. 2 fig. 3 fig. 4 fig. 5 isolated spots or very small flakes removed spots removed or very small flakes forming in 1 approximation of the ring or disc, spots or very small flakes forming almost a full ring or discs m a full ring or discs of spots or very small flakes removed; ¦ large full flakes removed, forming approximately the discs severe loss of adhesion other than when under stress; 'total or nearly total loss of adhesion * 7 83 640 8 steel 16, 18 or 20 BG, as a finishing steel in a rolling mill or polished steel, and the tests are carried out under ambient conditions. of the test carried out with a 7.0 mm die is the same as in the case of the pressure test, except that instead of measuring the removed surface, the system of gradual loss of adhesion from zero to total in 8 degrees was used, as shown in Table 1. after bringing each of the samples to the desired state, the mean is calculated from the obtained degrees (the two extreme degrees are not taken into account). In interpreting the results, a difference of 2 or more degrees compared to the control value is significant. One degree differences may arise from experimental variations. As with the interpretation of the compression test results, the SLA or CLA score points to more serious deficiencies. The corrosion resistance is assessed by comparison, with the results referring to the amount of rust developing according to the pattern shown in Table 2. All figures listed are average from 3 plates - samples, 140 mm x 74 mm in size, exposed to a relative humidity of 85-90% at a temperature of 30 ° ± 1 ° C. Table 2 is the model table for microscopic and macroscopic corrosion testing according to Champion ( Oorrosion Testing Ptfocedures, FA Champion Second Edition L.964, pp 1203-205). Table 2 Standard Table for Microscopic and Macroscopic Corrosion Testing Fig. 6, Fig. VI, Fig. 8, Fig. 9, Fig. 11, Fig. 12, Fig. Very small small amount medium amount large amount numerous very numerous Table 3 gives the relationship between the descriptive number, the standard term and the number of rust flakes per square decimeter. Observed sizes of individual rust spots were always smaller than 8 mm2 (evaluation according to Champion method) Table 3 m Rust evaluation Descriptive number 1 2 3 4 5 6 7 Exemplary term very small few small amount average amount large amount numerous - very numerous number per square meter 33 100-330 1000 3300 10000 33000 10 15 25 30 35 50 55 60 In order to determine the concentration of phosphates deposited on the steel surface in the method according to the invention, tests are carried out using a radioactive tracer. In solutions of 0.01, 0.05 and 0.1% (by volume) of radioactive orthophosphoric acid 10 seconds, 20 seconds, 60 seconds, clean steel plates (degreased for 30 minutes in trichlorethylene vapors) and steel plates covered with octyl sebate (15 mg / m 2 and 100 mg / m 2), soluble salts, and a combination of the two. The amount of radioactive phosphoric acid remaining on the surface of the steel plates after drying is determined using a Geiger-Miller counter. The table below summarizes the amounts of phosphoric acid (phosphate) deposited on the surface of the steel immersed for 20 seconds at 0.05 % solution. The values are given in mg H3PO4 / m2 The coating of the steel plates is given in Table 4 Table 4 Concentration of phosphoric acid (90%) Dipping time (seconds) Coating on the surface Steel * degreased with trichlorethylene Steel with sodium nitrite 50 mg / m2 Steel with octyl sebacate 15 mg / m2 Steel with octyl sebacate 100 mg / m2 Steel with 50 mg / m2 sodium nitrite and 15 mg / m2 octyl sebacinate Steel with 50 mg / m2 sodium nitrite and 100 mg / m2 sebacate of cctil 1 0.05% by volume 20 25 30 16 9 5 12 Coating of H8PO4 by weight in mg / m2 Example I. An emulsion is prepared containing 1% by volume octyl sebacate, 0.1% by volume 90% orthophosphoric acid, 0.2% by weight of sodium nitrite and 0.05% by volume of Triton X-45 surfactant. Cold reduced mild steel plates are immersed in this emulsion for 10 seconds, dried and left in an upright position at ambient temperature for 1 hour. It was found that 47 mg / m 2 of octyl sebacate was deposited on the steel surface. These tiles are subjected to the above-described paintability and corrosion resistance test. The results obtained are summarized in the quoted tables 5 and 6. Example II. An aqueous solution was prepared containing 0.39% (by weight) of sodium nitrite, 0.12% (by weight) of triethanolamine and 0.05% (by weight) of Pluronic 164 surfactant. in this solution for 10 seconds, allowed to drain, and then dried at ambient temperature. It was found that on the surface 83 640 Table 5 Paintability 10 Ambient conditions Soaking for 1 day in water Erichsen pressure test Erichsen pressure steel Steel degreased with trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated in the above-mentioned manner removed 100 mm2 grade 3 stripped 65 mm 2 grade 4 Table 6 Corrosion resistance Conditions immediately 24 hours at 85—90% RH 7 days at RH. In addition, 85-90%. Steel degreased with trichlorethylene 1 2 5 Steel treated in the above-mentioned manner 1 1 1 of these plates was lost with 50 mg / m 2 of sodium nitrite. In turn, emulsions were prepared containing 1% (by volume) octyl sebacate, 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) triton - 45. Steel plates coated with sodium nitrite immersed in the emulsion for 10 seconds, allowed to settle and dried in an upright position for 1 hour at ambient temperature. It was found that 108 mg / m 2 of octyl sebacate was deposited on the steel surface. These steel plates were subjected to the above-described paintability and corrosion resistance test. Results are summarized in Tables 7 and 8. 30 40 Table 8 Corrosion resistance Condition immediately 24 hours at 1 RH 85 - | —90% 7 days at relative humidity of 85 - 90%. Steel degreased with trichlorethylene 1 2 5 Steel treated with the method given above 1 1 1 1 | Example III. An emulsion was prepared containing 1% (by volume) of linseed oil, 0.1% (by volume), 90% of phosphoric acid and 0.05% of triton X-45. Cold-reduced mild steel plates are immersed in this emulsion for 10 seconds, allowed to drain, and dried vertically at ambient temperature for 1 hour. It was found that 84 mg / m2 of linseed oil was deposited on the steel surface. These steel plates were subjected to the above-described tests for their susceptibility to painting and resistance to corrosion; The results are summarized in Tables 9 and 10. Table 7 Susceptibility to painting Ambient conditions Soaking in water for 1 day Erichsen's pressure test Erichsen's pressure Steel degreased with trichloroethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated in the 1 above manner removed 60 mm2 grade 1 1 removed 25 mm2 grade 4 \ 11 83 640 Table 9 Paintability 12 Ambient conditions Soaking in water for 1 day Erichsen compression test of Erichsen compression Steel degreased with trichlorethylene stripped 55 mm2 grade 3 SLA grade 5 / SLA Steel treated in the above-mentioned manner removed 25 mm2 grade 1 removed 15 mm2 grade 1 Table 10 Corrosion resistance Conditions Immediately 24 hours at a relative humidity of 85 - 90% and 7 days at a relative humidity of 85 - 90%. Steel degreased with trichlorethylene 1 2 5 Steel treated by the above-mentioned method m 1 1 1 Example IV. An emulsion is prepared containing 1% (by volume) octyl sebacate, 0.01% (by volume) 90% orthophosphoric acid and 0.05% (by volume) triton X-45. when cold, it was immersed in the emulsion for 10 seconds, allowed to sink and dried in an upright position for 1 hour at ambient temperature. 43 mg / m 2 of octyl sebacate was found to be deposited on the steel surface. These steel plates are subjected to the above-described paintability and corrosion resistance tests. The results are summarized in Tables 11 and 12. Table 12 Corrosion Resistance Conditions immediately 24 hours at 85 - 90% RH 7 days at humidity 85 - 90% RH. Steel degreased with trichlorethylene 1 2 5 Steel treated by the above-mentioned method 1 1 1 'Example 5 An emulsion is prepared containing 1% (by volume) octyl sebacate in water, 1% (by volume) 90% "orthophosphoric acid and 0.05% (by volume) triton X-45. Cold reduced mild steel plates are immersed in this emulsion for 10 seconds, allowed to drain and dried. in an upright position at ambient temperature for 1 hour It was found that 97 mg / m 2 of cktyl sebate was deposited on the steel surface and the steel plates were then subjected to the paintability and corrosion resistance tests described above. The results are presented in Tables 13 and 14. Table 11 Paintability Ambient conditions soaking in water for 1 day Erichsen pressure test Erichsen pressure test Steel degreased with trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated with the above described method removed 90 mm2 grade 3 removed 50 mm2 grade 413 83 640 Table 13 Paintability 14 Ambient conditions soaking for 1 day in water Erichsen pressure test Erichsen pressure test Steel degreased with trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated with the above described method removed 40 mm2 grade 1 removed 35 mm2 stage 2 Table 14 Corrosion resistance Conditions immediately 24 hours at relative humidity | 85-90% 7 days at a relative humidity of 85-90%. Steel degreased with trichlorethylene 1 2 5 Steel treated with the above-described method and 1 1 1 20 30 Table 16 Corrosion resistance Conditions immediately 24 hours with a relative humidity of 85 - 90% 7 days with a relative humidity of 85 - 90%. Steel degreased with trichlorethylene 1 2 5 Steel treated as described above | 2 1 2 | 1 1 Example VI. A solution is prepared containing 0.025% (by volume) octyl sebacate, 0.01% (by volume) 90% orthophosphoric acid in 60% (by volume) isopropyl alcohol and 40% (by volume) water. Cold reduced mild steel plates are immersed in this solution for 10 seconds, allowed to settle, and dried vertically at ambient temperature for 1 hour. It was found that 20 mg / m2 octyl sebacate was deposited on the steel surface. These tiles are subjected to the above-described paintability and corrosion resistance tests. The results are summarized in Tables 15 and 16. Example VII. A water emulsion is prepared containing 1% (by volume) octyl sebacate, 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) of X-45 triton. Hot-rolled and oiled steel plates are degreased with trichlorethylene and then immersed in the emulsion for 10 seconds; it is allowed to drain and dried vertically at ambient temperature for 1 hour. It was found that 156 mg / m 2 of octyl sebacate was deposited on the steel surface. These steel plates are then subjected to the above-described tests to have paintability and corrosion resistance. The results obtained are summarized in Tables 17 and 18. Table 15 Paintability Conditions | Soaking for 1 day in water Erichsen pressure test Erichsen pressure test Steel degreased with trichlorethylene removed 55 mm2, grade 3 SLA grade 5 / SL.A Steel treated with the above-described method removed 60 mm2 grade 1 removed 50 mm2 grade 315 83 640 Table 17 Paintability 16 Ambient conditions Soaking for 1 day in water Erichsen pressure test Erichsen pressure test Steel degreased with trichlorethylene removed 90 mm2 grade 2 CLA CLA Steel treated with the above described method removed 40 mm2 grade 2 1 removed 30 mm2 grade 3 Table 18 Resistance against corrosion Conditions immediately 1 24 hours at | Relative humidity 85-90% 7 days at a relative humidity of 85-90%. Steel defatted with trichlorethylene 1 1 1 Steel treated as above 1 1 1 | Example VIII. An emulsion was prepared containing 0.025% (by volume) octyl sebacate, 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) triton X-45. When cold, the emulsion is applied with a brush until a clearly uniform liquid level is obtained. The plates are then allowed to drain and dried vertically at ambient temperature for 1 hour. It was found that 54 mg / m 2 of octyl sebacate was deposited on the surface of the steel. The plates were then subjected to the paintability and corrosion resistance tests described above. 30 35 Table 20 Corrosion Resistance Conditions Immediately 24 hours at 85 - 90% RH 7 days at 85 - 90% RH Steel trichlorethylene degreased 1 2 5 Steel treated as described above 1 1 1 | The obtained results are summarized in Tables 19 and 20 '. Example IX. An emulsion was prepared containing 0.25% (by volume) sunflower oil, 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) triton X-45. reduced cold, it is immersed in the emulsion for 10 seconds, allowed to drain and dried in an upright position at ambient temperature for 1 hour. It was found that 112 mg / m2 of oil was deposited on the surface of the steel. Subsequently, these tiles are subjected to the above-described tests for paintability and corrosion resistance. The results obtained are summarized in Tables 21 and 22. Table 19 Susceptibility to painting Ambient conditions soaking for 1 day in water Erichsen's compression test Erichsen's pressure Degreased steel with trichloroethyl Nem removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated as described above removed 95 mm2 grade -5 1 removed 35 mm2 grade 517 83 640 Table 21 Paintability 18 Ambient conditions Soaking for 1 day in water Erichsen pressure test Erichsen pressure test Steel degreased with trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated as described above removed 50 mm2 grade 1 removed 45 mm2 grade 3 Table 22 Corrosion resistance Conditions Immediately 24 hours at relative humidity | 85-90% 7 days at RH 85-90%. Steel degreased with trichlorethylene 1 2 5 Steel treated as described above 1 1 1 Example X. An emulsion is prepared containing 0.025% (by volume) of lubricating oil in water (Croda fluid G 6938), 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) triton X-45. Cold reduced mild steel plates are immersed in this emulsion for 10 seconds, allowed to drain and dried in a vertical position for 1 hour at ambient temperature. It was found that 135 mg / m2 of oil was deposited on the surface of the steel. . The tiles are then subjected to the above-described paintability and corrosion resistance tests. The results obtained are summarized in Tables 23 and 24. Table 24 Corrosion resistance Conditions immediately 24 hours at 85-90% relative humidity 7 days at humidity 85-90% RH - Steel degreased with trichlorethylene 1 2 5 Steel treated as above 1 1 1 | Example XI. An emulsion is prepared containing 0.25% (by volume) of epoxy linseed oil in water. 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) tritone X-45. Cold reduced mild steel plates are immersed in this emulsion for 10 seconds and, after draining, dried vertically for 1 hour at ambient temperature. It was found that 61 mg / m2 of epoxidized linseed oil was deposited on the steel surface. Subsequently, the tiles are subjected to the above-described tests for paintability and corrosion resistance. The obtained results are summarized in Tables 25 and 26. Table 23 Susceptibility to painting Ambient conditions soaking for 1 day in water Erichsen's compression test Erichsen's compression Steel degreased with 55 mm2 trichlorethylene removed grade 3 SLA grade 5 / SLA Steel treated as above removed 50 mm2 grade 2 removed 50 mm2 grade 319 83 640 Table 25 Paintability 20 Conditions | ambient soaking for 1 day in water Erichsen pressure test Erichsen pressure test Steel degreased with trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated as described above removed 50 mm2 grade 1 removed 55 mm2 grade 3 Table 26 Corrosion resistance Conditions Immediately 24 hours at relative humidity | 85-90% 7 days at a relative humidity of 85-90%. Steel degreased with trichlorethylene 1 2 6 Steel treated by the method described above 1 1 2. An emulsion is prepared containing in water 1% (by volume) octyl sebacate, 0.1% (by volume), 90% orthophosphoric acid and 0.05% (by volume) of triton X-45. This emulsion is poured over plates of cold reduced mild steel and then passed through a wrapping roller. The time from flooding the plates to passage through the wrapping roller is 10 seconds. The plates are then dried in a vertical position for 1 hour at ambient temperature. It was found that 108 mg / m2 of octyl sebacate was deposited on the steel surface. The tiles are then subjected to the above-described paintability and corrosion resistance tests. The results obtained are summarized in Tables 27 and 28. 30 45 Table 28 Corrosion resistance Conditions immediately 24 hours at 85-90% relative humidity 7 days at humidity 85-90% RH. Steel degreased with trichlorethylene 1 2 5 Steel treated 1 by the method described above 1 1 | 2 | Example XIII. An aqueous solution is prepared containing 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) triton X-45. Cold reduced mild steel plates are poured with this solution and then passed through the roller. the smuggler. The time from flooding the plates to passing through the baking roller is 10 seconds. The plates are then placed vertically and dried at ambient temperature for an hour. A water emulsion is also prepared containing 1% (by volume) octyl sebacate and 0.05% (by volume) X-45 triton. Cold reduced mild steel plates are immersed in this emulsion for 10 seconds and then drained and dried vertically at ambient temperature for 1 hour. Table 27 was found to be deposited. Susceptibility to painting Ambient conditions soaking for 1 day in water Erichsen pressure test Erichsen pressure test Steel degreased with trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated 1 as described above removed 55 mm2 grade 2 and removed 50 mm2 grade 421 83 640 Table 29 Paintability 22 Ambient conditions soaking Erichsen pressure test Erichsen pressure test Steel degreased with trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated according to / removed 70 mm2 grade 3 removed 60 mm2 grade 4 Steel treated to b / removed 40 mm2 0 CLA * CLA * CLA = total loss of adhesion Table 30 Corrosion resistance Conditions Immediately 24 hours at 85-90% RH 7 days at 85-90% RH Steel degreased trichlorethylene 1 2 5 Steel treated according to A / 1 1 6 Steel processed according to b / 1 1 1 61 mg / m2 of octyl sebacate. These plates were subjected to the paintability and corrosion resistance tests described above. The results are summarized in Tables 29 and 30. Example XIV. The plates of cold reduced mild steel are precoated with oil (289 mg / m 2 octyl sebacate containing 2.5% triton X-45 surfactant). The plates are then flooded with an aqueous solution of 0.1% (by volume) 90% orthophosphoric acid and then passed through a winding roller. The time from flooding the plates to being taken over by the winding roller is 10 seconds. The plates are then placed vertically and dried for 1 hour at ambient temperature. Then the tiles are subjected to the above-described tests for paintability and corrosion resistance. The results are summarized in Tables 31 and 32. Table 31 Paintability Ambient conditions Soaking for 1 day in water Erichsen's compression test Erichsen's compression Degreased steel trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA steel treated as above removed 40 mm2 grade 1 removed 20 mm2 "grade 423 83 640 24 ethylene oxide surfactants (12p / wt), immersed in 0.1% (by volume) a solution of 90% phosphoric acid for 10 seconds, then placed vertically, allowed to drain and dried for 1 hour at ambient temperature. The steel plates are then subjected to the above-described paintability and corrosion resistance tests. The results are summarized in Tables 33 and 34. EXAMPLE XVI. An emulsion is prepared containing 1% (by volume) octyl sebacate, 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) triton X-45. These emulsions are sprayed on on a mild steel plate, cold reduced to an even liquid level. The emulsions are left on the plates for 10 seconds, after which the plates are dried in a stream of air under high pressure. The plates are then left at room temperature for 1 hour. 49 mg / m 2 of octyl sebacate was found to be deposited on the steel surface. These tiles were subjected to the paintability and corrosion resistance tests described above. The obtained results are summarized in Tables 35 and 36. Table 33 Paintability The surfaces were covered with a paint coat pigmented toluidine red; a pressure test with a 2.5 mm indentation was used.Conditions Ambient soaking for 1 day in water soaking for 7 days in water Contaminated steel, not treated with phosphoric acid removed 45 mm2 CLA CLA Contaminated steel, treated with phosphoric acid removed 40 mm2 removed 30 mm2 removed 20 mm2 Table 34 Corrosion resistance Conditions immediately 1 24 hours at 85-90% RH 7 days 85-90% RH Contaminated steel, not treated with phosphoric acid 1 1 1 Contaminated steel, treated with phosphoric acid 1 1 1 Table 32 Resistance to corrosion Conditions immediately 24 hours at 85-90% relative humidity 7 days at 85-90% relative humidity Steel degreased with trichlorethylene 1 2 5 Steel treated as above 1 1 1 1, Example XV . Cold reduced mild steel plates with a contaminated surface area of 50-100 mg / m 2 octyl sebacate (20% by weight based on the weight of the sediment), soluble inorganic salts (25% by weight based on the weight of the sediment), iron sediment ( 13% by weight), dirt and insoluble silica (2% by weight), triethanolamine (28% by weight) and detergents, 25 83 640 Table 35 Paintability 26 Ambient conditions Soaking for 1 day in water Erichsen's compression test Erichsen's compression Steel degreased with trichlorethylene removed 55 mm2 grade 3 SLA grade 5 / SLA Steel coated with the method described above removed 50 mm2 grade 1 removed 40 mm2 grade 4 Table 36 Corrosion resistance Conditions immediately 24 hours at relative humidity 85-90% 7 days at humidity relative 85-90%. Steel degreased with trichlorethylene 1 2 ° C. Steel treated by the method described above 1 1 2 | Example XVII. An emulsion is prepared containing 1% (by volume) octyl sebacate, 1% (by volume) 901% (by volume) orthophosphoric acid and 0.05% (by volume) X-45 triton. These emulsions are sprayed onto mild steel plates. cold reduced until an even level of liquid is obtained. The emulsions are left on the plates for 10 seconds, then they are dried in a stream of air under high pressure. The plates are then left for 1 hour at ambient temperature. It was found that 58 mg / m.sup.2 of ccyl sebacate was deposited on the surface of the steel. These tiles are subjected to the above-described paintability and corrosion resistance tests. The results are summarized in Tables 37 and 38. Table 38. relative humidity 85-90%. Steel degreased with trichlorethylene 1 2 5 Steel treated as described above 1 1 | 3 | Example XVIII. An emulsion 35 was prepared containing in water / 1% (by volume) octyl sebacate, 0.1% (by volume) 88% orthophosphoric acid and 0.05% (by volume) triton X-45. when cold, it was immersed in this emulsion for 10 seconds, and after dripping, it was dried vertically for 1 hour at ambient temperature. It was found that 83 mg / m * octyl sebacate was deposited on the steel surface. An emulsion was also prepared containing 1% (by volume) octyl sebacate and 0.05% (by volume) triton X-45. Cold reduced mild steel plates, which have been phosphated (500 mg / m2), are immersed in this emulsion for 10 seconds, allowed to drain and dried in an upright position for 1 hour at the temperature of Table 37. for painting Ambient conditions Soaking for 1 day in water Erichsen pressure test Erichsen pressure steel Steel degreased with trichlorethylene. removed 55 mm2 grade 3 SLA grade 5 / SLA Steel treated * as described above removed 65 mm2 grade 1 removed 85 mm2 grade 427 83 640 28 It was found that 42 mg / m2 of octyl sebacate was deposited on the phosphated steel plates. These tiles were subjected to the above-described paintability and corrosion resistance tests. The results are summarized in Tables 39 and 40. Example XIX. Slices 1.25 mm thick are cut from soft, cold-rolled steel sheet. Some of these plates are immersed for 5 seconds in a bath containing tap water, 0.02% tritcin X - 100 and the percentage of acid given in the table below. Erichsen 7 days of soaking in Erichsen's ambient water 1 day of matches in water 7 days of soaking in water T ab 1 ica 39 Steel degreased with trichlorethylene, (60 microns) 20 55 65 2 2 3 Steel degreased with trichloroethylene with ethylene (15-18 microns) 0 0 0 0 0 0 Phosphated steel immersed in an octyl sebate emulsion (15-18 microns) 40 65 75 4 5 5 Carbon steel immersed in the emulsion octyl sebacate and phosphoric acid (60 microns) 0 20 1 2 1 • 1 | Table 40 Corrosion resistance Conditions immediately 24 hours at 85-90% RH 7 days at 85-90% RH Phosphated steel immersed in an octyl sebacate emulsion 1 1 1 Carbon steel immersed in an emulsion of octyl sebacate and phosphoric acid 1 1 1 1 30 Then the plates are dried. Another part of the plates is processed in the same way, except that after treatment they are immersed for 5 seconds in a solution containing 5 g octyl sebacate in 1 liter methyl ethyl ketone. These plates are then left to dry. The result is a coating of 80 - 100 mg / m 2 octyl sebacate. Still other plates are treated first with octyl sebacate and then with each acid in the manner described above. Finally, for comparison, the plates 40 are turned on without any treatment and the plates are only immersed in the octyl sebacate solution above. The plates are exposed to free air for 5 days, after which the percentage is determined visually 45% H3P04 Polyphosphoric acid (82% P205) 30% phosphorous acid Granodine 20i (*) g / l - "* 1 1 1 30% rust Treatment without octyl sebacate 100 90 90 90 95 Phosphating agent followed by treatment with octyl sebacate 90 20 20 30 5 octyl sebacate followed by treatment with phosphating agent 90 30 20 25 5 (*) Conditions according to supplier's instructions with a 4-minute immersion period at 90 ° C. 29 83 640 Table 42 30 Treatment Type 85% H3PO4 polyphosphoric acid (82% P205) 30% phosphorous acid Granodine 20 without treatment g / l 1 1 1 30 Loss of paint adhesion | Phosphating agent and subsequent treatment with O-ktyl sebacate 3 3 5 5 SLA O-ktyl sebacate and subsequent treatment with phosphating agent 4 4 4 5 Some of the plates are then coated with a 25-30 micron layer of gray paint alkyd. After heating for 24 hours, the plates are immersed in distilled water at 40 ° C for 24 hours. An Erichsen test with a die of 7.0 mm is then carried out to determine the percentage of loss in adhesion of the paint. A low-adhesion paint is removed with a pressure-sensitive tape; the adhesion loss according to this method is determined according to the data in Table I. The results are summarized in Table 42. Example XX. In order to demonstrate the superior lubricating performance when the method of the invention is applied to steel to be formed, established methods of assessing lubricity (slipperiness) have been applied in both methods for the deformation by pressing and stretching described by J.C. Wright (Sheet Metal Industries, '38, No. 414, October 1961, p 731-74), D.H. Lloyd (Sheet Metal Industries, 39, No. 419, March 1962, p 158-166), J.F. Wallace (The British Iron and Steel Research US RAO (Sheet Metal Industries, 44, No. 486, Associaion Report No. MW/E/62/55), October 1967, p 673-678). mm of cold reduced mild steel, each unit being degreased in trichlorethylene vapor and treated as shown in the table provided. The disc assemblies also include discs with no grease and a low-density polyethylene coating, 100 µm thick, applied on both sides. The lubricating properties of the samples were measured using an Erichsen 1126 hydraulic measuring apparatus, equipped with screw elements. Agitation, applied load and displacement data. Tensile forming lubrication is assessed by means of Erichsen pressure tests on blanks (starting material) with a diameter of 55 mm, the total being the depth of extrusion to crack formation and ¬ maximum load applied. Large soil - Table 43 20 23 30 35 55 60 65 Steel treatment Pure steel used in excess of Croda-fluid *) 66938 used in excess of Tellus 15 oil 2) Octyl sebacate applied in the form of a thin film of an emulsion containing 1% in water (by volume) Octyl sebacate and 0.05% (by volume) tritone X - 45. Crodafluid G6938 applied as a thin film emulsion containing in water 025% (by volume) Crodafluid G6938 and 0.05% (by volume) X-45 triton. Tellus oil 15 was used as a thin film of an emulsion containing in water 1% (by volume) of Tellus oil and 0.05% (by volume), triton X - 45, octyl sebacate and ortho-acid. Phosphoric acid used according to the invention in an aqueous emulsion containing 1% (by volume) octyl sebate, 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) of X-45 triton. Crodafluid G6938 and orthophosphoric acid used according to the invention in an aqueous emulsion containing 0.25% (by volume) of Crodafluid G6938; 0.1% (by volume) 90% orthophosphoric acid and 01.05% (by volume) triton X - 45. Tellus 15 oil and orthophosphoric acid used in the invention in an emulsion containing 1% in water (by volume) (By volume) of Tellus 15 oil, 0.1% (by volume) 90% orthophosphoric acid and 0.05% (by volume) of triton X - 45.100 µm thick polythene coating of low density applied on both sides of the disc Concentration 1 oil * (mg / m2) 73 21 23 114 30 58-31 83 640 32 In all tested cases, the lubricating efficiency of the method according to the invention was better than those in which the components were used (independently and better than 5 high oil concentrations were used on the steel surface PL PL PL PL PL

Claims (5)

1. Claims 10 1. Method for the pretreatment of metal surfaces by using a phosphating agent and an oily material, characterized in that a phosphating agent and an oily material are used simultaneously or separately, excluding systems in which more than 50 mg. / m2 of the phosphating agent is deposited in a separate stage directly on the metal or in combination with more than 150 mg / m2 of the oily material. twenty 2. The method according to p. The process of claim 1, wherein the oleaginous material is dioctyl sebacimate. 3. The method according to p. The method of claim 1 or 2, characterized in that an accelerator phosphatizing system is used. 25 4. The method according to p. The method of claim 1, wherein the phosphating agent is an aqueous solution of 90% phosphoric acid in an amount of 0.01-1.0% by volume. Table 44 Pressure test Treatment of steel No grease was used (1) Clean steel, degreased (2) Treated with phosphoric acid 1 Used in excess of con-. 1 conventional lubricating oils | (1) Crodafluid G6938 (2) Tellus 15 Oils used as thin films from dilute aqueous emulsions (1) Octyl sebacate (2) Crodafluid G6938 (3) Oils used according to the invention (1) Octyl sebacate (2) ) Crodafluid G6938 (3) Tellus 15 Example of an extremely good grease Polyethylene film Maximum force applied (any units) 0 10 20 .30 40 50 60 55.3 out of 4 samples peclo X 38.0 33.9 36.7 34.1 45.6 1 of 3 peklo samples X 38.0 | 33.5 32.5 32.0 | 27.8 X specimen did not withstand the pressing and cracked under load 0 * 10 20 30 40 50 60 Maximum applied force (any units) cont. Table 43 Steel treatment Treatment with orthophosphoric acid by immersion in an aqueous solution containing 0.1% (by volume) 90% orthophosphoric acid Concentration of 1 oil (mg / m2) 1) Crodafluid G6938 obtained from Croda Chemicals Limited 2) Tellus 15 oil obtained from Shell-Mex and BP Limited stamping effort and low maximum load are indicative of effective lubrication, with a low density polyethylene coating ideal. Stamping lubrication is assessed using an Erichsen apparatus with a 33 mm die and 55 mm blank specimens. The relative lubricity (slippage) of the various systems was assessed by the work done to obtain the stamping and by the stamping peak load. Low work and peak load values are indicative of effective lubrication, with a low density polyethylene coating being ideal. The results obtained from the compression test are shown in Table 44.83 640 33 34. The process of claim 3, wherein NaNO 2 and NaNO 3 are used as the phosphating agent accelerator. 6. The method according to p. 7. The method of claim 1, wherein the oily material is "5 - 100 mg / m2. The method of claim 1, wherein the oily material and the phosphating agent are used in the form of an aqueous emulsion. The method of claim 1, wherein the oily material and the phosphating agent are used in an aqueous solution containing a solvent. The method of claim 1, wherein 0.01-40 mg of phosphate per m2 is deposited. Method according to claim 1, characterized in that steel is treated, the surface of which is already protected with an oily material. 11. A method according to claim 3, characterized in that prior to further processing, the steel is coated with a phosphating accelerator. , characterized in that the protective agent is brought into contact with the surface for up to 3 minutes, preferably up to 30 seconds. 10 \ 83 640 \ Fig. 2 Fig. 3 Fiq. 5. Fig. 6 Fig. 7 Fig. 8 Fig. 9 Fig. (0 '' ¦ •. •?: I «'. 1 F'9" Hi Fig. 12 OZGraf. Lz. 1238 (120 + 25 copies. ) Price 10 PLN PL PL PL PL PL