CN115612973A - Laser high-temperature flash forming method for surface oxide film of steel material - Google Patents
Laser high-temperature flash forming method for surface oxide film of steel material Download PDFInfo
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- CN115612973A CN115612973A CN202211363366.6A CN202211363366A CN115612973A CN 115612973 A CN115612973 A CN 115612973A CN 202211363366 A CN202211363366 A CN 202211363366A CN 115612973 A CN115612973 A CN 115612973A
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/12—Oxidising using elemental oxygen or ozone
- C23C8/14—Oxidising of ferrous surfaces
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The application discloses a laser high-temperature flash forming method of an oxide film on the surface of a steel material, which comprises the following steps: coating the Fe to be formed by the activating solution 3 O 4 Oxidizing the surface of the ferrous material to form a layer containing Fe on the surface of the ferrous material 2+ 、Fe 3+ An activated membrane of ions; heating by a laser beam for heating requires the generation of the Fe 3 O 4 The surface of the iron and steel material of the oxide film reaches 1450-1500 ℃, and the Fe is generated in a flash speed 3 O 4 And oxidizing the film, and spraying oxygen to the surface of the ferrous material while irradiating the surface of the ferrous material with a laser beam for heating.
Description
Technical Field
The invention relates to the technical field of preparation of an oxide film on the surface of a steel material, in particular to a laser high-temperature flash forming method of the oxide film on the surface of the steel material.
Background
Industrial parts are mostly made of steel materials such as rolls, which are important parts of rolling mills in hot rolling lines, and roll a steel strip under vertical pressure by a pair of rolling rolls, with direct material consumption of about 5 to 15% of the production cost of rolled steel.
In the production process of hot rolled steel strips, the working conditions of the roller are very severe, the roller is contacted with a rolled material with the temperature of 900-1200 ℃, the surface of the roller is subjected to high-temperature oxidation besides the strong high-temperature friction and wear action of the rolled material, an oxide film is generated on the surface of the roller, and the peeling of the oxide film aggravates the failure of the roller. In addition, the roller can be repeatedly heated by a rolled material and cooled by cooling water in the working process, and bears high-frequency chilling shock heat, fatigue thermal stress generated by the chilling shock heat can induce micro-cracks, and the fatigue micro-cracks continuously expand under the action of rolling force, so that the surface of the roller is finally cracked and even peeled off, and the failure of the roller is promoted. Therefore, the hot roll should have excellent oxidation resistance and thermal fatigue resistance in addition to high wear resistance and toughness.
The high-speed steel has the characteristics of high toughness and high hardness in physical properties, particularly high-temperature hardness, high wear resistance, good red hardness, good roughness and the like, and has better oxide film generation capacity, and the steel rolling quantity of single grinding can reach 2-4 times of that of high-chromium iron materials, so that the high-speed steel roll is widely applied to a front section rack (F1-4) of finish rolling, and new high-speed steel rolls are gradually developed and popularized and applied to a rough rolling rack and a rear section rack of finish rolling.
However, high-speed steel is expensive, and in practical application, in order to reduce cost, a composite high-speed steel roll is often adopted. The composite high-speed steel roll is formed by sleeving a high-speed steel roll sleeve on a core roll, wherein the core roll can be a nodular cast iron roll and the like. In the process of hot finish rolling of the steel plate, the steel plate needs to be rolled by 6-8 stands in sequence, wherein the rolling temperature of the first four stands is high, about 900-1200 ℃, the rolling reduction is large, the rolling force is large, and a high-speed steel roller is generally adopted.
In the process of hot rolling steel plates, as the surface of the roller is contacted with the red hot high-temperature steel billet, a layer of oxide scale is generated on the surface of the roller, and the layer of oxide scale has positive and negative effects.
The hot rolling method has the beneficial effects that firstly, the friction force can be reduced, the roller abrasion can be reduced, secondly, the hot red steel billet can be prevented from being adhered to the surface of the roller, and thirdly, the oxide skin has low heat conductivity coefficient, the roller matrix and the hot red steel billet can be isolated, the temperature of the roller matrix is reduced, the thermal shock is reduced, and the thermal fatigue crack on the surface of the roller is inhibited.
The roll surface scale has a disadvantage in that loose ferrous oxide (FeO) is dominant due to the scale layer formed in the prior art. Therefore, the scale layer is easily peeled off during the subsequent rolling. The scale which is peeled off is pressed into the surface of the slab and further elongated into a chain shape as the rolling proceeds, deteriorating the surface quality of the slab, resulting in that the rolled steel sheet can be degraded or discarded for use.
According to statistics, the scrap rate of the hot-rolled high-strength steel plate caused by the scale peeling is about 20%, for example, a production line producing 600 ten thousand tons every year, 120 ten thousand tons of steel materials are scrapped or degraded for use every year, and the sale price is different by 500 yuan/ton after the grade is reduced, so that 3000 yuan is lost every year by only one hot-rolled production line of 600 ten thousand tons. The loose scale is peeled off along with the rolling process, so that the roller is seriously abraded, and when a high-quality steel plate is rolled, the roller is usually rolled for less than 3 times on average in order to improve the plate surface quality, and the roller needs to be taken off the mill for re-grinding, so that the roller is extremely high in loss. And frequent grinding of the roller can lead to frequent shutdown and replacement of the roller, cause shutdown loss and cause unstable quality of the rolled plate blank.
The iron oxide is three, one is ferrous oxide (FeO), and the FeO is a p-type semiconductor with insufficient metal and has about 5 to 16 percent of cation defects, so that the FeO layer has higher cation vacancy concentration, which causes the mobility of cations and electrons in the FeO layer to be very high, and the growth rate of the FeO layer is very fast. However, feO is black, has a loose structure and is easily peeled off.
The second one is ferric oxide (Fe 2O 3), fe2O3 is an n-type semiconductor with insufficient oxygen, has high oxygen content, has many oxygen ion defects inside, forms anion vacancy, and is favorable for oxygen diffusion inside in the outside, and Fe 2 O 3 gamma-Fe having two crystal structures and being metastable at low temperatures 2 O 3 Cubic crystal of alpha-Fe having a rhombohedral structure at temperatures above 400 DEG C 2 O 3 ，Fe 2 O 3 It is red. The main component of the red brown rust is iron oxide with n crystal waters (Fe) 2 O 3 ·nH2O)。
Third ferroferric oxide (Fe) 3 O 4 ) Fe3O4 is a p-type semiconductor, and is more stoichiometric than FeO, so it is unfavorable for Fe 2+ Diffusion of Fe 3 O 4 From one Fe 2+ And two Fe 2+ 、Fe 3+ Composition of spinel structure, fe 2+ And Fe 2+ 、Fe 3+ Respectively located in the interstitial positions of tetrahedrons and octahedrons. Fe 3 O 4 Black, compact, high hardness, can be used as abrasive and polishing agent and can play a role in protection, so a layer of Fe is generated on the surface of a steel part by blackening or bluing treatment in industry 3 O 4 The film plays a role in corrosion prevention. Therefore, if a layer of Fe closely bonded to the substrate can be formed on the surface of the roll 3 O 4 The film greatly improves the high-temperature wear resistance of the roller, prolongs the service life of the roller and improves the surface quality of the rolled plate strip.
As shown in FIG. 1, there are two cases in which Fe can be stably produced according to the phase diagram of ferrite reaction 3 O 4 In one case, low temperature generation of Fe 3 O 4 When the temperature is lower than 570 ℃ and the oxygen content is less than 57at%, the iron and the oxygen can generate ferroferric oxide, and further according to the relationship between Gibbs free energy and temperature in the oxidation reaction, the pure iron contains Fe in the oxidation product below 567 DEG C 3 O 4 Most stable, the generated thermodynamic tendency is the largest; in another case, fe is generated at a high temperature 3 O 4 Namely, iron and oxygen can generate ferroferric oxide at 1450-1582 ℃ and when the oxygen content is more than 58at percent. In other cases, a mixture of ferrous oxide, trisomy tetroxide and ferric oxide is typically produced.
For example, CN114622154A discloses a device and a process for laser forming a prefabricated oxide film on the surface of a hot roller, which is used for manufacturing an oxide film at 800-900 ℃. However, according to the ferrite reaction phase diagram, at this temperature, a large amount of pumice is produced, and a high proportion of Fe cannot be obtained no matter how long the temperature is maintained 3 O 4 。
Actually, in the prior art, there are two general approaches to form an Fe3O4 oxide film at a temperature lower than 570 ℃.
One is a specific method for treating high-temperature water vapor, which is to place the steel piece in high-temperature water vapor with the temperature of 540-570 DEG CIn the method, a layer of blue ferroferric oxide (Fe) is generated on the surface of the iron core 3 O 4 ) A thin film having a thickness of 4 to 6 μm. The oxide film has a fine structure and can be firmly adhered to the surface of metal, and the principle is that water vapor is contacted with hot iron to decompose and release active oxygen atoms, and then the active oxygen atoms react with the metal iron to generate Fe 3 O 4 And the core is deposited on the surface of the workpiece after growing up. The high-temperature steam treatment needs to heat the workpiece to about 550 ℃, the high-temperature steam treatment time needs about 1 hour, and the working procedure time that the roller is heated from room temperature to 550 ℃ and slowly cooled to room temperature after the bluing treatment is finished needs about 3 hours for small-sized workpieces, so that the method has the problems of high energy consumption and long time. If the method is adopted to carry out bluing treatment on the surface of the high-speed steel roller, the length of the high-speed steel roller is 5.5 meters, the maximum diameter can reach 1 meter, and the weight can reach 30 tons. For example, it is difficult to find such a huge heating furnace, the heating cost is too high, a roller weighing 30 tons needs more than 10 hours for heating to 550 ℃, a high-speed steel roller is softened by tempering once heated to 550 ℃, the hardness of the roller is reduced, and the roller is scrapped, and the high-speed steel roller is fragile and the surface of the roller is likely to crack in the air cooling process. Therefore, it is not feasible to treat high-speed steel rolls by high-temperature bluing.
Second generation of Fe 3 O 4 The oxidation film is prepared by alkali boiling oxidation at 140 deg.C by adding NaOH and NaNO into steel piece 2 In the mixed solution, fe is generated through chemical reaction 3 O 4 Oxide film, thickness and compactness of film and NaOH and NaNO during oxidation 2 The concentration, temperature and treatment time of Fe, if the temperature is too low 3 O 4 The nucleation rate and growth rate of (2) are low, the oxide film is difficult to form, the temperature is too high, and the oxide film is easy to dissolve, so the treatment temperature needs to be strictly controlled between 130 ℃ and 150 ℃. The method has serious pollution, and the working environment is severe after the strong alkali liquor is volatilized. For high speed steel with high alloy content, cooking in alkaline solutionThe time is far longer than that of common carbon steel, and about 80 minutes is needed. If the alkali cooking oxidation method is adopted to generate Fe on the surface of the high-speed steel roll 3 O 4 Firstly, the treatment time is long, only 80 minutes are needed for alkaline cooking, in addition, a roller of 30 tons can be placed into a high-temperature alkaline solution pool after being heated to 130 ℃, otherwise, the temperature of the alkaline solution in the whole alkaline cooking pool can be reduced, the roller of 5.5 meters in length, 1m in diameter and 30 tons in weight can be heated to about 140 ℃ after being heated for at least 3 hours, and in addition, the surface cleaning and other procedures after being lifted out of the alkaline cooking pool are added, and the treatment of one roller needs at least 6 hours; secondly, serious pollution exists, alkali liquor volatilizes to pollute the working environment, and residual alkali liquor on the surface of the roller needs special treatment; thirdly, the treatment cost is high, and a high-temperature alkali liquor pool with huge volume is needed; and fourthly, the quality of oxide skin is difficult to ensure, the thickness and the uniformity of the oxide film are greatly influenced by the concentration and the temperature of alkali liquor, the concentration and the temperature of the alkali liquor in the huge alkali liquor pool fluctuate greatly, the consistency of the quality of the oxide film generated on the surfaces of different rollers is difficult to ensure, and even if the same roller is used, the quality of the oxide film is uneven and inconsistent due to the difference of the concentration, the temperature and the flow speed of the alkali liquor.
The prior art does not use high temperature (1450-1582 ℃) to form Fe 3 O 4 The first of the existing technologies is that the whole workpiece is heated, the energy consumption is too high, and the whole workpiece is heated to such a high temperature, the workpiece is softened, the workpiece is cracked due to uneven internal and external temperatures in the cooling process, the material is also phase-changed, the treatment time is long, the required field is large, the equipment is complex, and a high-concentration oxygen atmosphere (the oxygen content is more than 58 at%) needs to be formed, which is difficult to implement in terms of performance, cost and efficiency.
Secondly, as can be seen from the ferrite reaction phase diagram shown in FIG. 1, fe 3 O 4 The area of the oxide film formed under the high temperature condition is narrow, the condition is strictly controlled and is lower than 1450 ℃, and Fe can not be formed 3 O 4 The oxide film, which is formed above 1500 ℃, causes the steel material to melt, so that the treatment temperature needs to be precisely controlled. On the other hand, if only air is passed or oxygen is supplied, since oxygen supplied in air and oxygen is molecular oxygenBut not active oxygen atoms, can not react with steel rapidly to generate an oxide film. .
Disclosure of Invention
One advantage of the invention is to provide a laser high-temperature flash forming method of an oxide film on the surface of a steel material, which firstly provides a flash generation method of Fe at high temperature (1450-1500 ℃) 3 O 4 The method for oxidizing the film solves the problem of the traditional generation of Fe 3 O 4 The oxide film can only slowly proceed at a low temperature.
An advantage of the present invention is to provide a laser high-temperature flash forming method of an oxide film on a surface of a ferrous material, in which Fe can be generated in situ on the surface of the ferrous material by the laser high-temperature flash forming method of the oxide film on the surface of the ferrous material 3 O 4 The oxide film is tightly combined with the steel material substrate, thereby solving the problems of easy generation of FeO and low binding force of the traditional oxidation method.
An advantage of the present invention is to provide a laser high-temperature flash forming method of an oxide film on a surface of a steel material, which can form stable Fe on the surface of the steel material by the laser high-temperature flash forming method of the oxide film on the surface of the steel material 3 O 4 The oxidation film has simple operation condition and low manufacturing cost, and solves the problems of long oxidation time, high temperature and large energy consumption of the traditional oxidation method.
Another advantage of the present invention is to provide a method for forming an oxide film on a surface of a steel material by laser flash at a high temperature, wherein the method comprises applying an activating solution on the surface of the steel material to form an activated film, wherein the activated film can absorb light and increase the laser absorption rate, and further, active Fe can be formed in the activated film in advance or at the same time when the laser forms a high temperature 2 + 、Fe 3+ Ions, and at the same time, active oxygen atoms and active Fe can be released when the activated film is heated and decomposed at high temperature 2+ 、Fe 3+ The ions and active oxygen atoms can be rapidly combined to generate Fe in a flash memory 3 O 4 The oxidation film solves the problems of high laser reflectivity and low light absorption rate of the surface of the steel, and also solves the problem of the traditional steel oxidation reactionThe problem of long time is solved, so that millisecond-level flash oxidation is possible.
Another advantage of the present invention is to provide a laser high temperature flash forming method of an oxide film on a surface of a ferrous material, in which Fe can be formed in an extremely short time (e.g., 0.01 to 10 msec) by the laser high temperature flash forming method of an oxide film on a surface of a ferrous material 3 O 4 And (5) oxidizing the film.
Another advantage of the present invention is to provide a laser high-temperature flash forming method for an oxide film on a surface of a steel material, wherein a laser beam with high energy for heating is used to rapidly scan the surface of the steel material, and a local high temperature is formed only at a depth of micrometer scale of a laser spot on the surface of the steel material, thereby solving the problems of overall heating, complex equipment, large area, high energy consumption and low efficiency of the conventional method.
To achieve at least one of the above advantages, the present invention provides a method for laser high-temperature flash formation of an oxide film on a surface of a ferrous material, including:
in the presence of Fe 3 O 4 Coating an activating solution on the surface of the iron and steel material with the oxide film to form an activated film on the surface of the iron and steel material; and
the Fe is required to be generated by laser beam scanning for heating 3 O 4 Oxidizing the surface of the steel material with the film to heat the laser scanning spot on the surface of the steel material to 1450-1500 ℃ to generate the Fe in a flash manner 3 O 4 And (5) oxidizing the film.
According to an embodiment of the present invention, the activation film contains Fe 2+ 、Fe 3+ Ions.
According to an embodiment of the present invention, the surface of the ferrous material is pretreated, including:
grinding the surface of the steel material to remove the surface fatigue layer; and/or
Cleaning the emulsion or the oil stain on the surface of the steel material by alkali, and removing the emulsion or the oil stain on the surface of the steel material by water washing; and/or
Wiping the surface of the steel material with alcohol.
According to an embodiment of the present invention, the activation solution is an activation solution containing an oxygen-containing acid ion.
According to an embodiment of the present invention, the activation solution containing the oxide ion is an activation solution containing either a phosphate ion and/or a sulfate ion and/or a nitrate ion and/or a hypochlorite ion.
According to an embodiment of the present invention, the laser high temperature flash forming method of the oxide film on the surface of the steel material includes the steps of:
and coating a light absorbing agent on the surface of the activated film before or at the same time of scanning the laser beam.
According to an embodiment of the present invention, the light absorber is a carbon-based light absorber.
According to an embodiment of the invention, the ferrous material is a roll.
According to an embodiment of the present invention, oxygen is sprayed to the surface of the ferrous material at the laser spot while irradiating the surface of the ferrous material with the laser beam for heating.
According to an embodiment of the present invention, the flow rate of the oxygen is 0.1 to 15L/min.
According to an embodiment of the present invention, the time for forming the oxide film is 0.01 to 10 milliseconds.
According to an embodiment of the present invention, the color of the activated film is dark.
According to an embodiment of the present invention, the activation solution is an activation solution free of oxygen radical ions, and the laser high temperature flash forming method of the oxide film on the surface of the steel material includes:
and spraying oxygen to the laser spot on the surface of the ferrous material while irradiating the surface of the ferrous material with a laser beam for heating.
According to an embodiment of the present invention, the activating solution is a halogen-containing activating solution.
Drawings
Figure 1 shows a phase diagram for the ferrite reaction.
Fig. 2 is a flowchart illustrating a laser flash forming method of an oxide film on a surface of a ferrous material according to an embodiment.
Detailed Description
The following description is presented to disclose the invention so as to enable any person skilled in the art to practice the invention. The preferred embodiments described below are by way of example only, and other obvious variations will occur to those skilled in the art. The underlying principles of the invention, as defined in the following description, may be applied to other embodiments, variations, modifications, equivalents, and other technical solutions without departing from the spirit and scope of the invention.
It will be understood by those skilled in the art that in the present disclosure, the terms "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for convenience in describing the invention and simplicity in description, but do not indicate or imply that the device or component being referred to must have a particular orientation, be constructed in a particular orientation, and be constructed in a particular manner of operation, and thus, the terms are not to be construed as limiting the invention.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
Referring to fig. 2, a method for laser flash formation of an oxide film on a surface of a ferrous material according to a preferred embodiment of the present invention will be described in detail below. The laser high-temperature flash forming method of the surface oxide film of the steel material comprises the following steps:
s1001, coating the activating solution on Fe to be generated 3 O 4 The surface of the ferrous material being oxidized, e.g. by coating it on the surface of a roll, to form a layer containing Fe on the surface of the ferrous material 2+ 、Fe 3+ An ion activated membrane.
In one embodiment, the activation liquid is implemented as an activation liquid containing an oxyanion.
Illustratively, the activating solution is sulfuric acid or/and sulfate, the surface of the steel material such as a roller is coated with sulfuric acid or/and sulfate to carry out pre-activation treatment on the surface of the roller, so that iron elements on the surface of the steel material react with sulfate ions, and a layer of FeSO is generated according to different concentrations and different reaction temperatures of the sulfate ions 4 Or Fe 2 (SO 4 ) 3 Activation film of Fe atoms, as compared with Fe atoms 2+ 、Fe 3+ The activity of the ions is greater, and the activity of the oxidation reaction is further improved, so that a layer of Fe can be generated on the steel material in a flash manner at high temperature 3 O 4 And (5) oxidizing the film.
In addition, SO 4 2— Decomposition at high temperature to generate active [ O ]]Elements, activity [ O ] produced by these decompositions]Element, promoting Fe more easily than oxygen 3 O 4 And (5) forming an oxide film.
By forming a layer containing Fe on the surface of the steel material 2+ 、Fe 3+ An activated film of ions due to Fe 2+ 、Fe 3+ High ion activity and can form Fe in high temperature environment 3 O 4 And (5) oxidizing the film.
For example, in one example, a layer containing Fe is formed on the surface of a steel material by coating sulfuric acid or/and sulfate 2+ 、Fe 3+ An ion activated membrane. The sulfuric acid or sulfate reacts with iron on the surface of the steel material such as the roller to produce FeSO 4 、Fe 2 (SO 4 ) 3 Film, feSO 4 、Fe 2 (SO 4 ) 3 The film color is yellow, yellow brown, brown or brownish black and other dark colors, the specific color is determined by the action time, and the longer the action time is, the darker the color is.
If the deep color activation film is not arranged, the surface color of the ground roller is bright silver, the reflectivity of the ground roller is extremely high, on one hand, the laser efficiency is low, on the other hand, because the surface of the roller is a circular arc curved surface, the reflectivity of the laser on the surface of the roller is different, namely, the different light absorptions of the same light spot at different positions are different, the different light absorptions can cause different temperatures, and the different temperatures can cause oxidationThe film is not uniform, thereby causing Fe to be generated subsequently 3 O 4 The oxide film is not uniform. Therefore, the activation treatment by the activating solution on the surface of the roller has three functions, namely forming active Fe 2+ 、Fe 3+ Ions and active [ O]Element, promoting Fe 3 O 4 The oxide film is formed rapidly, the dark ferric nitrate film can greatly improve the light absorption rate, and the third is to ensure the generated Fe 3 O 4 Uniformity and consistency of quality.
More importantly, the activated membrane can release activity [ O ] after decomposing at high temperature]Elements, so that it is possible to rapidly form Fe on the surface of a steel material at a high temperature (1450-1500 ℃) without additional introduction of oxygen 3 O 4 And (5) oxidizing the film.
Preferably, in the step S1001, when sulfuric acid or/and sulfate is used as the activation liquid, sulfate ions [ SO ] in the activation liquid 4 2- ]The concentration of (B) is 0.5-15 mol/L.
In yet another embodiment, the oxygen-containing acid radical ion activation solution is embodied to contain nitrate ions (NO) 3 - ) To form active Fe on the surface of the ferrous material 2+ 、Fe 3+ Ionic ferrous nitrate, ferric nitrate activated membranes. It is understood that the nitrate ion (NO) is contained 3 - ) Can also provide activity [ O ] when the activated film is formed at a high temperature under subsequent laser beam irradiation]Element, thereby being capable of promoting Fe 3 O 4 The oxide film is formed rapidly. In addition, nitrate ion (NO) is generated 3 - ) After the activating solution is used, the surface of the steel material is gradually changed into dark color such as yellow, brown and brownish black from silvery white, and the activating solution can play a role in improving the laser absorptivity and greatly reducing the laser reflection.
In yet another embodiment, the oxygen-containing ion activation solution is embodied to contain hypochlorite ions (ClO) - ) To form active Fe on the surface of the steel material 2+ 、Fe 3+ Ionic ferrous hypochlorite, chlorinationThe iron activates the membrane. It is understood that the hypochlorite ion (ClO) is contained - ) Can provide activity [ O ] by decomposition at a high temperature in the subsequent laser beam formation]Element thereby promoting Fe 3 O 4 The oxide film is formed rapidly. In addition, chlorine hypochlorite (ClO) is generated - ) After the film is activated, the surface of the steel material is gradually changed from silvery white to dark color, such as green, yellow-green and yellow, so that the effects of improving the laser absorbance and reducing the laser reflection are achieved.
In yet another embodiment, the oxygen-containing acid ion activation solution is implemented as an iron-based phosphating solution containing phosphate ions.
Preferably, the main component of the iron-based phosphating solution is phosphoric acid (H) 3 PO 4 ) Sodium dihydrogen phosphate (NaH) 2 PO 4 ) The oxidant is NaNO 3 ，Fe 2+ 、Fe 3+ Is generated by the reaction of iron atoms on the surface layer of the steel material and phosphating solution.
It should be noted that, in this embodiment, the iron-based phosphating solution is an iron-based phosphating solution with a phosphate concentration of 10 to 30g/L and a pH value of 2.0 to 3.0.
According to the different components of the phosphating solution, the phosphating treatment comprises zinc series, manganese series, zinc-calcium series and iron series phosphating, wherein the iron series phosphating is characterized in that the phosphating solution contains Fe 2+ 、Fe 3+ The ions, iron ions, can be provided by the dissolution of the steel surface. Compared with zinc series, manganese series and zinc-calcium series, the iron series phosphorization has the advantages of thin thickness (less than 1 mu m), high porosity and low density (the film weight is 0.2-1 g/m) 2 ) The phosphorized film is mostly blue-purple in color, and can be iridescent and gray according to different reaction time, different film thicknesses and different components of phosphorized liquid. Therefore, the dark iron-based phosphating film can be used as a laser light absorber, has thin thickness and high porosity, and can ensure that oxygen can penetrate through the phosphating film to be contacted with iron elements of a steel substrate. Therefore, the invention selects the iron-based phosphating solution to carry out activation treatment on the surface of the steel workpiece.
In the process of phosphating, the surface of a steel substrate reacts with phosphoric acid or hypophosphite in phosphating solution, wherein atoms on the outer layer of a steel workpiece react with the atoms in the solutionThe anion of the medium reacts, the soluble phosphate on the surface is continuously converted into insoluble phosphate, and finally a phosphate conversion film is deposited on the surface of the steel workpiece. The main component of the iron-based phosphating film is FePO 4 、Fe 3 (PO 4 ) 2 And Fe (OH) 3 。
Phosphate radical (PO) in the phosphating solution of the example 4 3- ) The concentration range is different from that of common phosphating solution, and phosphate radical (PO) is adopted in the invention 4 3- ) The concentration is 10-30 g/L, and the concentration of phosphate radical in common phosphating solution is generally more than 30g/L. In the present invention, if phosphate radical (PO) 4 3- ) When the concentration is less than 10g/L, the film is too thin and the color is too light, which is not beneficial to improving the light absorption rate, and when the concentration is less than 10g/L, the phosphate radical (PO) is used 4 3- ) When the concentration is more than 30g/L, the thickness of the membrane is overlarge, the compactness is improved, and the subsequent oxygen permeation is not facilitated. The invention aims to obtain a blue-purple, iridescent or gray, loose and porous phosphating film with thin thickness, so that the phosphating process parameters of the two phosphating solutions are different in selection range.
The phosphating film in the embodiment has the characteristics of bluish purple, iridescent or gray color, thin thickness and low corrosion resistance so as to improve the laser absorptivity.
The pH value of the phosphating solution in the embodiment is also different from that of the traditional phosphating solution, the pH value of the phosphating solution in the invention is 2.0-3.0, and the pH value of the traditional phosphating solution is generally 3.0-4.5. The pH value is low, the hydrogen evolution amount is large, the film layer is loose and porous, but the pH value is lower than 2.0, the local corrosion is too fast, the phosphating film is not uniform, the pH value exceeds 3.0, the film density is increased, the film thickness is increased, and the oxygen permeation of the subsequent oxygen spraying process is not facilitated. In the traditional phosphating treatment, in order to generate a phosphating film with good compactness, large thickness and corrosion resistance, the pH value of phosphating solution is higher. In another embodiment, the activation liquid may also be implemented as an activation liquid free of an oxygen radical ion.
Preferably, the activation liquid free of the oxygen acid ion may be implemented as an activation liquid containing a halogen ion.
For example, the anaerobic ion-free activation solution is implemented as a chloride ion (Cl) - ) To form active Fe on the surface of the ferrous material 2+ 、Fe 3+ The ionic ferrous chloride and ferric chloride activate the membrane. Active Fe contained in the activated film 2+ 、Fe 3+ The ion being in favour of Fe 3 O 4 The oxide film is formed rapidly. But contains chloride ions (Cl) as compared with the activation solution containing the oxygen radical ions - ) When the activated film of (2) is formed at a high temperature under the subsequent laser beam irradiation, the activity [ O ] is not provided]When the laser irradiates the surface of the steel material, oxygen must be simultaneously sprayed to the laser spot on the surface of the steel material.
In one embodiment, the activation solution free of the oxygen radical ion may be implemented as a chloride ion (Cl) containing activation solution - ) The activating solution of (4). Containing chloride ions (Cl) - ) After the activating solution is used, the surface of the steel material is gradually changed from silvery white to dark color, such as yellow, brown and brownish black, and the activating solution can play a role in improving the laser absorptivity and greatly reducing the laser reflection.
In yet another embodiment, the oxygen-free acid ion activation solution is embodied as a bromide-containing ion (Br) - ) To form active Fe on the surface of the ferrous material 2+ 、Fe 3+ Ionic ferrous bromide and ferric bromide activated membranes. Active Fe contained in the activated film 2+ 、Fe 3+ The ion being in favor of Fe 3 O 4 The oxide film is rapidly formed. But contains chloride ions (Cl) as compared with the activation solution containing the oxygen radical ions - ) When the activated film of (2) is formed at a high temperature under the subsequent irradiation of a laser beam, it cannot provide an activity [ O ]]When the laser irradiates the surface of the steel material, oxygen must be simultaneously sprayed to the laser spot on the surface of the steel material. In addition, it contains chloride ion (Cl) - ) After the activating solution is used, the surface of the steel material is gradually changed into dark color from silvery white, such as tan, reddish brown and tan, and the activating solution can play a role in improving the laser absorptivity and greatly reducing the laser reflection.
It will be appreciated by those skilled in the art that the Fe-containing is formed using the above-described activating solution 2+ 、Fe 3+ The surface of the ion activated film is dark, and compared with the steel material without the activated film, the surface of the ion activated film is darker and more uniform in color, so that the reflection of subsequent laser can be effectively prevented, the light absorption consistency is kept, the surface of the steel material can be uniformly heated to high temperature by the laser, and the subsequent formation of the Fe is further ensured 3 O 4 Uniformity of oxide film thickness.
The laser high-temperature flash forming method of the surface oxide film of the steel material comprises the following steps:
s1002 heating the Fe to be generated by a laser beam for heating 3 O 4 The surface of the iron and steel material of the oxide film reaches 1450-1500 ℃, and the Fe is generated in a flash speed 3 O 4 And (5) oxidizing the film.
Specifically, in the step S1002, a laser beam derived by a laser head is irradiated on a surface of the ferrous material, such as a surface of a roll.
The roller rotates at a high speed at a rotating speed omega of 50-500 rpm, the laser head and the oxygen injection pipe perform linear feeding motion along the axial direction of the roller at a speed v, the feeding speed v of the roller is 50-500 mm/min, the spot area of the laser beam is 0.05-2 mm & lt 2 & gt, the lap joint rate is 30-80%, and the laser power is 2000-6000W.
When the laser scans the surface of a workpiece, if the activation film is generated by coating oxygen-free acid on the surface of a steel material, oxygen needs to be sprayed to a laser irradiation spot on the surface of the workpiece through an oxygen spraying pipe, and if the activation film is generated by coating oxygen-containing acid on the surface of the steel material, oxygen can be sprayed to the laser irradiation spot on the surface of the workpiece through the oxygen spraying pipe or oxygen does not need to be sprayed. The flow rate of the oxygen is 0.1-15L/min, the temperature of the laser spot on the surface of the roller is instantaneously raised to 1450-1500 ℃ under the irradiation of high-energy laser beams, and Fe is instantaneously produced in situ on the surface of the roller 3 O 4 And (5) oxidizing the film. .
Preferably, the laser high-temperature flash forming method of the surface oxide film of the ferrous material comprises the following steps:
s1003, pretreating the surface of the steel material. As will be understood by those skilled in the art, the step S1003 includes:
s100331, grinding the surface of the ferrous material to remove the surface fatigue layer.
More preferably, the step S1003 includes:
s10032, cleaning the emulsion or the oil stain on the surface of the steel material by alkali, and removing the emulsion or the oil stain on the surface of the steel material by water washing.
Preferably, after the step S10032, the pre-treating the surface of the ferrous material further includes:
s10033, wiping the surface of the steel material with alcohol.
In particular, if emulsion or oil stains remain on the surface of the steel material, the uniformity of an activated film in the subsequent pre-activation process cannot be ensured.
In addition, in the step S1002, the surface of the ferrous material is irradiated by the high-energy laser beam, so that heat enough for heating the surface of the roller to the required temperature can be instantly provided, and in order to rapidly heat the surface of the roller to 1450 to 1500 ℃, the invention adopts high power, which means a laser with power of 2000W to 10000W, and a small light spot to obtain high energy density. If the laser power is less than 2000W, the energy is insufficient, the facula is too small, the generation efficiency of the oxide film is reduced, if the laser power is more than 10000W, the energy is too large, overburning is possibly caused, the moving speed of the steel material is required to be too high, and the matching of a corresponding moving mechanism is difficult, so that the laser power is preferably 2000W-10000W.
The shape of a light spot formed by the laser beam can be a small light spot of a circle, a square or a rectangle, wherein the small light spot refers to the light spot with the area of 0.05-10 mm 2 . If the laser spot area is less than 0.05mm 2 The production efficiency is seriously lowered. And the area of the light spot is more than 10mm 2 If the energy density is insufficient, the surface temperature of the steel material is difficult to reach 1450-1500 ℃, so that the area of the light spot is 0.05-10 mm 2 It is preferable. The overlapping rate of the light spots is 30-80%, the overlapping rate of the light spots is less than 30%, and the laser light spot edgeDue to the false light effect, the laser energy is insufficient, so that Fe can not be formed 3 O 4 If the ratio of the oxide film to be overlapped is more than 80%, the ferrous material may be melted and the production efficiency may be lowered.
In one embodiment, the ferrous material is set as a roller, the rotation speed range of the roller with the rotation speed omega in the preparation process is 50-500 rpm, the laser power is high, the rotation speed can be properly increased, and if the rotation speed is lower than 50rpm, the production efficiency is low; if the rotating speed exceeds 500rpm, the rotating speed is preferably 50-500 rpm because the weight of the roller can reach 30 tons and the excessive rotating speed can cause potential safety hazards in production.
Correspondingly, in the embodiment, the linear feeding speed v of the laser head along the axial direction of the roller ranges from 50mm/min to 500mm/min, if the feeding speed is lower than 50mm/min, the production efficiency is low, and the roller surface is melted due to overburning caused by overhigh power density; if the feed rate is more than 500mm/min, the surface power density of the roll is too low to generate Fe 3 O 4 And (5) oxidizing the film.
Further, the second condition for forming an oxide film at a high temperature is that the oxygen content is more than 58at%, while the oxygen content in the atmosphere is only 21at%, and if the oxygen content is not sufficient, fe cannot be formed even if the temperature reaches 1450 to 1500 ℃ 3 O 4 The activation film can be generated by coating oxyacid or oxyacid activation liquid on the surface of the steel material, and if the activation film is generated by coating oxyacid activation liquid on the surface of the steel material, the activation film can provide a large amount of active oxygen atoms when being heated by laser irradiation, so that the Fe can be formed 3 O 4 And (3) the condition required by the oxide film is that if the activation film is generated by coating the surface of the steel material with the oxygen-free acid activation solution, oxygen needs to be sprayed to the laser spot on the surface of the steel material.
Of course, preferably, the laser high-temperature flash forming method of the surface oxide film of the ferrous material comprises the following steps:
and S1004, spraying oxygen to the laser spot on the surface of the ferrous material while irradiating the surface of the ferrous material with the laser beam.
It should be noted that this step is optional if the activated film is formed by coating the oxyacid activation solution on the surface of the steel material, and is necessary if the film is formed by coating the oxyacid activation solution on the surface of the steel material.
It is worth mentioning that the oxygen gas sprayed is positive to the spot formed on the surface of the ferrous material by the laser beam.
The invention provides a method for spraying oxygen to the surface of a roller, for example, the oxygen can be sprayed to a laser spot from a gas nozzle to provide sufficient oxygen element for the oxidation of the surface layer of the roller, the flow of the oxygen is 0.1-15L/min, the oxygen flow is less than 0.1L/min, the oxygen supply is insufficient, and the oxygen flow is more than 15L/min, the oxygen is excessive.
Further, it was found that if the surface of the iron and steel material is not coated with the activating solution, no activating film is formed, and Fe is formed even if oxygen is sprayed to the surface of the roll 3 O 4 The effect of the oxide film is not satisfactory, and the oxide film is thin and uneven. The reason for this is that if Fe is to be formed rapidly 3 O 4 Oxide film, desirably Fe 2+ 、Fe 3+ Ions. For forming Fe on the surface of the roller before laser oxidation 2+ 、Fe 3+ Ion, by coating the roll surface with said activating liquid containing and/or free of oxygen acid ions, e.g. sulphate ions [ SO ] 4 2- ]Activating liquid to react the iron element on the surface of the roller with sulfate ions to form Fe-containing on the surface of the roller 2+ 、Fe 3+ The activated film of ions further increases the activity of the oxidation reaction and, on the other hand, contains (SO) 4 2- ) The activated film of (a) is decomposed at a high temperature to generate an activity [ O ]]Elements, [ O ] produced by these decompositions]High element activity, and promoting Fe by utilizing more than oxygen 3 O 4 And (5) forming an oxide film. Said (SO) 4 2- ) The concentration of (A) is controlled to be 0.5-15 mol/L, and is lower than 0.5mol/L, the reaction is too slow, is more than 15mol/L, and is too high, the reaction volatilizes to cause environmental pollution, and the concentration is too high, so that the surface can be passivated, and the generation of iron ions is not facilitated. The activating solution can be added after the coating of the activating solution is finished for 3 to 60 minutesLaser oxidation treatment is carried out for less than 3min, the reaction is incomplete, the activation degree is low, the oxide film is thin, and over 60 minutes, over-reaction is generated, so that the thickness and the color of the activated film are not uniform, and the generated Fe is caused 3 O 4 The oxide film is not uniform. Preferably, the laser high-temperature flash forming method of the surface oxide film of the ferrous material comprises the following steps:
s1005, further coating a light absorbing agent on the surface of the activated film of the steel material to form a light absorbing layer on the surface of the steel material, and further improving the light absorption rate.
It is worth mentioning that, in a modified embodiment, the activating liquid may not be applied to the surface of the ferrous material, but the light absorbing agent may be directly applied to the surface of the ferrous material, and the oxygen may be sprayed to the laser spot on the surface of the ferrous material while irradiating the surface of the ferrous material with the laser beam. Thus, the Fe can be formed on the surface of the steel material at the high temperature of 1450-1500 ℃ in a flash manner 3 O 4 The oxide film is an oxide film.
It can be understood that, since the surface of the ferrous material is coated with the light absorbent, the efficiency of the ferrous material absorbing the laser can be improved when the surface of the ferrous material is irradiated with the laser beam, so that the surface of the ferrous material can be flash-heated to 1450-1500 ℃. It will be appreciated that high speed steel typically has a melting point of between 1500 and 1600 c, beyond which the ferrous material melts and therefore the temperature of the laser oxidation should be controlled below 1500 c. And forming the Fe on the surface of the iron and steel material 3 O 4 The temperature of the oxide film is necessarily controlled to be 1450-1500 ℃, and the temperature interval is very close to the interval of the iron and steel materials melting. If the temperature of the ferrous material is raised by using the laser alone and the surface of the ferrous material has low light absorption efficiency, the absorption rate of the laser is difficult to control, which may cause the ferrous material to melt during the heating process. In other words, the coated light absorbent can effectively stabilize the temperature of laser heating and prevent the steel material from melting in the heating process.
The light absorber is preferably a carbon-based light absorber. The carbon-based light absorbent can be set as a carbon-based micro powder dispersion liquid, and the carbon-based micro powder is uniformly dispersed in the solvent. For example, the carbon-based micro powder can be a carbon-based powder material such as flake graphite, graphene, carbon nanotubes and the like with the characteristic size of 10 nm-100 μm. The solvent is formed by adding surfactants such as sodium carboxymethylcellulose, polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), sodium dodecyl benzene sulfonate and the like into organic or inorganic solvents such as water, ethanol, ethylene glycol or acetone and the like, and then carbon-based micro powder can be uniformly dispersed in the solvent through processes such as stirring, ultrasonic vibration and the like.
When the light absorber is embodied as a carbon-based light absorber, the carbon-based light absorber will be in the Fe 3 O 4 The surface of the oxide film is covered with a carbon-based lubricating film, and the carbon-based lubricating film can reduce the surface friction of the steel material, so that the abrasion of the steel material is reduced.
According to another aspect of the present invention, there is also provided a method for forming an oxide film on a surface of a ferrous material by laser flash at high temperature, the method including forming the oxide film on the surface of the ferrous material with Fe 3 O 4 And (4) rolling the oxide film.
Example 1
In a certain 1780 production line of finish hot rolling, the roll of an F1 rolling mill is changed into a high-speed steel roll, and a layer of Fe is prepared on the basis of the high-speed steel roll 3 O 4 Oxide film with thickness of 5 μm and average millimeter rolling amount of 4300 ton, and adopting novel Fe 3 O 4 After the oxide film is compounded with the roller, the millimeter rolling amount reaches 12360 tons, and the service life is prolonged by 3 times. Fe 3 O 4 The preparation method of the oxide film comprises three steps, namely, the first step, the pretreatment of the roller surface, the grinding of the off-machine F1 roller on a grinding machine, the surface roughness after the grinding is 0.5 mu m, the oil is removed by alkali washing, and finally, the roller is washed by water and dried, and the surface of the pretreated roller is bright silver; secondly, the surface is pre-activated, and the activating solution is H with the concentration of 3mol/L 2 SO 4 Coating an activating solution on the surface of the roller to form a yellow activating film on the surface of the roller to form an active layerFe (Fe) property 2+ 、Fe 3+ Ion, wherein the roller surface after the surface pre-activation treatment is yellow brown; thirdly, performing laser rapid oxidation, wherein the laser power is 6kw, the diameter of a round spot is 3mm, the lap joint rate is 50%, the rotating speed of the roller is 160rpm, the axial feeding speed of a laser head is 200mm/min, the oxygen flow is 5L/min, the roller is completely subjected to laser oxidation, and the whole body of the roller is black Fe 3 O 4 And (5) oxidizing the film.
Example 2
In a certain hot finish rolling 1422 production line, an F2 mill roll is changed into a high-speed steel roll, and a layer of black Fe is prepared on the basis of the high-speed steel roll 3 O 4 The thickness of the oxide film is 7 mu m, the average millimeter rolling amount of the original roller is 8200 tons, and novel Fe is adopted 3 O 4 After the oxide film is compounded with the roller, the millimeter rolling amount reaches 46300 tons, and the service life is prolonged by more than 5 times. Fe 3 O 4 The preparation method of the oxide film comprises three steps, namely, the first step, the pretreatment of the roll surface, the grinding of the off-machine F2 roll on a grinding machine, the surface roughness after grinding being 0.3 mu m, the oil removal by alkali washing, and finally the water washing and drying; secondly, surface preactivation is carried out, and the activating solution is NiSO with the concentration of sulfate ions of 6mol/L 4 Forming a layer of yellow-green activated film on the surface of the roller by using the solution to form active Fe 2+ 、Fe 3+ Ions; and thirdly, rapidly oxidizing the laser, wherein the laser power is 8kw, the round light spots are adopted, square light spots are adopted, the side length is 2.5mm, the lap joint rate is 30%, the roller rotating speed is 200rpm, the axial feeding speed of the laser head is 260mm/min, and the oxygen flow is 10L/min.
Example 3
In a certain hot finish rolling 2250 production line, an F4 rolling mill roller is changed into a high-speed steel roller, and a layer of black Fe is prepared on the basis of the high-speed steel roller 3 O 4 Oxide film with thickness of 8 μm and average millimeter rolling amount of 6500 ton, and adopting novel Fe 3 O 4 After the oxide film is compounded with the roller, the millimeter rolling amount reaches 26370 tons, and the service life is prolonged by more than 4 times. Fe 3 O 4 The preparation method of the oxide film comprises three steps, namely, the first step, the roller surface pretreatment,grinding the F4 roller after being taken off the machine on a grinding machine, wherein the surface roughness after grinding is 0.6 mu m, removing oil by alkali washing, and finally washing and drying; secondly, the surface is pre-activated, and the activating solution is Cu (NO) with nitrate ion concentration of 12mol/L 3 ) 2 、Y(NO 3 ) 3 Mixing the solution to form a brown activated film on the surface of the roller to form active Fe 2+ 、Fe 3+ Ions; and thirdly, performing laser rapid oxidation, wherein the laser power is 10000kw, a rectangular laser spot is adopted, the length of the spot is 3mm, the width of the spot is 2mm, the lap joint rate is 50%, the rotating speed of a roller is 300rpm, the axial feeding speed of a laser head is 300mm/min, and the oxygen flow is 12xL/min.
Example 4
In a certain 1780 production line of finish hot rolling, the roll of an F3 rolling mill is changed into a high-speed steel roll, and a layer of black Fe is prepared on the basis of the high-speed steel roll 3 O 4 Oxide film with thickness of 4 μm and average millimeter rolling amount of 9100 ton, and adopting novel Fe 3 O 4 After the oxide film is compounded with the roller, the millimeter rolling amount reaches 27650 tons, and the service life is prolonged by more than 3 times. Fe 3 O 4 The preparation method of the oxide film comprises three steps, namely, the first step, the pretreatment of the roller surface, the grinding of the off-machine F3 roller on a grinding machine, the surface roughness after the grinding is 0.3 mu m, the oil removal by alkali washing, and finally the water washing and drying; secondly, the surface is pre-activated, and the activating solution is FeCl with the chloride ion concentration of 7mol/L 3 Mixing the solution to form a layer of brownish black activated film on the surface of the roller to form active Fe 2+ 、Fe 3+ Ions; and thirdly, carrying out laser rapid oxidation with laser power of 6000kw, adopting rectangular laser spots, wherein the length of each spot is 2mm, the width of each spot is 2mm, the lap joint rate is 50%, the rotating speed of a roller is 200rpm, the axial feeding speed of a laser head is 200mm/min, and the oxygen flow is 15L/min.
It will be appreciated by persons skilled in the art that the embodiments of the invention described above and shown in the drawings are given by way of example only and are not limiting of the invention. The advantages of the present invention have been fully and effectively realized. The functional and structural principles of the present invention have been shown and described in the examples, and any variations or modifications of the embodiments of the present invention may be made without departing from the principles.
Claims (10)
1. The laser high-temperature flash forming method of the oxide film on the surface of the steel material is characterized by comprising the following steps of:
and coating a light absorbing agent on the surface of the activated film.
The generation of the Fe is required by laser beam scanning for heating 3 O 4 Oxidizing the surface of the steel material with a film to heat the laser scanning spot on the surface of the steel material to 1450-1500 ℃ to flash-generate Fe 3 O 4 An oxide film;
and spraying oxygen to the laser spot on the surface of the steel material while irradiating the surface of the steel material with a laser beam for heating.
2. The laser high-temperature flash forming method of an oxide film on the surface of a ferrous material according to claim 1, wherein the pre-treating the surface of the ferrous material comprises:
grinding the surface of the steel material to remove the surface fatigue layer; and/or
Cleaning the emulsion or the oil stain on the surface of the steel material by alkali, and removing the emulsion or the oil stain on the surface of the steel material by water washing; and/or
Wiping the surface of the steel material with alcohol.
3. The method for laser high-temperature flash formation of an oxide film on the surface of a steel material according to claim 1, wherein the light absorber is a carbon-based light absorber.
4. The method for laser high-temperature flash formation of an oxide film on a surface of a ferrous material according to claim 1, wherein the flow rate of the oxygen gas is 0.1 to 15L/min.
5. The method for laser high-temperature flash forming an oxide film on the surface of a ferrous material according to any one of claims 1 to 3, wherein the time for forming the oxide film is 0.01 to 10 milliseconds.
6. The method for laser high-temperature flash forming of an oxide film on a surface of a ferrous material according to any one of claims 1 to 3, wherein the laser beam forms a spot shape selected from a small spot of a circle, a square or a rectangle.
7. The laser high-temperature flash forming method of an oxide film on a surface of a ferrous material according to claim 6, wherein the small spot is a spot area of 0.05 to 10mm 2 。
8. The method for laser high-temperature flash formation of an oxide film on the surface of a ferrous material as claimed in claim 6, wherein the ferrous material is a roll.
9. The laser high-temperature flash forming method of an oxide film on the surface of a ferrous material according to claim 6, wherein the rotation speed range of the roller at ω is 50 to 500rpm during the preparation process.
10. The method of claim 6, wherein a linear feeding speed v of a laser head for forming the laser beam in an axial direction of the roll is in a range of 50 to 500mm/min.
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Effective date of registration: 20241021 Address after: Building C, No.888, Huanhu West 2nd Road, Lingang New District, China (Shanghai) pilot Free Trade Zone, Pudong New Area, Shanghai Applicant after: Shanghai Jibo Laser Technology Co.,Ltd. Country or region after: China Address before: 201306 Room A-171, Building 1, No. 1758, Luchaogang Road, Lingang New Area, China (Shanghai) Pilot Free Trade Zone, Pudong New Area, Shanghai Applicant before: SHANGHAI DALU TIANRUI LASER SURFACE ENGINEERING CO.,LTD. Country or region before: China |