CN101085586A - Chemical method for drawing pattern on tropism silicon steel surface - Google Patents
Chemical method for drawing pattern on tropism silicon steel surface Download PDFInfo
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- CN101085586A CN101085586A CN 200710052599 CN200710052599A CN101085586A CN 101085586 A CN101085586 A CN 101085586A CN 200710052599 CN200710052599 CN 200710052599 CN 200710052599 A CN200710052599 A CN 200710052599A CN 101085586 A CN101085586 A CN 101085586A
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Abstract
The chemical way of drawing on the surface of silicon steel comprises the carbon annealing, coating, high temperature annealing, acid rinsing with the coating composed of crystalline control agent and coating crystalline on the pattern. It can show the pattern on the silicon steel without damage to the surface.
Description
Technical field
The present invention relates to method, the particularly method that draws a design at the orientation silicon steel surface of the work at metal works surface rendering pattern (as picture, image, literal etc.).
Background technology
At present, the required method of patterning of metal works surface rendering has two big class methods usually, and the one, Mechanical Method (as sandblast, laser, mechanical engraving etc.), another kind of is chemical corrosion method.
Chemical corrosion method: as the disclosed a kind of printed pattern corroding technique for stainless steel products of CN86108399, this method is transferred to print film on the stainless steel surfaces, after the process burn into is crossed alkali treatment, forms floral designs in its surface.
Mechanical Method: as the disclosed a kind of surface treatment method that makes the canister surface present two kinds of colors and/or surface effect of CN1450206, it is a part of covering protection with the canister behind the plastic polishing, the appearance part is corroded or blasting treatment, then whole canister is carried out electroplating processes and form the smooth plating layer surface of same color and two kinds of surface effects of floral designs or sandblast coating surface; Perhaps earlier the canister behind the plastic polishing is carried out electroplating processes, a part of covering protection wherein again plates the coating of new color again after appearance part strip handled, make the canister surface form two kinds of different colours overlay coatings; Can also obtain two or more surface color and polishes and two or more surface effects with such surface treatment method, make the surface color and polish of canister abundanter, floral designs can be changeful, and surface effect is also varied, strengthened the decoration function of canister greatly.
The disclosed a kind of method and apparatus of handling thin metal layer on the substrate of CN1404627 by with the first excimer laser impulse radiation metal level, can be controlled granularity, particle shape and particle circle position and orientation in this metal level.The intensity pattern that described pulse is limited by mask has the district of covering and transparent area.Its whole thickness fusing is run through in each zone that metal level is covered by transparent area, and that each zone that the covered district of metal level covers is retained to small part is molten.Each is to the adjacent fusion zone of small part unmelted region adjacency.After the first excimer laser impulse radiation, allow the fusion zone of metal level solidify again.Setting up period again makes particle activation growth and produces bigger particle to the small part unmelted region in the fusion zone of adjacency.After the first excimer laser impulse radiation makes the fusion zone finish curing more again,, make the covering district cover metal level and have the still less zone of larger particle with the second excimer laser impulse radiation metal level of intensity pattern skew.Its whole thickness fusing is run through in each zone that metal level is covered by the transparent area of a skew, and that each zone that metal level is covered by the covering district of a skew is retained to small part is molten.After the second radiation beam impulse radiation, the fusion zone is at setting up period again, activation growth even bigger particle in the fusion zone of larger particles in adjacency to the small part unmelted region.As required, can repeat radiation, curing and radiation more again to metal level, up in metal level, obtaining desired grain structure.
Though above-mentioned these methods all can be at metal works surface rendering pattern, all can cause in various degree destruction to the metal works surface.
Summary of the invention
Technical problem to be solved by this invention is: a kind of chemical method that draws a design at the orientation silicon steel surface of the work is provided, and this method can make orientation silicon steel surface of the work crystal grain located growth form required pattern, can not damage the orientation silicon steel surface of the work.
The present invention solves the problems of the technologies described above the technical scheme that is adopted:
A kind of chemical method that draws a design at the orientation silicon steel surface of the work, it may further comprise the steps and comprises:
(1) step of decarburizing annealing;
(2) in the step of surface of the work applying coatings;
(3) step of high annealing;
(4) step of pickling;
Above-mentioned coating comprises crystal controlling agent;
Crystal controlling agent comprises water, MgO, additive, and the percentage by weight proportioning of each component of crystal controlling agent is: MgO1-20%, additive 0.1-20%, all the other are water;
Additive is CaO, chloride, boride, sulfide, Al
2O
3, carbon dust, pure aluminium powder, Sn the compound of compound, Sr of compound, Sb in one or more combination;
Step (2) comprises the step according to the required coating crystal controlling agent that draws a design on workpiece.
In the such scheme, above-mentioned coating comprises interleaving agent, and step (2) is included in the step of surface of the work coating interleaving agent.
In the such scheme, step (2) is specially: at surface of the work coating interleaving agent, apply crystal controlling agent again on release agent coating earlier.
In the such scheme, step (2) is specially: apply crystal controlling agent earlier on surface of the work, apply interleaving agent again on surface of the work and crystal controlling agent coating.
In the such scheme, step (2) is specially: apply earlier crystal controlling agent on surface of the work, again the coating of the surface of the work beyond crystal controlling agent coating interleaving agent.
In the such scheme, crystal controlling agent also comprises TiO
2, the percentage by weight proportioning of each component of crystal controlling agent is: MgO1-10%, TiO
21-10%, additive 1-40%, all the other are water.
In the such scheme, the thickness of the thickness of release agent coating, crystal controlling agent is 0.1-0.5 μ m on the workpiece.
The inventive method adopts in the coating of orientation silicon steel surface of the work and comprises that the crystal controlling agent of additive controls the secondary recrystallization process, because additive is CaO, chloride, boride, sulfide, Al
2O
3, carbon dust, pure aluminium powder, Sn the compound of compound, Sr of compound, Sb in one or more combination.These materials produce secondary recrystallization or produce thin crystalline substance the silicon steel workpiece and exert an influence, thereby the growth of control orientation silicon steel surface microstructure reaches the purpose that crystal grain is arranged in required pattern.Its operation principle is: in the decarburizing annealing stage, crystallite dimension size of orientation silicon steel is about 8～15 μ m, and when high annealing, if normal secondary recrystallization takes place, Gauss's crystal grain will be annexed on every side crystal grain and grow up, and the crystallite dimension size is 5～100mm.Otherwise thin crystalline substance will occur, grain size is 0.1～2mm.Different based on secondary recrystallization crystal grain and thin brilliant size, grain size and position are to different and form required pattern, appointed positions displays on the orientation silicon steel surface can to make pattern (as picture, image, literal etc.), and can not damage the orientation silicon steel surface of the work.
Being also advantageous in that of the inventive method:
1, after the decarburizing annealing of the inventive method orientation silicon steel workpiece, surface of the work also applies interleaving agent, bonding (as the steel band rolling time) in the time of can preventing the workpiece high annealing.
2, the step at the surface of the work applying coatings is simple, convenient, can apply crystal controlling agent again on release agent coating earlier at surface of the work coating interleaving agent; Also can on surface of the work, apply crystal controlling agent earlier, on surface of the work and crystal controlling agent coating, apply interleaving agent again; Also can on surface of the work, apply crystal controlling agent earlier, again the coating of the surface of the work beyond crystal controlling agent coating interleaving agent; Also can only on surface of the work, apply crystal controlling agent.
3, in crystal controlling agent, add TiO
2, can improve the glass-film quality and reduce iron loss.
The orientation silicon steel workpiece that the inventive method is handled, its picture on surface is made of the macrostructure of silicon steel plate, and third dimension is strong.Have practicality and reserve value.The inventive method can be applicable to aspects such as orientation silicon steel production, the making of orientation silicon steel process product, decoration.
Description of drawings
Fig. 1 is the technological process of production block diagram of orientation silicon steel
Fig. 2 is the orientation silicon steel production technology FB(flow block) that comprises the inventive method
The specific embodiment
The chemical method embodiment 1 that the present invention draws a design at the orientation silicon steel surface of the work, it is the chemical method that the high magnetic induction grain-oriented silicon steel surface of the work draws a design, it may further comprise the steps:
(1) step of decarburizing annealing;
800～900 ℃ of decarburization temperature, decarburization time 1～10min.
(2) in the step of surface of the work applying coatings; Coating comprises crystal controlling agent, interleaving agent.
Step (2) comprises according to the step of the required coating crystal controlling agent that draws a design on workpiece, in the step of surface of the work coating interleaving agent.Be specially earlier and apply interleaving agent, on release agent coating, apply crystal controlling agent again at surface of the work.
The thickness of the thickness of release agent coating, crystal controlling agent is 0.1-0.5 μ m on the workpiece.
The percentage by weight proportioning of each component of crystal controlling agent is: MgO 2%, TiO
21%, KCl 0.2%, boric acid 0.2%, carbon dust 0.1-2%, all the other are deionized water.
The percentage by weight proportioning of each component of interleaving agent is: MgO 5%, TiO
25%, all the other are deionized water.
(3) step of high annealing; Identical with this area common processes.
(4) step of pickling, pickling gets final product to manifesting the orientation silicon steel macrostructure, makes the pattern of orientation silicon steel surface of the work display.
Pickling with sulfuric acid or hydrochloric acid all can, 0～100 ℃ of pickling temperature, pickling time 0.5～200min.
The present embodiment method is carried out in the production technology of high magnetic induction grain-oriented silicon steel, the production technology of conventional orientation silicon steel as shown in Figure 1, comprise the inventive method orientation silicon steel production technology as shown in Figure 2.
The high magnetic induction grain-oriented silicon steel sample is after pickling, and measurement result is as shown in table 1:
Table 1
| Carbon dust addition (part) | Non-word position crystal grain big (mm) | Become word position grain size (mm) | Whether font is clear |
| 0.1 | 5-20 | 0.05-2 | Be |
| 0.5 | 5-20 | 0.05-1 | Be |
| 1 | 5-20 | 0.05-1 | Be |
| 2 | 5-20 | 0.05-1 | Be |
In the present embodiment 1, step (2) also can apply crystal controlling agent earlier on surface of the work, apply interleaving agent again on surface of the work and crystal controlling agent coating; Also can on surface of the work, apply crystal controlling agent earlier, again the coating of the surface of the work beyond crystal controlling agent coating interleaving agent.
Surface of the work coating interleaving agent bonds in the time of can preventing the workpiece high annealing, and its principle is: MgO and steel strip surface SiO when high annealing is raised to 950～1020 ℃
2Oxide-film generation chemical reaction (2MgO+SiO
2→ Mg
2SO
4), form magnesium silicate glass film bottom, promote desulfurization and denitrification reaction during high temperature purification annealing.
The chemical method embodiment 2 that the present invention draws a design at the orientation silicon steel surface of the work, it may further comprise the steps and comprises:
(1) step of decarburizing annealing;
(2) in the step of surface of the work applying coatings;
Coating is crystal controlling agent, and step (2) is specially: apply the step of crystal controlling agent according to required drawing a design on workpiece.The thickness of crystal controlling agent is 0.1-0.5 μ m on the workpiece.
The percentage by weight proportioning of each component of crystal controlling agent is: MgO 20%, Al
2O
32%, CaO 2%, FeS 2%, all the other are water.
(3) step of high annealing;
(4) step of pickling; Pickling gets final product to manifesting the orientation silicon steel macrostructure, makes the pattern of orientation silicon steel surface of the work display.
The crystal controlling agent that uses in the inventive method, the percentage by weight proportioning of its each component is: MgO 1-20%, additive 0.1-20%, all the other are water.
Additive is CaO, chloride, boride, sulfide, Al
2O
3, carbon dust, pure aluminium powder, Sn the compound of compound, Sr of compound, Sb in one or more combination.
Wherein:
CaO can make MgO aquation rate increase, and promptly water imbibition [forms Mg (OH)
2] strong, can improve the MgO tack; CaO also plays catalysis, impels to form good glass-film.In the crystal controlling agent, the percentage by weight of CaO≤0.5% the best.
Chlorion in the chloride and H
2O reacts, and forms HCl, the etch glass-film; Adding the low melting point chloride in MgO can reduce in the oxide-film FeO content and make SiO
2Finer and close, thus the glass-film quality improved.In the crystal controlling agent, muriatic percentage by weight 〉=1% o'clock can destroy oxide-film and accelerate the infiltration of various elements in the coating, therefore, generally requires muriatic percentage by weight≤0.2%.
Boride is at MgO+5%TiO
2Be to add 3%～5%Na in the masking liquid
2B
4O
7, NaBO
2Or H
3BO
4(NH
4)
2SO
4, be equivalent to boron addition 0.05%～0.3%, can prevent the nitrogen of steel hyperabsorption.Boride plays catalysis, impels to form good glass-film and make secondary recrystallization perfect.When adding B amount surpasses 5%, because the atomic radius of B is bigger, gather partially in the crystal boundary generation, produce thin brilliant thereby will seriously hinder grain growth.
Sulfide adds 10%Al in MgO solution
2(SO
4)
3Or 5%FeS, can improve magnetic strength and reduce iron loss.Add 2%～5%SrSO
4, MgSO
4, FeSO
4Or sulphur also plays same purpose.Add SrS and can prevent that also glass-film from bright spot occurring and making the interface more smooth.
The compound of Sb or Sr is at MgO+TiO
2Be to add in the masking liquid to be equivalent to 0.2%～3% Sb amount, can make secondary recrystallization more perfect.Begin front surface at secondary recrystallization and infiltrate antimony etc. and strengthened restraint, impel top layer subgrain development, magnetic is improved, also make the glass-film attenuate, be coated with the stress coating later on and can produce bigger tension.For improving its dispersed and reactive in MgO, it is thin that the particle of adding is wanted.Add Sb
2(SO
4)
3Can prevent the temperature rise period surface devulcanization, and the effect of protection oxide-film is arranged.When adding Sb amount surpasses 5%, because the atomic radius of Sb is bigger, gather partially in the crystal boundary generation, produce thin brilliant thereby will seriously hinder grain growth.
In MgO, add 0.25%～3% alkali metal compound, SiO in the oxide-film
2React with them, can stop nitrogen in steel to be run out of and nitriding, guarantee that the tiny AlN separated out does not change, but and etch crystal boundary at high temperature, the control crystal boundary moves, and makes secondary recrystallization perfect, iron loss reduces, magnetic strength improves.If can also improve the glass-film quality with alkali borate.
Al
2O
3, when the preparation crystal controlling agent, add 2-20%Al
2O
3Spinel oxides MgAl
2O
4Or ZnAl
2O
4, can prevent from MgO, to add TiO
2The time since high annealing with TiO
2Decompose and Ti is infiltrated in the steel.Add TiO simultaneously
2Glass-film outward appearance and tack are improved.At 5%TiO
2And 2-20%2MgO2Al
2O
35SiO
2, the glass-film of formation is even, and tack is good.Use Al
2O
3Dry-coated or wet being coated with as interleaving agent of fine powder do not form glass-film behind the high annealing, formed even oxide-film is reduced by pure dry hydrogen, and the interface is smooth, the oxide-free particle.If at Al
2O
3In add 3%～40% silicate mineral powder (as serpentine, kaolin etc.), Al during high annealing
2O
3Not bonding, the annealing rear surface can not form oxide-film yet.
Carbon dust, carbon during content 50～150ppm, can play the effect that promotes secondary recrystallization in orientation silicon steel, will seriously hinder grain growth and produce thin crystalline substance but surpass 250ppm.If in the high annealing stage, infiltrate certain carbon in the steel and will produce thin brilliant.
Pure aluminium powder, well-known, the main inhibitor of high magnetic induction grain-oriented silicon steel is AlN, if in the high annealing stage, the certain aluminium of infiltration will destroy the inhibitor in the oriented steel in the steel, secondary recrystallization can not take place, thereby produces thin brilliant.
When the configuration crystal controlling agent, add 1-10%TiO
2, purpose is to improve the glass-film quality and reduce iron loss.TiO
2At H
2+ N
2Emit oxygen when being heated to high temperature in the reducing atmosphere, thus the atmosphere between each circle of control coil of strip.This is to being that the Hi-B steel effect of main inhibitor is more obvious with AlN, with Al
sContent increases, TiO
2Addition increases.The ability of the glass-film absorbed nitrogen that forms is strengthened, and denitrification effect is good when making high temperature purification annealing.Work as TiO
2Measure when excessive Al in the steel
sWhen diffusion into the surface, will reduce TiO
2Generate Ti, destroy the magnesium silicate bottom, the secondary recrystallization imperfection, substrate itself is not attractive in appearance.
Claims (7)
1, a kind of chemical method that draws a design at the orientation silicon steel surface of the work, it may further comprise the steps and comprises:
(1) step of decarburizing annealing;
(2) in the step of surface of the work applying coatings;
(3) step of high annealing;
(4) step of pickling;
Above-mentioned coating comprises crystal controlling agent;
Crystal controlling agent comprises water, MgO, additive, and the percentage by weight proportioning of each component of crystal controlling agent is: MgO 1-20%, additive 0.1-20%, all the other are water;
Additive is CaO, chloride, boride, sulfide, Al
2O
3, carbon dust, pure aluminium powder, Sn the compound of compound, Sr of compound, Sb in one or more combination;
Step (2) comprises the step according to the required coating crystal controlling agent that draws a design on workpiece.
2, the method for claim 1 is characterized in that: above-mentioned coating comprises interleaving agent, and step (2) is included in the step of surface of the work coating interleaving agent.
3, method as claimed in claim 2 is characterized in that: step (2) is specially: at surface of the work coating interleaving agent, apply crystal controlling agent again on release agent coating earlier.
4, method as claimed in claim 2 is characterized in that: step (2) is specially: apply crystal controlling agent earlier on surface of the work, apply interleaving agent again on surface of the work and crystal controlling agent coating.
5, method as claimed in claim 2 is characterized in that: step (2) is specially: apply earlier crystal controlling agent on surface of the work, again the coating of the surface of the work beyond crystal controlling agent coating interleaving agent.
6, the method for claim 1 is characterized in that: crystal controlling agent also comprises TiO
2, the percentage by weight proportioning of each component of crystal controlling agent is: MgO 1-10%, TiO
21-10%, additive 1-40%, all the other are water.
7, method as claimed in claim 2 is characterized in that: the thickness of the thickness of release agent coating, crystal controlling agent is 0.1-0.5 μ m on the workpiece.
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|---|---|---|---|
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|---|---|---|---|
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| Publication Number | Publication Date |
|---|---|
| CN101085586A true CN101085586A (en) | 2007-12-12 |
| CN100581841C CN100581841C (en) | 2010-01-20 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812570B (en) * | 2009-02-24 | 2011-11-23 | 宝山钢铁股份有限公司 | Method for drawing patterns on surface of high magnetic induction oriented silicon steel |
| CN103114181A (en) * | 2013-01-24 | 2013-05-22 | 广东盈泉钢制品有限公司 | Coating formula of oriented silicon steel barrier coat |
| CN103122461A (en) * | 2012-11-09 | 2013-05-29 | 新万鑫（福建）精密薄板有限公司 | Production method for cold-rolled oriented silicon steel continuously passing through pickling line without shot blasting |
| CN103255274A (en) * | 2012-08-10 | 2013-08-21 | 新万鑫（福建）精密薄板有限公司 | Production method of general oriented silicon steel with twice cold rolling changed into one time cold rolling |
| CN106319174A (en) * | 2016-09-23 | 2017-01-11 | 武汉钢铁股份有限公司 | Annealing isolation agent capable of improving quality of low-temperature casting blank heating high induction grain oriented silicon steel bottom layer |
| CN109880982A (en) * | 2019-02-28 | 2019-06-14 | 首钢智新迁安电磁材料有限公司 | A method of improving orientation silicon steel MgO interleaving agent coating quality |
| CN111996354A (en) * | 2020-08-27 | 2020-11-27 | 上海实业振泰化工有限公司 | Preparation method of liquid additive for oriented silicon steel |
-
2007
- 2007-06-29 CN CN200710052599A patent/CN100581841C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812570B (en) * | 2009-02-24 | 2011-11-23 | 宝山钢铁股份有限公司 | Method for drawing patterns on surface of high magnetic induction oriented silicon steel |
| CN103255274A (en) * | 2012-08-10 | 2013-08-21 | 新万鑫（福建）精密薄板有限公司 | Production method of general oriented silicon steel with twice cold rolling changed into one time cold rolling |
| CN103255274B (en) * | 2012-08-10 | 2015-06-03 | 新万鑫（福建）精密薄板有限公司 | Production method of general oriented silicon steel with twice cold rolling changed into one time cold rolling |
| CN103122461A (en) * | 2012-11-09 | 2013-05-29 | 新万鑫（福建）精密薄板有限公司 | Production method for cold-rolled oriented silicon steel continuously passing through pickling line without shot blasting |
| CN103122461B (en) * | 2012-11-09 | 2016-06-01 | 新万鑫（福建）精密薄板有限公司 | The cold-rolled orientation silicon steel production method of pickling line is continued through without throwing ball |
| CN103114181A (en) * | 2013-01-24 | 2013-05-22 | 广东盈泉钢制品有限公司 | Coating formula of oriented silicon steel barrier coat |
| CN106319174A (en) * | 2016-09-23 | 2017-01-11 | 武汉钢铁股份有限公司 | Annealing isolation agent capable of improving quality of low-temperature casting blank heating high induction grain oriented silicon steel bottom layer |
| CN106319174B (en) * | 2016-09-23 | 2018-10-16 | 武汉钢铁有限公司 | Improve the annealing separating agent of low temperature casting blank heating high magnetic induction grain-oriented silicon steel bottom layer quality |
| CN109880982A (en) * | 2019-02-28 | 2019-06-14 | 首钢智新迁安电磁材料有限公司 | A method of improving orientation silicon steel MgO interleaving agent coating quality |
| CN111996354A (en) * | 2020-08-27 | 2020-11-27 | 上海实业振泰化工有限公司 | Preparation method of liquid additive for oriented silicon steel |
| CN111996354B (en) * | 2020-08-27 | 2022-04-19 | 上海实业振泰化工有限公司 | Preparation method of liquid additive for oriented silicon steel |
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|---|---|
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