CN101591495A - The preparation method of a kind of non-oriented electrical steel chromium-free insulating environment-friendly coating and coating thereof - Google Patents
The preparation method of a kind of non-oriented electrical steel chromium-free insulating environment-friendly coating and coating thereof Download PDFInfo
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Abstract
The preparation method of a kind of non-oriented electrical steel chromium-free insulating environment-friendly coating and coating thereof belongs to the electrical steel dope technical field.Each component is pressed the dry weight of material and is calculated: 0%～70% aluminium dihydrogen phosphate, 0%～70% potassium primary phosphate, 0% ~ 70% primary zinc phosphate, 0%～70% monocalcium phosphate and 0%～70% primary magnesium phosphate, 5%～30% acrylic ester emulsion, 1%～20% boric acid and 0.5%～6% silicon sol; All be weight percentage.Coating of the present invention is a kind of environmental protection coating material that does not contain chromium, the coatingsurface of preparation light evenly, have good insulativity, tack, a thermotolerance; It is little that this coating also has water absorbability, the advantage that antirust ability is strong.
Description
Technical field
The invention belongs to the electrical steel dope technical field, especially relate to the preparation method of a kind of non-oriented electrical steel chromium-free insulating environment-friendly coating and coating thereof.
Background technology
Electrical sheet is a kind of important magneticsubstance, and non-oriented electrical steel is widely used in the iron core of motors such as genemotor, generator, miniature transformer.When making iron core, need continuously the electrical sheet punching to be become the blank of core configuration, fix by the chip edge that welds the some amount that will fold.In order to reduce eddy losses, need to apply insulating coating, so that make between each synusia insulated from each other at surface of steel plate.
Coating is last procedure that electrical steel is produced, the kind of coating, technology and quality will produce great effect to mutually insulated, tack, punching, weldability and solidity to corrosion between electrical sheet etc., thereby further influence the iron loss level of electrical steel itself and even the performance of product.
The cold rolling non-oriented electrical steel top coat mainly comprises: inorganic coating, organic coating, half organic coating three major types.Producing now and going up widely used chromic salt+organic resin is half organic coating of main component, as zinc chromate mentioned in the patents such as the special public clear 50-15013 of Japanese Patent, U.S. Pat 3909313 or magnesium chromate+Emulsion acrylic resin or vinylbenzene, acetate emulsion, this kind coating has higher interlamination resistance, good tack and rust-preventing characteristic, and have good punching performance and a resistance toheat, therefore since eighties of last century the seventies until today, still at home and abroad use in a large number in each big electrical steel production firm.But because of it contains chromic salt, can pollute environment, more and more countries and area have been carried out strict restriction to chromic salt as the electrical steel of coating.
Exploitation chromium-free environment-friendly coating has become the key subjects of current electrical steel coatings development, mentioned a kind of masking liquid of forming with aluminium dihydrogen phosphate, silicon sol and organic emulsion in the U.S. Pat 5945212, with aluminium dihydrogen phosphate substitute chromium hydrochlorate, effectively solved environmental issue.This method with phosphalugel or phosphoric acid magnesium salts replacement chromic salt can cause coatingsurface to turn white, and has influence on the surface of steel plate outward appearance.And, cause steel plate to be clamminess because the silicon steel specimen surface free phosphorus content after the baking is higher, in industrial production, can produce disadvantageous effects such as adhesion.Therefore, need on original prescription, further improve.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of non-oriented electrical steel chromium-free insulating environment-friendly coating and coating thereof, this coating does not contain human body and the deleterious chromic salt of environment, and guaranteeing under the situation of interlamination resistance rate preferably, reduced the content of free phosphorus acid group, and solved the problem that surperficial moisture absorption is clamminess by the interaction of itself and emulsion.
For achieving the above object, coating of the present invention consists of the following components: each component is pressed the dry weight (quality behind the removal moisture) of material and is calculated:
Phosphate dihydrogen aluminum solution: 0～70%,
The biphosphate calcium solution: 0～70%,
The biphosphate zinc solution: 0～70%,
Potassium dihydrogen phosphate: 0～70%,
The biphosphate magnesium solution: 0～70%,
Acrylic ester emulsion: 5～30%,
Boric acid: 1～20%,
Silicon sol: 0.5～6%,
Below all be weight percentage
Contain one or several mixing of phosphate dihydrogen aluminum solution, biphosphate magnesium solution, biphosphate zinc solution, potassium dihydrogen phosphate, biphosphate calcium solution in the insulation compound of the present invention.Phosphate dihydrogen salt solution concentration is 30%～50% (weight percent), and does not contain free phosphoric acid substantially, and the consumption of dihydrogen phosphate calculates with dry weight, accounts for 20%～70% of whole composition weights;
Another essential characteristic of the present invention is to contain acrylic ester emulsion in the insulating coating, and this emulsion is the multipolymer of water miscible vinylformic acid and ester thereof, and each component is by weight ratio:
Methyl methacrylate 20～30%
Ethyl propenoate 20～25%
Acrylamide 0.5～3%
Surplus is a water
The emulsion addition calculates with resin solid content, accounts for 5～30% of whole compositions, and the interpolation of emulsion can significantly improve the punching performance of steel plate, but addition should not surpass 30%, otherwise can cause the welding property variation of steel plate.Emulsion should be neutrality or weakly alkaline, and solid content should be between 40%～50%, and viscosity is 400～3000cps, dissolves each other fully with above-mentioned phosphate solution, does not produce precipitation.
Coating of the present invention also contains boric acid, and boric acid can increase the compactness and the surface luster of film, can also increase the formation ability of film when low temperature and the thermotolerance during stress relieving, and the addition of boric acid is 1%～20% of whole composition weights.
Also contain silicon sol in the coating of the present invention, silicon sol is the abbreviation of colloid silica, and it is a kind of good mineral binder bond, has nontoxic, high temperature resistant, heat insulation, good insulation preformance, an advantage such as specific surface area is big, adsorptive power is strong, thermal expansivity is low.Its solid content of general requirement is 30%～31%, and pH value is 9.5～10.5, particle diameter 10～20nm, and viscosity 50c.p, proportion 1.14～1.24, and stability is preferably arranged.Add outward appearance and the tack that can improve coating in the masking liquid to, addition accounts for 0.5%～6% of whole coating wt with dry weight basis.
Among the present invention, add water in aforementioned coating composition, the density of final treatment solution is controlled at 1.00～1.20g/cm
3Masking liquid is uniformly applied to the non-oriented electromagnetic steel sheet surface, in 250～500 ℃ drying oven, dried in 30～60 seconds, can obtain the insulating film of excellent performance.
The coated weight that solidifies caudacoria should be 0.5～10g/m
2
The invention has the advantages that this coating is not chromate-containing environment-friendly coating.This coatingsurface light evenly, have good insulativity, tack, a thermotolerance; This coating also because lower free phosphorus content is arranged, has well solved the problem that the coating moisture absorption is clamminess, and therefore has good rustless property.
Embodiment
Each component and the content thereof of embodiments of the invention and corresponding Comparative Examples are as shown in table 1, press table 1 preparation coating of the present invention.
Table 1: (content of following all components all calculates according to the material dry weight coating composition, unit: g)
The coating that makes by embodiments of the invention and corresponding Comparative Examples is coated in the thick non-oriented electromagnetic steel sheet surface of 0.5mm, carries out the 1min sintering in 450 ℃ retort furnace, promptly forms uniform insulating film at surface of steel plate after the taking-up cooling.The performance index that record this coating are as shown in table 2:
Table 2: coating performance test
| Masking liquid character | Coating rear surface outward appearance | Tack | Free phosphorus content (μ g/Ep) | |
| Embodiment 1 | Milky white has fine particle | Smooth, evenly | A | 500 |
| Embodiment 2 | Milky white | Slightly jaundice is coarse | A | 1254 |
| Embodiment 3 | Milky white has fine particle | Smooth, evenly | A | 308 |
| Embodiment 4 | Milky white | Smooth, evenly | A | 1883 |
| Embodiment 5 | Milky white | Decorative pattern is arranged, inhomogeneous | A | 783 |
| Embodiment 6 | Milky white | Smooth, evenly | A | 166 |
| Embodiment 7 | Milky white has fine particle | Slightly turn white | A | 275 |
| Embodiment 8 | Can not dissolve each other | - | - | - |
| Embodiment 9 | Milky white | Slightly turn white | A | 238 |
| Embodiment 10 | Milky white | Smooth, evenly | A | 182 |
| Embodiment 11 | Milky white | Smooth, evenly | A | 296 |
| Embodiment 12 | Milky white | Smooth, evenly | A | 144 |
| Comparative example 1 | Milky white | Slightly turn white | A | 733 |
| Comparative example 2 | Orange | Smooth, evenly | A | - |
Annotate:
1. masking liquid character is the apparent condition after each component is mixed.
2. coating back outward appearance is the apparent conditions of 450 ℃ of bakings after 1 minute.
3. tack: testing method is with reference to GB2522-2007, sample is pulled behind crooked 180 ° of copper rod straight, the cracking of observing coating with peel off situation, performance class is divided into A, B, four ranks of C, D from high to low.
4. the free phosphorus testing method is used Shoudu Iron and Steel Co patent 200810222009.1, the content＜200 μ g/Ep of general requirement control free phosphorus in the production.
From above The performance test results as can be seen, the content of free phosphorus all can be controlled at＜200 μ g/Ep in the coating example 6,10,12 of the present invention, has solved the problem that surface of steel plate is clamminess; Has smooth uniform appearance simultaneously, good insulation performance and tack; And wettability is good, is convenient to coating.It is a kind of good non-oriented electrical steel chromium-free environment-friendly coating.
Claims (6)
1. a non-oriented electrical steel chromium-free insulating environment-friendly coating is characterized in that, each component is pressed the dry weight of material and calculated:
Aluminium dihydrogen phosphate: 0～70%,
Primary magnesium phosphate: 0～70%,
Potassium primary phosphate: 0～70%,
Primary zinc phosphate: 0～70%,
Monocalcium phosphate: 0～70%,
Acrylic ester emulsion: 5～30%,
Boric acid: 1～20%,
Silicon sol: 0.5～6%,
All be weight percentage, described dry weight is meant the quality behind the removal moisture.
2. coating as claimed in claim 1 is characterized in that: contain in aluminium dihydrogen phosphate, primary magnesium phosphate, potassium primary phosphate, primary zinc phosphate, the biphosphate calcium solution one or more; Phosphate dihydrogen salt solution concentration is 30 weight %～50 weight %, does not contain free phosphoric acid; The consumption of dihydrogen phosphate calculates with dry weight, accounts for 20%～70% of whole composition weights.
3. coating as claimed in claim 1 is characterized in that: acrylic ester emulsion is the multipolymer of water miscible vinylformic acid and ester thereof, and each component is by weight ratio:
Methyl methacrylate 20～30%
Ethyl propenoate 20～25%
Acrylamide 0.5～3%
Surplus is a water
Emulsion should be neutrality or weakly alkaline, and solid content should be between 40%～50%, and viscosity is 400～3000cps, dissolves each other fully with above-mentioned phosphate solution, does not produce precipitation.
4. coating as claimed in claim 1 is characterized in that: also be added with a spot of boric acid, the addition of boric acid is 1%～20% of whole composition weights.
5. coating as claimed in claim 1 is characterized in that: said silicon sol is a colloid silica, and its solid content is 30%～31%, and pH value is 9.5～10.5, particle diameter 10～20nm, and viscosity 50c.p, proportion 1.14～1.24, and stability is preferably arranged.
6, a kind of method that adopts the described coating of claim 1 to prepare coating is characterized in that, adds water in coating, and the density of final treatment solution is controlled at 1.00～1.20g/cm
3, masking liquid is uniformly applied to the non-oriented electromagnetic steel sheet surface, in 250～500 ℃ drying oven, dried in 30～60 seconds, obtain the insulating film of excellent performance;
The coated weight that solidifies caudacoria should be 0.5～10g/m
2
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| CN102477235A (en) * | 2010-11-29 | 2012-05-30 | 攀钢集团钢铁钒钛股份有限公司 | Chromium-free insulating coating, electrical sheet material and preparation method thereof |
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