CN102041368A - Method for producing oriented electrical steel with excellent surface quality - Google Patents
Method for producing oriented electrical steel with excellent surface quality Download PDFInfo
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Abstract
The invention discloses a method for producing oriented electrical steel with excellent surface quality, and belongs to the technical field of oriented electrical steel production. The method comprises the following processes of: heating a casting blank at the temperature of between 1,000 and 1,190 DEG C, and then performing hot rolling; normalizing the hot rolled plate at the temperature of between 980 and 1,100 DEG C, and washing the plate by using acid; cold-rolling the plate to the thickness of a finished product under high rolling reduction rate of 86 to 93 percent; heating the cold rolled steel plate to the temperature of between 750 and 860 DEG C, and nitriding in ammonia-containing nitrogen and hydrogen mixed gas; performing decarburizing annealing at the temperature of between 800 and 860 DEG C; then coating a magnesium oxide isolation layer; raising the temperature to 1,200+/-50 DEG C at the speed of 10 to 20 DEG C per hour in the nitrogen and hydrogen mixed gas, preserving the heat for 10 to 20 hours in hydrogen, and completing high-temperature annealing to obtain a finished product of secondary re-crystallization textures; and coating an insulating stress coating. The method has the advantage of producing the oriented electrical steel without defect on the surface and with strong adhesive force and uniform magnesium silicate bottom layer.
Description
Technical field
The present invention relates to the oriented electrical steel technical field, a kind of oriented electrical steel production method of surface quality excellence particularly is provided.
Background technology
Grain oriented electrical steel is a kind of have " Goss texture ", i.e. (110)＜001〉crystallographic texture, silicone content is usually below 4.5%, thickness is at the metal soft magnetic material of 0.10～0.35mm.Because along the excellent magnetic of rolling direction, oriented electrical steel mainly is used as the core material of transformer.The production method of oriented electrical steel is that N.P.Goss proposes in U.S. Patent No. 1965559, produces by the secondary cold-rolling mode of band process annealing.Discover that the good magnetic property of grain-oriented electrical steel sheet comes from its " Goss texture " of forming by secondary recrystallization in final high-temperature annealing process.In order to obtain secondary recrystallization tissue preferably, require to adjust the primary recrystallization grain-size before the secondary recrystallization, and quantity, the form of tiny precipitate as inhibitor.Material as inhibitor has the MnS that adopts in the aforementioned production method, S.Taguchi etc. are at the AlN of U.S. Patent No. 3159511 and U.S. Patent No. 3287183 propositions, the MnSe that T.Imanaka etc. propose in U.S. Patent No. 3932234 etc., they suppress the growing up of primary recrystallization crystal grain of non-" Goss orientation " in the high temperature annealing temperature-rise period.
Have three kinds of oriented electrical steel industrial production to represent technology with above-mentioned three kinds of inhibitor are corresponding: MnS is the secondary cold-rolling method of inhibitor; AlN+MnS is the once cold rolling method of inhibitor; The secondary cold-rolling method of MnSe+Sb.These oriented electrical steel production methods need strand to heat in＞1350 ℃ of process furnace, so that the product magnetic stability.Because the Heating temperature height, brought following problem: (1) blank surface is melt into slag, causes the artificial increase of process furnace maintenance; (2) form thick crystal grain in the heat-processed, secondary recrystallization can not take place in the part with coarse grain, thereby produces the line crystalline substance; (3) be difficult to guarantee that strand is in the ideal temperature in course of hot rolling, thereby easily produce the inhibitor non-uniform phenomenon, finally cause secondary recrystallization of poor quality; (4) owing to limit in the course of hot rolling is split greatly, lumber recovery is low.Main electrical steel manufacturer all produces the oriented electrical steel technology in the exploitation low-temperature heat both at home and abroad in recent years, mainly contains two classes, and all has been used for industrial production.
One class is with the lower inhibitor of new solid solubility temperature, propose with Cu2S in U.S. Patent No. 5653821 as GyuSeung Choi etc., AlN etc., replace traditional inhibitor, and part Ni, Cr etc. have been added based on MnS, adopt 1250-1280 ℃ of low temperature slab addition, decarburization when secondary cold-rolling process annealing, low temperature recovery annealing is coated with magnesium oxide separant, high temperature annealing then behind the secondary cold-rolling.Full decarburizing annealing is carried out in the requirement of this method when interior thickness, yet because the decarburizing annealing time is longer, the surface oxidation bed thickness, this zone of oxidation is broken in the secondary cold-rolling process, not firm with combining of steel strip substrate, be difficult to form good bottom, easily produce in the finished product surface insulation coating and reveal brilliant, obscission.
Another kind of method does not require the complete solid solution of inhibitor forming element in slab heat-processed, but obtains inhibitor by the method for carrying out the nitriding processing before high temperature annealing, thereby can further reduce slab heating temperature.(Al, Si) N is as inhibitor in nitriding formation after proposing by decarburizing annealing in U.S. Patent No. 4994120 as T.Takashima etc.The deficiency of this method is, the zone of oxidation that forms in the decarburizing annealing process is damaged when the later stage nitriding, weakens with the bonding force of steel strip substrate, is difficult to form good bottom, easily produces phenomenons such as revealing crystalline substance in the finished product surface insulation coating.
Overcome the above problems, need heat-up rate, the furnace atmosphere of strict control decarburizing annealing, also want strict control furnace atmosphere simultaneously in the high-temperature annealing process, like this, the production difficulty strengthens, and has brought many inconvenience to production.
Summary of the invention
The object of the present invention is to provide a kind of oriented electrical steel production method of surface quality excellence, produce oriented electrical steel surperficial zero defect, strong adhesion, uniform Magnesium Silicate q-agent bottom, and process stabilizing is feasible.
Production technique of the present invention is: adopt strand hot rolling behind 1000-1190 ℃ of temperature range internal heating; Hot-rolled sheet is cold-rolled to finished product thickness with the draft of 86-93% after 980-1100 ℃ of normalizing, pickling; Cold-rolled steel sheet is warming up to 750-860 ℃, in ammoniated nitrogen and hydrogen mixture atmosphere, carries out nitriding; Then carry out decarburizing annealing at 800-860 ℃; Then, be coated with the magnesium oxide sealing coat; Speed with 10-20 ℃/hour in the nitrogen and hydrogen mixture atmosphere is raised to 1200 ± 50 ℃, and is incubated 10-20 hour in hydrogen, finishes high temperature annealing, obtains the finished product of secondary recrystallization tissue; At last, be coated with mainly the stress coating of preparing by 95 liters of 50wt% aluminium dihydrogen phosphate aqueous solutions, 200 liters of 30wt% colloidal silicon dioxide solution, 10 kilograms of chromium sesquioxides and 1.5 kilograms of silica powders and pure water on the surface.
Described strand composition is: C:0.03-0.10wt%, Si:2.50-4.50wt%, Mn:0.02-1.00wt%, Als:0.015-0.065wt%, N:0.003-0.012wt%, S :≤0.012wt%, P:0.02-0.30wt%, Cr:0.02-0.30wt%, Cu:0.01-0.40wt%, Sn:0.01-0.30wt%, surplus is iron and unavoidable impurities.
C:0.03-0.10wt% crosses low secondary recrystallization imperfection, too high then decarburization difficulty.
Si:2.50-4.50wt%, the too high then rolling difficulty of Si is crossed low then product iron loss height.
Mn:0.02-1.00wt% improves resistivity, reduces iron loss.It is hot-short to cross low easily generation, and effect is saturated during 1.00wt%, so upper limit 1.00wt%.
Als:0.015-0.065wt%, if Al is too high, the thick reduction magnetic of AlN inclusion then; Cross low restraint deficiency.
N:0.003-0.012wt%, N is too high then to produce air blister defect at casting billet surface, crosses low restraint deficiency.
S :≤0.012wt%, harmful to magnetic, so its content is low more good more.
P:0.02-0.30wt% improves resistivity, improves magnetic, and the too high steel that makes becomes fragile, cold rolling difficulty.
Cr:0.02-0.30wt% improves resistivity, improves magnetic; Under suboxide degree situation, form the iron-based oxide compound less, improve the quality of oxide film in the decarburizing annealing process, improve the Magnesium Silicate q-agent bottom.
Cu:0.01-0.40wt% improves resistivity, improves magnetic; Effect is saturated during 0.40wt%, so upper limit 0.40wt%.
The poly-partially element of Sn:0.01-0.30wt%, crystal boundary makes secondary recrystallization stable, improves texture.Cross low then DeGrain, when surpassing 0.30wt%, unfavorable to the Magnesium Silicate q-agent bottom.
Surplus is iron and unavoidable impurities.
Production technique of the present invention is: molten iron is through converter smelting, the RH vacuum-treat, and continuous casting becomes the strand of 200-250mm) 1150 ℃ of heating; hot rolling, to hot-rolled sheet normalizing, pickling, once cold rolling is to finished product thickness then; decarburizing annealing after the nitriding is coated with the magnesium oxide separant, and high temperature annealing obtains finished product.
Slab heating temperature is at 1000-1190 ℃.
Hot rolling: start rolling temperature is 900-1050 ℃, and finishing temperature is 800-950 ℃, and coiling temperature is 400-600 ℃, rolls into the thick hot-rolled sheet of 1.5-3.0mm.
Normalizing: hot-rolled sheet is heated to 980-1100 ℃ in nitrogen, is incubated 30 seconds to 10 minutes, is chilled to 950-850 ℃, is incubated 30 seconds to 10 minutes, with 150-300 ℃/second speed of cooling cooling.
Cold rolling: as to adopt the heavy reduction rate of 86-93 ℃ of % to be cold-rolled to finished product thickness.Before the passage second from the bottom, carry out 2-3 time 150-300 ℃, the time was 5-30 minute ageing treatment.
Nitriding and decarburizing annealing: cold-rolled steel sheet is warming up to 750-860 ℃, nitrogen hydrogen mixeding gas at the ammonia that contains the 0.3-10% volume is incubated 15 seconds to 3 minutes, and the nitrogen in the steel is increased to 0.015-0.035wt%, then at 800-860 ℃, dew point is 30-65 ℃, contains the H of 20-75% volume
2Wet nitrogen hydrogen mixeding gas in, be incubated 1 to 10 minute, carbon in the steel is taken off to below 0.003%.
Separant coating and high temperature annealing: at surface of steel plate is the separant of main component coated with MgO.Speed with 10-20 ℃/hour in the nitrogen and hydrogen mixture atmosphere is raised to 1200 ± 50 ℃, and is incubated 10-20 hour in hydrogen, finishes high temperature annealing.
Be coated with stress coating by 95 liters of 50wt% aluminium dihydrogen phosphate aqueous solutions, 200 liters of 30wt% colloidal silicon dioxide solution, 10 kilograms of chromium sesquioxides and 1.5 kilograms of silica powders and pure water preparation on the surface.
With the common orientated electrical steel that this method is produced, magnetic strength B
800Can reach more than the 1.91T, surperficial zero defect, tack are good.
Embodiment
Embodiment 1
Strand such as table 1, surplus are iron and unavoidable impurities.Strand heats after 3 hours in 1150 ℃ of process furnace, and hot rolling is to 2.3mm.Hot-rolled sheet is heated to 1100 ℃ in nitrogen, be incubated 2 minutes, is chilled to 900 ℃ again, is incubated 2 minutes, in the boiling water of quenching fast, cools off with the speed of cooling more than 150 ℃/second; Pickling then; Be cold rolled to 0.28mm, the centre is carried out 250 ℃, the ageing treatment of 10 minutes time 2 times; Then sample is divided two A and B part: A part sample is warming up to 830 ℃, is 75%H in volume ratio
2, 25%N
2, dew point is in 60 ℃ the nitrogen hydrogen mixeding gas, to be incubated 2 minutes, carbon in the steel is taken off to 0.003wt%; Then, at 750 ℃, the nitrogen hydrogen mixeding gas that contains the ammonia of 3% volume is incubated 30 seconds, and the nitrogen in the steel is increased to 0.023wt%.B part sample is warming up to 750 ℃, the nitrogen hydrogen mixeding gas of the ammonia that contains 3% volume insulation 30 seconds, the nitrogen in the steel is increased to 0.025wt%, and then at 830 ℃, dew point is 60 ℃, and volume ratio is 75%H
2, 25%N
2In the mixed gas, be incubated 2 minutes, carbon in the steel is taken off to 0.003wt%; Then, A and B sample are coated with MgO; In the nitrogen and hydrogen mixture atmosphere, be raised to 1200 ℃ with 15 ℃/hour, atmosphere is changed to pure hydrogen, be incubated 20 hours, finish high temperature annealing; At last, be coated with the coating that mainly constitutes on the surface by aluminium dihydrogen phosphate and silica gel.The product that obtains is like this carried out Magnetic Measurement, and sticking power crooked test, surface quality be viewed as main insulating coating evaluation, the results are shown in Table 2.
As can be seen from Table 2, the product of the explained hereafter of decarburization after the first nitriding of employing patent, not only magnetic is good, and surface quality is good, strong adhesion.
The chemical ingredients of table 1 strand (wt%)
| C | Si | Als | Mn | Cu | S | P | N | Cr | Sn |
| 0.048 | 3.15 | 0.029 | 0.12 | 0.30 | 0.007 | 0.025 | 0.0085 | 0.12 | 0.08 |
Table 2 finished product magnetic property and surface quality
| Sample number | The nitriding mode | P 17/50(W/Kg) | B 800(T) | Bending quality (mm) | Appearance of coat | Explanation |
| A | Nitriding after the decarburization | 1.102 | 1.911 | 40 | Defectiveness | Comparative example |
| B | Decarburization after the nitriding | 0.988 | 1.928 | 20 | Zero defect | Example |
Embodiment 2
Strand C, D composition see Table 3, and surplus is iron and unavoidable impurities, and strand C was 1250 ℃ of process furnace heating 2.5 hours, and strand D heated 3 hours in 1150 ℃ of process furnace; Roll 2.3mm; Hot-rolled sheet is heated to 1050 ℃ in nitrogen, be incubated 2 minutes, is chilled to 900 ℃ again, is incubated 2 minutes, in the boiling water of quenching fast; Pickling then is cold rolled to 0.22mm, and the centre is carried out 250 ℃, the ageing treatment of 10 minutes time 2 times; Be warming up to 750 ℃,, the nitrogen in the steel increased to 0.025wt% the nitrogen hydrogen mixeding gas of the ammonia that contains 3% volume insulation 30 seconds; Then at 830 ℃, dew point is 60 ℃, and volume ratio is 75%H
2, 25%N
2Mixed gas in, be incubated 2 minutes, carbon is taken off to 0.003wt%; Be coated with MgO; In the nitrogen and hydrogen mixture atmosphere, be raised to 1200 ℃ with 15 ℃/hour, atmosphere is changed to pure hydrogen, be incubated 20 hours, finish high temperature annealing; At last, be coated with the coating that mainly constitutes on the surface by aluminium dihydrogen phosphate and silica gel.The product that obtains is like this carried out Magnetic Measurement, and sticking power crooked test, surface quality be viewed as main insulating coating evaluation, the results are shown in Table 4.
As can be seen from Table 4, in the slab heating temperature scope that this patent requires, product excellent magnetic, strong adhesion.
The chemical ingredients of table 3 continuously cast bloom (wt%) surplus is iron and unavoidable impurities
| Sample number | C | Si | Als | Mn | Cu | S | P | N | Cr | Sn |
| C | 0.046 | 3.15 | 0.027 | 0.11 | 0.35 | 0.006 | 0.032 | 0.0080 | 0.20 | 0.07 |
| D | 0.046 | 3.15 | 0.028 | 0.11 | 0.35 | 0.006 | 0.031 | 0.0080 | 0.21 | 0.07 |
Table 4 finished product magnetic property and surface quality
| Sample number | Slab heating temperature | P 17/50(W/Kg) | B 800(T) | Bending quality (mm) | Appearance of coat | Explanation |
| C | 1250℃ | 1.565 | 1.752 | 25 | Zero defect | Comparative example |
| D | 1150℃ | 0.975 | 1.931 | 20 | Zero defect | Example |
Embodiment 3
The composition of steel sees Table 5, and surplus is iron and unavoidable impurities.Strand heated 3 hours in 1150 ℃ of process furnace; Hot rolling is to 2.3mm; Hot-rolled sheet is heated to 1050 ℃ in nitrogen, be incubated 2 minutes, is chilled to 900 ℃ again, is incubated 2 minutes, in the boiling water of quenching fast; Pickling; Be cold rolled to 0.22mm, the centre is carried out 250 ℃, the ageing treatment of 10 minutes time 2 times; Then sample is divided two E, F, G three parts: E part sample is warming up to 700 ℃, the nitrogen hydrogen mixeding gas of the ammonia that contains 3% volume insulation 30 seconds, the nitrogen in the steel is increased to 0.022wt%; Then at 830 ℃, dew point is 60 ℃, and volume ratio is 75%H
2, 25%N
2Mixed gas in, be incubated 2 minutes, carbon is taken off to below 0.003%; F part sample is warming up to 860 ℃, the nitrogen hydrogen mixeding gas of the ammonia that contains 3% volume insulation 15 seconds, the nitrogen in the steel is increased to 0.023%; Then, at 830 ℃, dew point is 60 ℃, contains the H of 75% volume
2Nitrogen hydrogen mixeding gas in, be incubated 2 minutes, carbon is taken off to 0.003wt%; G part sample is warming up to 900 ℃, the nitrogen hydrogen mixeding gas of the ammonia that contains 3% volume insulation 15 seconds, the nitrogen in the steel is increased to 0.023wt%; Then, at 830 ℃, dew point is 60 ℃, and volume ratio is 75%H
2, 25%N
2In the mixed gas, be incubated 2 minutes, carbon is taken off to 0.003wt%; Sample is coated with MgO; In the nitrogen and hydrogen mixture atmosphere, be raised to 1200 ℃ with 15 ℃/hour, atmosphere is changed to pure hydrogen, be incubated 20 hours, finish high temperature annealing; At last, be coated with the coating that mainly constitutes on the surface by aluminium dihydrogen phosphate and silica gel.The product that obtains is like this carried out Magnetic Measurement, and sticking power crooked test, surface quality be viewed as main insulating coating evaluation, the results are shown in Table 6.
As can be seen from Table 6, in the nitriding temperature scope that this patent requires, product excellent magnetic, strong adhesion.
The chemical ingredients of table 5 continuously cast bloom (wt%) surplus is iron and unavoidable impurities
| C | Si | Als | Mn | Cu | S | P | N | Cr | Sn |
| 0.048 | 3.15 | 0.028 | 0.12 | 0.25 | 0.006 | 0.028 | 0.0075 | 0.15 | 0.08 |
Table 6 finished product magnetic property and surface quality
| Sample number | Nitriding temperature | P 17/50(W/Kg) | B 800(T) | Bending quality (mm) | Appearance of coat | Explanation |
| E | 700℃ | 1.482 | 1.832 | 35 | Zero defect | Comparative example |
| F | 860℃ | 0.875 | 1.923 | 20 | Zero defect | Example |
| G | 900℃ | 1.367 | 1.853 | 35 | Zero defect | Comparative example |
Claims (2)
1. the oriented electrical steel production method of a surface quality excellence is characterized in that, production technique is:
The strand heating: temperature is at 1000-1190 ℃;
Hot rolling: start rolling temperature is 900-1050 ℃, and finishing temperature is 800-950 ℃, and coiling temperature is 400-600 ℃, rolls into the thick hot-rolled sheet of 1.5-3.0mm;
Normalizing: hot-rolled sheet is heated to 980-1100 ℃ in nitrogen, is incubated 30 seconds to 10 minutes, is chilled to 950-850 ℃, is incubated 30 seconds to 10 minutes, with 150-300 ℃/second speed of cooling cooling;
Cold rolling: as to adopt the heavy reduction rate of 86-93% to be cold-rolled to finished product thickness; Before the passage second from the bottom, carry out 2-3 time 150-300 ℃, the time was 5-30 minute ageing treatment;
Nitriding and decarburizing annealing: cold-rolled steel sheet is warming up to 750-860 ℃, nitrogen hydrogen mixeding gas at the ammonia that contains the 0.3-10% volume is incubated 15 seconds to 3 minutes, and the nitrogen in the steel is increased to 0.015-0.035wt%, then at 800-860 ℃, dew point is 30-65 ℃, contains the H of 20-75% volume
2Wet nitrogen hydrogen mixeding gas in, be incubated 1 to 10 minute, carbon in the steel is taken off to 0.003%wt;
Separant coating and high temperature annealing: at surface of steel plate is the separant of main component coated with MgO; Speed with 10-20 ℃/hour in the nitrogen and hydrogen mixture atmosphere is raised to 1150-1250 ℃, and is incubated 10-20 hour in hydrogen, finishes high temperature annealing;
At last, be coated with the stress coating that constitutes by 50wt% aluminium dihydrogen phosphate aqueous solution, 30wt% colloidal silicon dioxide solution and pure water on the surface.
2. described strand composition is: C:0.03-0.10wt%, Si:2.50-4.50wt%, Mn:0.02-1.00wt%, Als:0.015-0.065wt%, N:0.003-0.012wt%, S :≤0.012wt%, P:0.02-0.30wt%, Cr:0.02-0.30wt%, Cu:0.01-0.40wt%, Sn:0.01-0.30wt%, surplus is iron and unavoidable impurities.
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| WO2016045157A1 (en) * | 2014-09-28 | 2016-03-31 | 东北大学 | Preparation method for oriented high-silicon steel |
| CN106591554A (en) * | 2016-09-30 | 2017-04-26 | 武汉钢铁股份有限公司 | One-time cold-rolling method capable of improving magnetic performance of low-temperature high-magnetic-induction oriented silicon steel |
| CN108474054A (en) * | 2015-12-24 | 2018-08-31 | Posco公司 | The manufacturing method of oriented electrical steel |
| CN108474055A (en) * | 2015-12-21 | 2018-08-31 | Posco公司 | The manufacturing method of oriented electrical steel |
| CN112522613A (en) * | 2020-11-19 | 2021-03-19 | 武汉钢铁有限公司 | High-magnetic-induction oriented silicon steel with excellent bottom layer quality and production method thereof |
| US11118092B2 (en) | 2018-09-04 | 2021-09-14 | Saudi Arabian Oil Company | Synthetic layered magnesium silicates and their derivatives for high performance oil-based drilling fluids |
| CN114107809A (en) * | 2021-11-12 | 2022-03-01 | 内蒙古科技大学 | Oriented electrical steel with copper precipitation as single inhibitor and production method thereof |
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| WO2016045157A1 (en) * | 2014-09-28 | 2016-03-31 | 东北大学 | Preparation method for oriented high-silicon steel |
| JP2017501296A (en) * | 2014-09-28 | 2017-01-12 | 東北大学Ｎｏｒｔｈｅａｓｔｅｒｎ Ｕｎｉｖｅｒｓｉｔｙ | Method for producing oriented high silicon steel |
| US10032548B2 (en) | 2014-09-28 | 2018-07-24 | Northeastern University | Preparation method of oriented high silicon steel |
| US11066717B2 (en) | 2015-12-21 | 2021-07-20 | Posco | Method for manufacturing grain-oriented electrical steel sheet |
| CN108474055B (en) * | 2015-12-21 | 2020-06-12 | Posco公司 | Method for manufacturing oriented electrical steel sheet |
| CN108474055A (en) * | 2015-12-21 | 2018-08-31 | Posco公司 | The manufacturing method of oriented electrical steel |
| CN108474054B (en) * | 2015-12-24 | 2020-06-05 | Posco公司 | Method for manufacturing oriented electrical steel sheet |
| JP2019507244A (en) * | 2015-12-24 | 2019-03-14 | ポスコＰｏｓｃｏ | Method for producing grain-oriented electrical steel sheet |
| CN108474054A (en) * | 2015-12-24 | 2018-08-31 | Posco公司 | The manufacturing method of oriented electrical steel |
| US11725254B2 (en) | 2015-12-24 | 2023-08-15 | Posco Co., Ltd | Method for manufacturing grain-oriented electrical steel sheet |
| CN106591554B (en) * | 2016-09-30 | 2018-11-23 | 武汉钢铁有限公司 | A kind of once cold rolling method that can improve low temperature high magnetic induction grain-oriented silicon steel magnetic property |
| CN106591554A (en) * | 2016-09-30 | 2017-04-26 | 武汉钢铁股份有限公司 | One-time cold-rolling method capable of improving magnetic performance of low-temperature high-magnetic-induction oriented silicon steel |
| US11118092B2 (en) | 2018-09-04 | 2021-09-14 | Saudi Arabian Oil Company | Synthetic layered magnesium silicates and their derivatives for high performance oil-based drilling fluids |
| US11414584B2 (en) | 2018-09-04 | 2022-08-16 | Saudi Arabian Oil Company | Viscosity supporting additive for water-based drilling and completions fluids |
| US11674069B2 (en) | 2018-09-04 | 2023-06-13 | Saudi Arabian Oil Company | Synthetic layered magnesium silicates and their derivatives for high performance oil-based drilling fluids |
| US11898084B2 (en) | 2018-09-04 | 2024-02-13 | Saudi Arabian Oil Company | Suspension supporting additive for water-based drilling and completions fluids |
| CN112522613A (en) * | 2020-11-19 | 2021-03-19 | 武汉钢铁有限公司 | High-magnetic-induction oriented silicon steel with excellent bottom layer quality and production method thereof |
| CN114107809A (en) * | 2021-11-12 | 2022-03-01 | 内蒙古科技大学 | Oriented electrical steel with copper precipitation as single inhibitor and production method thereof |
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Application publication date: 20110504 |