US 3,945,862 AGrant
Coated Ferrous Substrates Comprising an Amorphous Magnesia-Silica Complex
Issue Date:1976-03-23
•7 Claims
Abstract
Coatings for silicon steel comprised of MgO, an amorphous magnesia-silica complex and a boron bearing compound.
Metadata
Assignee
- Merck & Co., Inc.
Inventors
- Leonard S. Lee
- Howard M. Siegel
- Samuel W. Sopp
Application Information
Application Number:US 5240158
Filing Date:1974-11-15
Priority Date:1973-06-26
Art Unit:111
Classifications
IPC:
C22B 3569H01F 100
Field of Search:
14810642727;31.5;122;31.55;113;1125878;125
Patent Drawings
This patent does not have any drawings.
Description
A representative example of the preparation of a magnesia-silica complex for use in the coating composition of the invention is as follows:
Example 1
Two solutions are prepared as follows:
a. A magnesium chloride solution having a concentration of 213 grams of MgCl.sub.2 per liter is prepared from MgCl.sub.2. 6H.sub.2 O crystals.
b. A 12 percent solution of sodium silicate is prepared having a mole ratio of Na.sub.2 O:SiO.sub.2 of 1:1.6.
The two solutions (a) and (b) are reacted by simultaneously pumping into a reactor vessel (1 gallon capacity) equipped with an overflow spout. The flow rate of each stream is kept at 0.5-0.8 gallons per minute (gpm) with a combined flow rate of 1-1.5 gpm. The slurry is kept at 0.4-2.1 g. MgCl.sub.2 /1 excess by varying the flow of MgCl.sub.2 solution. The slurry after stirring for 10 hours is filtered with a leaf filter and washed with 45.degree.C. city water, dried at 220.degree.-250.degree.F. for 12 hours and hammer-milled to a fine powder. The resultant magnesia-silica complex has a MgO:SiO.sub.2 mole ratio of 1:1.6. Analysis of the complex is as follows:
MgO -- 25.0 percent
SiO.sub.2 -- 59.8 percent
Loss on ignition -- 15.3 percent
Na -- 0.03 percent
Bulk density -- 0.74 g/cc
X-ray diffraction analysis reveals that the product is completely amorphous indicating that it is a magnesia-silica complex rather than a crystalline form of MgO, silica or silicate. Differential thermal analysis followed by X-ray diffraction analysis of this material at temperatures from 20.degree. to 1200.degree.C. showed primarily an amorphous state with a poorly defined clinoenstatite phase at about 820.degree.C.
Example 2
The magnesia-silica complex prepared in Example 1 is heated in a muffle furnace at 1000.degree.C. for 3 minutes. X-ray diffraction analysis reveals that this material is largely amorphous.
Example 3
Two solutions are prepared as follows:
1. A magnesium chloride solution is made by dissolving 454 g. of MgCl.sub.2. 6H.sub.2 O in 1000 ml. of deionized water. The concentration of this solution is 213 g. MgCl.sub.2 /1.
2. A sodium silicate solution is prepared having a concentration of 12 percent solids and a mole ratio of Na.sub.2 O:SiO.sub.2 of 1.7:1.
The two solutions are reacted according to the procedure of Example 1. The excess MgCl.sub.2 measured is 1.75 g MgCl.sub.2 /1. The resultant magnesia-silica complex has a MgO:SiO.sub.2 mole ratio of 1.7:1.
Analysis of the complex shows:
MgO -- 42.5 percent
SiO.sub.2 -- 37.7 percent
Loss on Ignition -- 19.8 percent
Na -- 0.16 percent
Bulk Density -- 0.31 g/cc
Example 4
Two solutions are prepared as follows:
1. The magnesium chloride solution used in Example 1.
2. A sodium silicate solution having a concentration of 12 percent solids and a mole ratio of Na.sub.2 O:SiO.sub.2 of 13:1.
The two solutions are reacted according to the procedure described in Example 1. The excess MgCl.sub.2 measured is 1.92 g MgCl.sub.2 / 1. The resultant magnesia-silica complex has a MgO:SiO.sub.2 mole ratio of 13:1. Analysis of the complex shows:
MgO -- 63.2 percent
SiO.sub.2 -- 7.1 percent
Loss on Ignition -- 29.7 percent
Na -- 0.16 percent
Bulk density -- 0.35 g/cc
Example 5
Two solutions are prepared as follows:
1. The magnesium chloride solution used in Example 1.
2. A sodium silicate solution having a concentration of 12 percent solids and a mole ratio of Na.sub.2 O:SiO.sub.2 of 1:2.7.
The two solutions are reacted according to the procedure described in Example 1. The excess MgCl.sub.2 measured is 1.65 g MgCl.sub.2 /1. The resultant magnesia-silica complex has a MgO:SiO.sub.2 mole ratio of 1:2.7. Analysis of the complex shows:
MgO -- 16.5 percent
SiO.sub.2 -- 67.6 percent
Loss on Ignition -- 14.9 percent
Na -- 0.80 percent
Bulk density -- 0.26 g/cc
Example 6
Two solutions are prepared as follows:
1. An acidified magnesium chloride solution is prepared by adding 12.6 moles of hydrochloric acid to 1 mole of magnesium chloride. The concentration is expressed as 213 g. MgCl.sub.2 / 1.
2. A sodium silicate solution having mole ratio of Na.sub.2 O:SiO.sub.2 of 1:1.6 is prepared as described in Example 1. The concentration is 12percent solids.
The two solutions are reacted according to the procedure described in Example 1. The excess MgCl.sub.2 as measured is expressed as 1.07 g MgCl.sub.2 /1. The magnesia-silica complex after being dried has a MgO:SiO.sub.2 mole ratio of 1:14.2. Analysis of the powder shows:
MgO -- 4.2 percent
SiO.sub.2 -- 89.2 percent
Loss on Ignition -- 6.4 percent
Na -- 0.47 percent
Bulk density -- 0.11 g/cc
Example 7
Two solutions are prepared as follows:
a. Magnesium sulfate solution having a concentration of 180 g. MgSO.sub.4 /1 equivalent is prepared by neutralizing magnesium hydroxide with sulfuric acid.
b. A sodium silicate solution having a concentration of 9% and mole ratio, Na.sub.2 O:SiO.sub.2, of 1:1.6 is prepared.
The two solutions (a) and (b) are reacted by simultaneously pumping into a reactor vessel (1 gallon capacity) equipped with an overflow spout. The flow rate of each stream is kept at 0.5-0.8 gallons per minute (gpm) with a combined flow rate of 1-1.5 gpm. The slurry is kept at 15-20 g MgSO.sub.4 /1 excess by varying the flow of MgSO.sub.4 solution. The precipitate formed is immediately diluted 1:2 with city water and filtered on a rotary vacuum filter. A 7-minute cycle is used on the filter with slurry at the overflow level. City water at 35.degree.C. was used for washing. The filter cake after washing is dried at 500.degree.F. for 6-12 hours. The resulting magnesia-silica complex has a MgO:SiO.sub.2 mole ratio of 1:1.6.
Analysis of the complex is as follows:
MgO -- 25.9 percent
SiO.sub.2 -- 59.6 percent
Ignition loss -- 11.3 percent
Na -- 0.08 percent
So.sub.4 -- 0.007 percent
Example 8
Two solutions are prepared as follows:
a. Magnesium sulfate solution having a concentration of 180 g MgSO.sub.4 /1 is prepared by neutralizing magnesium hydroxide with sulfuric acid.
b. A sodium silicate solution having a concentration of 9 percent and mole ratio, Na.sub.2 O:SiO.sub.2, of 1:1.6 is prepared.
The two solutions (a) and (b) are reacted by simultaneously pumping into a reactor vessel (1 gallon capacity) equipped with an overflow spout. The flow rate of each stream is kept at 0.5-0.8 gallons per minute (gpm) with a combined flow rate of 1-1.5 gpm. The slurry is kept at 15-20 g MgSO.sub.4 /1 excess by varying the flow of MgSO.sub.4 solution. The precipitate formed is immediately diluted 1:2 with city water and filtered on a rotary vacuum filter. A 7-minute cycle is used on the filter with slurry at the overflow level. City water at 35.degree.C. was used for washing. The filter cake after washing is dried at 500.degree.F. for 6-12 hours. The resulting magnesia-silica complex has a MgO:SiO.sub.2 mole ratio of 1:1.6.
Analysis of the complex is as follows:
MgO -- 25.9 percent
SiO.sub.2 -- 59.6 percent
Ignition loss -- 11.3 percent
Na -- 0.15 percent
So.sub.4 -- 0.007 percent
Additional procedures for the preparation of magnesia-silica complexes to be employed in the practice of the invention are set forth in U.S. patent application Ser. No. 267,276, now abandoned, said procedures being incorporated herein by reference.
Representative compositions of boron material and a magnesia-silica complex in combination with MgO that may be employed in the practice of the invention are as follows:
a. 10 parts by weight of boric acid and 35 parts by weight of complex having an MgO:SiO.sub.2 mole ratio of 1:1.6 per 100 parts by weight of MgO.
b. 8 parts by weight of boric oxide and 180 parts by weight of complex having an MgO:SiO.sub.2 mole ratio of 7:1 per 100 parts by weight of MgO.
The unobvious and unexpected properties of the novel coating compositions of the invention are clearly evident from a consideration of the following resistivity studies wherein a composition of the invention is tested and the insulation produced is compared with that achieved by a commercial steel grade MgO by itself.
Example 9
a. A coating slurry is made by mixing in a Waring Blender 44.5 g. of a commercial steel grade MgO, 15.5 g. of the amorphous magnesia-silica complex prepared in Example 1 and 1.5 grams of reagent grade boric acid and 500 ml. of deionized water. The concentration of the slurry is approximately 1 lb. of solids per gallon. The mixture is allowed to stand to stabilize the viscosity. The resulting slurry is coated onto silicon steel strips (size 3 cm. X 30.5 cm.) at a coating weight of 0.061 oz./ft..sup.2 based upon MgO and dried at 250.degree.-275.degree.C. The coated strips are then box-annealed in hydrogen atmosphere for 30 hours at 1200.degree.C.
b. For comparative purposes a coating slurry is prepared according to the procedure (a) above having a concentration of 1 lb. of solids per gallon but containing only the commercial steel grade MgO of (a). Identical steel strips are coated as in (a).
After annealing and cooling, the excess coating was scrubbed off all samples with a nylon brush and a cloth. These strips were tested for resistance on both surfaces with a Franklin tester (ASTM-A344-60T). The results are as follows:
Example 10
a. A steel grade MgO containing boron additive is made by adding minute quantities of reagent grade boric acid to the magnesium material in the wet state. The material is dried and calcined to magnesium oxide. Analysis of the sample is as follows:
MgO -- 97.0 percent
NaCl -- 0.029 percent
CaO -- 0.22 percent
Ignition loss -- 1.52 percent
B -- 0.13 percent
Fe.sub.2 O.sub.3 -- 0.027 percent
b. A coating slurry is made by mixing in a Waring blender 60.0 g. of (a), 21.0 g. of the amorphous magnesia-silica complex prepared in Example 8 and 500 ml. of deionized water. The mixture is allowed to stand to stabilize the viscosity. The resulting slurry is coated onto high permeability type silicon steel strips (size 3 cm. .times. 30.5 cm.) at a coating weight of 0.074 oz./ft..sup.2 based upon MgO and dried at 250.degree.-275.degree.C. The coated strips are then annealed.
c. For comparative purposes a coating slurry is prepared according to the procedure (b) above, having the same slurry concentration but containing only the commercial steel grade MgO without the boron additive. Identical steel strips are coated as in (b).
After annealing and cooling, the excess coating is scrubbed off all samples with a nylon brush and a cloth. These strips are tested for resistance on both surfaces with a Franklin tester (ASTM-A344-60T). The results are as follows:
The above experiments unequivocally demonstrate that magnesium oxide currently employed to coat grain-oriented silicon steel gives relatively low resistance whereas the identical MgO coating containing a boron material and an amorphous magnesia-silica complex results in the production of a film having a considerably higher resistance. Comparable results to that indicated above are achieved employing other representative boron materials and non-crystalline magnesia-silica complexes encompassed within the scope of the invention.
Although specific embodiments of the invention have been described herein, it is not intended to limit the invention solely thereto but to include all of the obvious variations and modifications within the spirit and scope of the appended claims.
Claims
What is claimed is:
1. A method of producing a separator and electrical insulating coating on magnetic ferrous material which comprises applying a coating composition comprising MgO, Mg(OH).sub.2 or mixtures thereof, at least one boron compound and at least one amorphous magnesia-silica complex containing from about 0.001 to 2.0 percent by weight of an alkali metal oxide or hydroxide, wherein the mole-ratio of the MgO:SiO.sub.2 is from about 1:25 to 14:1, said magnesia-silica complex being amorphous as indicated by its X-ray powder diffraction pattern and exhibiting the following differential thermal behavior characteristics: an endothermic peak at about 250.degree.C., an exothermic peak at about 820.degree.C. and at about 980.degree.C., to preoxidized magnetic ferrous material and annealing said material at an elevated temperature from about 950.degree.-1500.degree.C. for from about 2 to 50 hours in a neutral or reducing atmosphere and wherein the boron compound is present at from about 0.01 to 30 parts by weight and the magnesia-silica complex is present from about 2 to about 200 parts by weight per 100 parts by weight of MgO.
2. The method of claim 1 wherein the magnesia-silica complex has a MgO:SiO.sub.2 mole-ratio of from about 1:13 to 7:1 and the alkali metal oxide or hydroxide is from about 0.01 to 1.0 percent by weight of the magnesia-silica complex and the boron compound is selected from the group consisting of metaboric acid, boron oxide, ammonium tetraborate, ammonium pentaborate, ammonium peroxyborate, beryllium orthoborate, orthoboric acid, tetraboric acid, boron phosphide, boron silenide, boron trisilicide, boron hexasilicide, boron trisulfide, boron pentasulfide, lead borate, zinc borate, magnesium borate, cesium borate and rubidium borate.
3. The process of claim 1 wherein the MgO:SiO.sub.2 mole-ratio is 1:1.6 and the alkali metal oxide or hydroxide is from about 0.01 to 1.0 percent by weight of the magnesia-silica complex and a boron compound is selected from the group consisting of metaboric acid, boron oxide, orthoboric acid and tetraboric acid.
4. Magnetic ferrous material having on its surface a separator and insulating coating formed in accordance with the method of claim 1.
5. Magnetic ferrous material having on its surface a coating comprised of MgO, Mg(OH).sub.2 or mixtures thereof, at least one boron compound and at least one magnesia-silica complex containing from about 0.001 to 2.0 percent by weight of an alkali metal oxide or hydroxide wherein the mole-ratio of MgO:SiO.sub.2 is from about 1:25 to 14:1, said magnesia-silica complex being amorphous as indicated by its X-ray powder diffraction pattern and exhibiting the following differential thermal behavior characteristics: an endothermic peak at about 250.degree.C., an exothermic peak at about 820.degree.C. and at about 980.degree.C.
6. The magnetic ferrous material of claim 5 wherein the magnesia-silica complex has a MgO:SiO.sub.2 moleratio of from about 1:13 to 7:1 and the alkali metal oxide or hydroxide is from about 0.01 to 1.0 percent by weight of the magnesia-silica complex and the boron compound is selected from the group consisting of metaboric acid, boron oxide, ammonium tetraborate, ammonium pentaborate, ammonium peroxyborate, beryllium orthoborate, orthoboric acid, tetraboric acid, boron phosphide, boron selenide, boron trisilicide, boron hexasilicide, boron trisulfide, boron pentasulfide, lead borate, zinc borate, magnesium borate, cesium borate and rubidium borate.
7. The magnetic ferrous material of claim 5 wherein the MgO:SiO.sub.2 mole-ratio is 1:1.6 and the alkali metal oxide or hydroxide is from about 0.01 to 1.0 percent by weight of the magnesia-silica complex and a boron compound is selected from the group consisting of metaboric acid, boron oxide, orthoboric acid and tetraboric acid.
Patent Citations (1)
| Patent | Date | Inventor | Cited By |
|---|---|---|---|
| US3765957 | 1973-10-01 | Hamachi et al. |