US2360717A - Method of eliminating aluminate and silicate inclusions - Google Patents
Method of eliminating aluminate and silicate inclusions Download PDFInfo
- Publication number
- US2360717A US2360717A US467152A US46715242A US2360717A US 2360717 A US2360717 A US 2360717A US 467152 A US467152 A US 467152A US 46715242 A US46715242 A US 46715242A US 2360717 A US2360717 A US 2360717A
- Authority
- US
- United States
- Prior art keywords
- steel
- cerium
- inclusions
- steels
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title description 12
- 150000004645 aluminates Chemical class 0.000 title description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title 1
- 229910000831 Steel Inorganic materials 0.000 description 48
- 239000010959 steel Substances 0.000 description 48
- 229910052684 Cerium Inorganic materials 0.000 description 33
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 29
- 229910052782 aluminium Inorganic materials 0.000 description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910000655 Killed steel Inorganic materials 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- QCCDYNYSHILRDG-UHFFFAOYSA-K cerium(3+);trifluoride Chemical compound [F-].[F-].[F-].[Ce+3] QCCDYNYSHILRDG-UHFFFAOYSA-K 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 230000001627 detrimental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- UQLLWWBDSUHNEB-CZUORRHYSA-N Cefaprin Chemical compound N([C@H]1[C@@H]2N(C1=O)C(=C(CS2)COC(=O)C)C(O)=O)C(=O)CSC1=CC=NC=C1 UQLLWWBDSUHNEB-CZUORRHYSA-N 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940081090 cefa Drugs 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- DRVWBEJJZZTIGJ-UHFFFAOYSA-N cerium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Ce+3].[Ce+3] DRVWBEJJZZTIGJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical class [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
- C21C7/00—Treating molten ferrous alloys, e.g. steel, not covered by groups C21C1/00 - C21C5/00
- C21C7/04—Removing impurities by adding a treating agent
- C21C7/06—Deoxidising, e.g. killing
Definitions
- the invention relates generally to a method of refining steel and has more particular reference to an improved refining method which will produce a'high quality steel that will be clean as judged by microscopic, macroscopic or magnafiux methods.
- the present invention aims to provide animproved refining method for producing a high quality, sound and clean steel by eliminating to a substantial degree the harmful non-metallic inclusions in the steel, and which'will have application to present day steel making processes.
- a further object is to .provide an improved refining method whichwill increase the'y ield of I sound clean steel in the ingot by approximately 50 percentage of cerium is a factor in the invention since it results in the production of a minimum' ten per cent.
- I a I The invention proposes to reduce the inclusions while the steel is in a molten state by chemical combination with one of the rare earthmetals, preferably cerium. The addition of cerium to killed steels in amounts of from -.01%
- Cerium oxides and sulphides are formed when cerium is used asthe rare earth metal but the reaction products of this metalare not objectionable since they do not agglomerate and are small and well distributed in the steel, whereas, .the inclusions such as theoxides of aluminum, silicon and the other deoxidizers do agglomerate to-form stringers following the rolling operation and are tough, brittle particles, considerably harder than the steel itself In this way subsequent machining operations on the steel are substantially improved in addition to the fundamental improvement as a result of great cleanliness.
- cerium tothe molten steel takes place after the introduction oi the final deoxidizers for deoxidizing the metal and thus the refractory non-metallic inclusions comprising the reaction products of the final deoxidizers are preseat for chemical combination with the cerium.
- the cerium may be added to the ladle as the 40 heat is tapped, although it is also within the invention to add the cerium to the molten steel as it is poured into the ingot molds.
- cerous fluoride having the chemical formula CeFs. This compound of cerium has a high melting point and the cerium is therefore liberated at the proper time for performing the functions desired.
- cerium for various carbon steels is given in the table below, The low of cerium inclusions. Only enough cerium is 7 added for combining chemically with the oxygen of the non-metallic inclusions formed by the addition of the final deoxidizers to the molten steel.
- cerium can be added in uni/ form but-I prefer to use:
- cerium in amounts and in a manner herein described is especially beneficial in making high aluminum steels wherein the aluminumconstitutes an alloying constituent and may be present in quantities ranging from 1% to 1.5%.
- Such steels are known as nitriding steels, and in the past considerable trouble has been encountered in maintaining uniform aluminum content for all the ingots poured from any one particular heat. In other words, the aluminum content has generally been progressively lower in successive ingots.
- cerium By the addition of cerium, the tailing off of aluminum in successive ingots is prevented and a uniform content of aluminum can be maintained for all the ingots poured from a heat.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
Description
Patented Oct. 17, 1944 METHOD OF ELIMIINATING ALUMINATE I AND SILICATE INCLUSIONS Harold E. Phelps, Detroit, Mich, assignor to The Cerium Corporation, tion of Illinois Chicago, 111., a corpora- No Drawing. Application November 27, 1942,
Serial No. 467,152
Claims.
The invention relates generally to a method of refining steel and has more particular reference to an improved refining method which will produce a'high quality steel that will be clean as judged by microscopic, macroscopic or magnafiux methods.
In the production of high quality steel the elimination of non-metallic inclusions is of the utmost importance. In fact, cleanliness in steel is in direct proportion to the absence of these inclusions. It is now universally recognized that many previous unexplained failures of steel have been due to these occluded oxidized particles, which may be considered as primarily the oxides of aluminum and silicon. The proportion of such particles in the ingot depends largely on the precautions taken during final stages in the steel making process, the opportunity allowed for the inclusions to separate out before and during teeming, and the care with which thefinal' deoxidizers such as aluminum, silicon .and zirconium are added to quiet the steel.
Since it has been known that the formation of inclusions in molten steel is largely due to the content of 'the steel by usual steel making processes before the final deoxidizers are. added. Thus, certain-methods maintain a reducing or deoxidizing slag for keeping the oxygen'content' I of the steel to a minimum. Other methods cantemplate the use of pure raw materials by which the bath' is oxidized to a minimum degree previous to final treatments. Final deoxidizers in a combined form, as alloys of iron, are also used. Thus ferro-silicon and ferro-aluminum and similar metals have been used in the final treatment for deoxidizing the steel.
The present invention aims to provide animproved refining method for producing a high quality, sound and clean steel by eliminating to a substantial degree the harmful non-metallic inclusions in the steel, and which'will have application to present day steel making processes.
A further object is to .provide an improved refining method whichwill increase the'y ield of I sound clean steel in the ingot by approximately 50 percentage of cerium is a factor in the invention since it results in the production of a minimum' ten per cent. I a I The invention proposes to reduce the inclusions while the steel is in a molten state by chemical combination with one of the rare earthmetals, preferably cerium. The addition of cerium to killed steels in amounts of from -.01%
'to 1.00% almost entirely eliminates the oxides, such as those of aluminum and silicon, namely, A120: and SiOz, through chemical combination of the cerium with the oxygen of the inclusion. This reduction of the aluminum and silicon oxides, liberates the metals so that they are free to alloy with'the steel. The same chemical combination takes place with respect to othe Ox des that'may be present in the molten steel. Their reduction freesthe metal which is kept in solution in the steel.
Cerium oxides and sulphides are formed when cerium is used asthe rare earth metal but the reaction products of this metalare not objectionable since they do not agglomerate and are small and well distributed in the steel, whereas, .the inclusions such as theoxides of aluminum, silicon and the other deoxidizers do agglomerate to-form stringers following the rolling operation and are tough, brittle particles, considerably harder than the steel itself In this way subsequent machining operations on the steel are substantially improved in addition to the fundamental improvement as a result of great cleanliness.
By reducing these hard, brittle oxides a double advantage is secured since in the first place-the metal, whether it be aluminum, silicon or manganese, is liberated for alloying with the steel, which is desirable, and secondly, even though other oxides are formed, they are small, well dis- *tributed and therefore not detrimental.
In accordance with the invention the addition of cerium tothe molten steel takes place after the introduction oi the final deoxidizers for deoxidizing the metal and thus the refractory non-metallic inclusions comprising the reaction products of the final deoxidizers are preseat for chemical combination with the cerium. The cerium may be added to the ladle as the 40 heat is tapped, although it is also within the invention to add the cerium to the molten steel as it is poured into the ingot molds.
cerous fluoride having the chemical formula CeFs. This compound of cerium has a high melting point and the cerium is therefore liberated at the proper time for performing the functions desired.
The preferred amounts of cerium for various carbon steels is given in the table below, The low of cerium inclusions. Only enough cerium is 7 added for combining chemically with the oxygen of the non-metallic inclusions formed by the addition of the final deoxidizers to the molten steel.
Also the cerium can be added in uni/ form but-I prefer to use:
Steels up to .20% C .03% to .06% Ce Steels from .20% C to .60% C .02% to .04% Ce Steels over .60% C .01% to .03% Ce For controlling grain size it has been common practice to add predetermined quantities of aluminum to the steel. Some of this metallic alumi: num is oxidized, forming alumina inclusions, with the result that its function as a grain-size controlling element is lost in addition to the production of the undesirable alumina inclusions. The addition of cerium according to theinvention has a stabilizing action in fine grained steels through the ability of the cerium to reduce the A120: inclusions. The aluminum is thereby kept in solution in the steel.
Also the addition of cerium in amounts and in a manner herein described is especially beneficial in making high aluminum steels wherein the aluminumconstitutes an alloying constituent and may be present in quantities ranging from 1% to 1.5%. Such steels are known as nitriding steels, and in the past considerable trouble has been encountered in maintaining uniform aluminum content for all the ingots poured from any one particular heat. In other words, the aluminum content has generally been progressively lower in successive ingots. By the addition of cerium, the tailing off of aluminum in successive ingots is prevented and a uniform content of aluminum can be maintained for all the ingots poured from a heat.
The advantages claimed for the present invention have been proved in actual practice. Electric steel has been produced substantially free of harmful non-metallic inclusions. Also the yield per ingot for this clean steel has been increased by approximately ten percent.
What is claimed is:
1. The process of manufacturing a clean steel, which consists in preparing a molten bath of killed steel, adding cerium to the killed steel in amounts ranging from .01% to 1.00%, and then pouring said steel to produce ingots in the usual manner.
2. The process of manufacturing a clean steel, which consists in preparing a molten bath of killed steel, adding cerium to the killed steel in amounts ranging from .01% to 1.00%, said cerium being added in combined form as cerous fluoride having the chemical formula CeFz, and then pouring said steel to produce ingots in the usual manner.
3. The process of manufacturing a clean steel which consists in preparing a molten bath of killed steel, adding cerium to the killed steel to reduce the inclusions by chemical combination with the oxygen of the inclusion, said cerium being added in the following amounts for the various carbon steels:
Steels up to .20% C .03%'to .06% Ce Steels from .20% to .60% C .02% to .04% Ce Steels over .60% C .01% to .03% Ce 4. The improvement in the manufacture of steel, which consists in adding the usual deoxidizers to the molten metal and then adding cerium to the molten metal in the following approximate amounts for the various carbon steels: Steels up to .20% C .03% to .06% Ce Steels from .20% to .60% C .02% to .04% Ce Steels over .60% C .01% to .03% Ce said cerium being added in combined form as cerous fluoride having the chemical formula CeFa.
5. The process of manufacturing a clean steel free of harmful inclusions, which consists in adding the final deoxidizers such as aluminum and silicon to the-molten steel for deoxidizing the same whereby refractory non-metallic inclusions are formed in the molten steel as reaction products of the final deoxidizers, then adding cerium for chemically reacting with said non-metallic inclusions in the following approximate amounts for the various carbonsteels:
Steels up to .20% C .03% to..06% Ce Steels from .20% to .60% C .02% to .04% Ce Steels over .60% C .01% to .03% Ce said cerium having the effect of reducing the said non-metallic inclusions and of leaving in the steel a minimum of small, well distributed particles which are not detrimental nor harmful to the steel. v
' HAROLD E. PHELPS.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US467152A US2360717A (en) | 1942-11-27 | 1942-11-27 | Method of eliminating aluminate and silicate inclusions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US467152A US2360717A (en) | 1942-11-27 | 1942-11-27 | Method of eliminating aluminate and silicate inclusions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2360717A true US2360717A (en) | 1944-10-17 |
Family
ID=23854581
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US467152A Expired - Lifetime US2360717A (en) | 1942-11-27 | 1942-11-27 | Method of eliminating aluminate and silicate inclusions |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2360717A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2683661A (en) * | 1951-10-31 | 1954-07-13 | Molybdenum Corp | Fine grain iron and method of production |
| US2683662A (en) * | 1951-10-31 | 1954-07-13 | Molybdenum Corp | Manufacture of iron and steel and products obtained |
| US2683663A (en) * | 1951-10-31 | 1954-07-13 | Molybdenum Corp | Stainless steel and method of production |
| US2702384A (en) * | 1949-12-07 | 1955-02-22 | Speed Products Company Inc | Stapling machine |
| US2705196A (en) * | 1952-02-20 | 1955-03-29 | Manufacturers Chemical Corp | Process for de-oxidizing a molten metal |
| US2813789A (en) * | 1952-04-08 | 1957-11-19 | Glaser Louis | Permanent magnet alloys |
| US2814559A (en) * | 1953-04-23 | 1957-11-26 | James A Clark | Process for the production of nodular cast iron |
| US2850381A (en) * | 1952-08-01 | 1958-09-02 | American Metallurg Products Co | Process and alloy for adding rare earth elements and boron to molten metal baths |
| US2980529A (en) * | 1956-12-07 | 1961-04-18 | American Metallurg Products Co | Method of making aluminum killed steel |
| US3218156A (en) * | 1963-10-16 | 1965-11-16 | Howe Sound Co | Process for vacuum deoxidation of alloys |
| US3865578A (en) * | 1972-01-25 | 1975-02-11 | Aikoh Co | Composition for treating steels |
| USRE28791E (en) * | 1969-07-16 | 1976-04-27 | Jones & Laughlin Steel Corporation | High-strength plain carbon steels having improved formability |
| USRE28790E (en) * | 1969-07-16 | 1976-04-27 | Jones & Laughlin Steel Corporation | High-strength low-alloy steels having improved formability |
| US4025368A (en) * | 1974-06-08 | 1977-05-24 | Kawasaki Steel Corporation | Weldable steel excellent in the toughness of the bond in a single layer welding with a large heat-input |
| US4131493A (en) * | 1974-01-22 | 1978-12-26 | Gurevich Samuil M | Flux-cored welding wire |
| US6142506A (en) * | 1998-09-14 | 2000-11-07 | Ford Global Technologies, Inc. | Energy absorbing vehicle trim with airbag |
-
1942
- 1942-11-27 US US467152A patent/US2360717A/en not_active Expired - Lifetime
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2702384A (en) * | 1949-12-07 | 1955-02-22 | Speed Products Company Inc | Stapling machine |
| US2683661A (en) * | 1951-10-31 | 1954-07-13 | Molybdenum Corp | Fine grain iron and method of production |
| US2683662A (en) * | 1951-10-31 | 1954-07-13 | Molybdenum Corp | Manufacture of iron and steel and products obtained |
| US2683663A (en) * | 1951-10-31 | 1954-07-13 | Molybdenum Corp | Stainless steel and method of production |
| US2705196A (en) * | 1952-02-20 | 1955-03-29 | Manufacturers Chemical Corp | Process for de-oxidizing a molten metal |
| US2813789A (en) * | 1952-04-08 | 1957-11-19 | Glaser Louis | Permanent magnet alloys |
| US2850381A (en) * | 1952-08-01 | 1958-09-02 | American Metallurg Products Co | Process and alloy for adding rare earth elements and boron to molten metal baths |
| US2814559A (en) * | 1953-04-23 | 1957-11-26 | James A Clark | Process for the production of nodular cast iron |
| US2980529A (en) * | 1956-12-07 | 1961-04-18 | American Metallurg Products Co | Method of making aluminum killed steel |
| US3218156A (en) * | 1963-10-16 | 1965-11-16 | Howe Sound Co | Process for vacuum deoxidation of alloys |
| USRE28791E (en) * | 1969-07-16 | 1976-04-27 | Jones & Laughlin Steel Corporation | High-strength plain carbon steels having improved formability |
| USRE28790E (en) * | 1969-07-16 | 1976-04-27 | Jones & Laughlin Steel Corporation | High-strength low-alloy steels having improved formability |
| US3865578A (en) * | 1972-01-25 | 1975-02-11 | Aikoh Co | Composition for treating steels |
| US4131493A (en) * | 1974-01-22 | 1978-12-26 | Gurevich Samuil M | Flux-cored welding wire |
| US4025368A (en) * | 1974-06-08 | 1977-05-24 | Kawasaki Steel Corporation | Weldable steel excellent in the toughness of the bond in a single layer welding with a large heat-input |
| US6142506A (en) * | 1998-09-14 | 2000-11-07 | Ford Global Technologies, Inc. | Energy absorbing vehicle trim with airbag |
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