US2452914A - Process and composition for producing magnesium-zirconium alloys - Google Patents
Process and composition for producing magnesium-zirconium alloys Download PDFInfo
- Publication number
- US2452914A US2452914A US684262A US68426246A US2452914A US 2452914 A US2452914 A US 2452914A US 684262 A US684262 A US 684262A US 68426246 A US68426246 A US 68426246A US 2452914 A US2452914 A US 2452914A
- Authority
- US
- United States
- Prior art keywords
- magnesium
- zirconium
- fluoride
- composition
- chloride
- Prior art date
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- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title description 19
- 238000000034 method Methods 0.000 title description 4
- 229910001093 Zr alloy Inorganic materials 0.000 title 1
- QRNPTSGPQSOPQK-UHFFFAOYSA-N magnesium zirconium Chemical compound [Mg].[Zr] QRNPTSGPQSOPQK-UHFFFAOYSA-N 0.000 title 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 31
- 229910052749 magnesium Inorganic materials 0.000 description 31
- 239000011777 magnesium Substances 0.000 description 31
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Inorganic materials [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 19
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 15
- 229910052726 zirconium Inorganic materials 0.000 description 15
- 239000000126 substance Substances 0.000 description 13
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 238000005275 alloying Methods 0.000 description 12
- 235000003270 potassium fluoride Nutrition 0.000 description 11
- 239000011698 potassium fluoride Substances 0.000 description 10
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 150000001805 chlorine compounds Chemical class 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- 229910052791 calcium Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000013024 sodium fluoride Nutrition 0.000 description 5
- 229910052712 strontium Inorganic materials 0.000 description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 150000001340 alkali metals Chemical class 0.000 description 4
- 229910052788 barium Inorganic materials 0.000 description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000011775 sodium fluoride Substances 0.000 description 4
- 239000011876 fused mixture Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- -1 i. e Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical class [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003112 inhibitor Substances 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
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
Definitions
- zirconium to magnesium or magnesium base alloys facilitates the: production of castings and wrought goods having a fine grained crystalline texture" and desirable mechanical properties.
- an alloying substance to introduce zirconium into magnesium consists of mixtures of one or more chlorides of alkali and alkaline earth metals including magnesium with the aforesaid mixtures or compounds of zirconium fluoride with potassium or sodium fluorides.
- the alloying substance may be cast into lumps which may be stirred into the melted magnesium or the magnesium may be poured on the alloying substance which is flrst placed in the bottom of the crucible.
- the alloying substance may be contacted with the molten magnesium Whilst itself in molten condition.
- the alloying substance may also incorporate reducible halides of permissible alloying elements.
- the ratio of zirconium fluoride to potassium fluoride may exceed that in K2ZIF6.
- a composition for introducing zirconium into magnesium and magnesium base alloys consisting essentially of a fused mixture of at least one of the alkali metal chlorides, zirconium fluoride, and at least one of the fluorides of the group consisting of potassium fluoride and sodium fluoride.
- a composition for introducing zirconium into magnesium and magnesium base alloys consisting essentially of a fused mixture of at least one chloride selected from the group consisting of the chlorides of the metals calcium, barium, strontium, magnesium and alkali metals, together with zirconium fluoride, at least one of the fluorides of the group consisting of potassium fluoride and sodium fluoride and any reaction products of the aforementioned salts.
- composition as claimed in claim 1 which 3 also contains at least one reducible halide of metals which do not form high melting point com pounds with zirconium in molten magnesium.
- a composition for introducing zirconium into magnesium and magnesium base alloys consisting essentially of a mixture of at least one chloride selected from the group consisting of the chlorides of calcium, barium, strontium, and magnesium and optionally at least one alkali metal chloride with a product which is a chemical association of potassium fluoride and zirconium fluoride, in which product the ratio of the zirconium fluoride to potassium fluoride exceeds that in K2ZrFc, and reaction products of such chloride and product.
- a method of preparing a composition for introducing zirconium into magnesium and magnesium base alloys consisting in fusing together at least one chloride selected from the group consisting of the chlorides'of the metals calcium, barium, strontium, magnesium, and alkali metals, with at least one'substance selected from the group consisting of mixtures and compound salts of zirconium fluoride with at least one of the fluorides of potassium and sodium.
- a method of preparing a composition for introducing zirconium into magnesium and magnesium base alloys consisting of making a fused mixture of zirconium fluoride with at least one of the fluorides of potassium and sodium, and addtroducing zirconium into magnesium and magnesium base alloys consisting in fusing together at least one chloride selected from the group consisting of the chlorides of the metals calcium, barium, strontium, magnesium and alkali metals, with a product which is a chemical association of zirconium fluoride and potassium fluoride, in which product the ratio of the zirconium fluoride to potassium fluoride exceeds that in KzZrFs.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
Patented Nov. 2, 1948 Y UNITED STATES PATENT OFFICE r 2,452,914
OC ND C ITION F R OD ING MAGNESIUM-ZIRCONIUM ALLOYS Edward Frederick Emley, Clifton Junction Works,
near Manchester, Englan assignor to Mag- .nesium Elektron Limited, London, England, a
British com any This invention relates to magnesium base alloys which contain zirconium. g l
The addition of zirconium to magnesium or magnesium base alloys facilitates the: production of castings and wrought goods having a fine grained crystalline texture" and desirable mechanical properties.
However, considerable difliculties have been experienced in alloying zirconium with magnesium in amounts of at least 0.4% zirconium which are necessary if alloys having the most desirable mechanical properties are to be produced. Research on this problem resulted in the invention described in British Patentv No.;5ll,l3'7 according to whichelements such as aluminium, silicon, tin, manganese, cobalt, nickel, and antimony, which form high melting point compounds with zirco nium, and which We term fzirconium alloying inhibitor elements, are omitted from the alloy, whilst other elements (which we term permissible alloying elements) such as zinc and cadmium may be included.
In order to introduce the zirconium into the alloy I have experimented with the addition of zirconium chloride and various other compounds or mixtures which, however, are attended by various disadvantages.
Amongst other substances I have tried mixtures or compounds consisting of zirconium fluoride with potassium and/or sodium fluoride. I have found however that when these substances are used in the form of powder considerable burning of the magnesium occurs, and very little zirconium is taken up into the alloy. If however these substances are added to the magnesium in the molten form or in the form of prefused lumps, reaction is still more violent, and indeed frequently results in dangerous explosions.
I have now ascertained that such mixtures or compounds when mixed with certain chlorides can be reacted with molten magnesium without violent reaction. This even applies when the chloride employed is that of the same alkali metal, the fluoride of which has been incorporated in the alloying mixture, i. e, potassium chloride will inhibit the violent reaction in the presence of potassium fluoride and similarly sodium chloride will inhibit the violent reaction in the presence of sodium fluoride.
According to the present invention, therefore, an alloying substance to introduce zirconium into magnesium consists of mixtures of one or more chlorides of alkali and alkaline earth metals including magnesium with the aforesaid mixtures or compounds of zirconium fluoride with potassium or sodium fluorides.
For the purpose of alloying zirconium with magnesium the use of magnesium, calcium, and to a lesser extent, strontium and barium chlorides, was originally found to be undesirable as this is '8- Claims. (01. 15-168) accompanied by more orless marked volatilisation of zirconium chloride. This diificulty can however be overcome by taking suitable precautions e. g; (a), the composition of the chloride mixture is. preferably selected so that it is substantially fluid at 700 C. or less, (b) the fluozirconate is. melted separately from the chloride melt. and. the two melts at comparatively low tempera tures e. g. below 750 C, are then mixed, (-c). the molten mixture is either cast rapidly into moulds for subsequent. use or' the magnesium required to make the final alloy is poured on without delay,
ride with one of the aforesaid mixtures or com- I pounds of zirconium fluoride with potassium fluoride and a good example of a suitable alloying substance is as follows:
Per cent KzzrFfi The zirconium fluoride goes into chemical association with the other fluoride. It cannot be separated by mere physical processes.
The alloying substance may be cast into lumps which may be stirred into the melted magnesium or the magnesium may be poured on the alloying substance which is flrst placed in the bottom of the crucible. The alloying substance may be contacted with the molten magnesium Whilst itself in molten condition. The alloying substance may also incorporate reducible halides of permissible alloying elements.
The ratio of zirconium fluoride to potassium fluoride may exceed that in K2ZIF6.
I claim:
1. A composition for introducing zirconium into magnesium and magnesium base alloys consisting essentially of a fused mixture of at least one of the alkali metal chlorides, zirconium fluoride, and at least one of the fluorides of the group consisting of potassium fluoride and sodium fluoride.
2. A composition for introducing zirconium into magnesium and magnesium base alloys consisting essentially of a fused mixture of at least one chloride selected from the group consisting of the chlorides of the metals calcium, barium, strontium, magnesium and alkali metals, together with zirconium fluoride, at least one of the fluorides of the group consisting of potassium fluoride and sodium fluoride and any reaction products of the aforementioned salts.
.3. A composition as claimed in claim 1 which 3 also contains at least one reducible halide of metals which do not form high melting point com pounds with zirconium in molten magnesium.
4. A composition for introducing zirconium into magnesium and magnesium base alloys consisting essentially of a mixture of at least one chloride selected from the group consisting of the chlorides of calcium, barium, strontium, and magnesium and optionally at least one alkali metal chloride with a product which is a chemical association of potassium fluoride and zirconium fluoride, in which product the ratio of the zirconium fluoride to potassium fluoride exceeds that in K2ZrFc, and reaction products of such chloride and product.
5. A method of preparing a composition for introducing zirconium into magnesium and magnesium base alloys consisting in fusing together at least one chloride selected from the group consisting of the chlorides'of the metals calcium, barium, strontium, magnesium, and alkali metals, with at least one'substance selected from the group consisting of mixtures and compound salts of zirconium fluoride with at least one of the fluorides of potassium and sodium.
6. A method of preparing a composition for introducing zirconium into magnesium and magnesium base alloys consisting of making a fused mixture of zirconium fluoride with at least one of the fluorides of potassium and sodium, and addtroducing zirconium into magnesium and magnesium base alloys consisting in fusing together at least one chloride selected from the group consisting of the chlorides of the metals calcium, barium, strontium, magnesium and alkali metals, with a product which is a chemical association of zirconium fluoride and potassium fluoride, in which product the ratio of the zirconium fluoride to potassium fluoride exceeds that in KzZrFs.
EDWARD FREDERICK EMLEY.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number I Name Date 2,193,363 Adamoli Mar. 12, 1940 2,250,687 Zeppelin July 29, 1941
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2452914X | 1945-08-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2452914A true US2452914A (en) | 1948-11-02 |
Family
ID=10907310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US684262A Expired - Lifetime US2452914A (en) | 1945-08-14 | 1946-07-17 | Process and composition for producing magnesium-zirconium alloys |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2452914A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2497529A (en) * | 1945-03-22 | 1950-02-14 | Magnesium Elektron Ltd | Process for production of magnesium base alloys containing zirconium |
| US2497530A (en) * | 1945-03-22 | 1950-02-14 | Magnesium Elektron Ltd | Master alloy for introducing zirconium into magnesium |
| US2497537A (en) * | 1946-05-17 | 1950-02-14 | Magnesium Elektron Ltd | Zirconium carrying alloying substance |
| US2604394A (en) * | 1949-07-04 | 1952-07-22 | Magnesium Elektron Ltd | Magnesium base alloys |
| US2911297A (en) * | 1956-05-05 | 1959-11-03 | Hugo Wachenfeld | Processes for the introduction of alloying constituents into metal melts |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2193363A (en) * | 1936-06-06 | 1940-03-12 | Perosa Corp | Process for obtaining beryllium and beryllium alloys |
| US2250687A (en) * | 1938-03-02 | 1941-07-29 | Walther H Duisberg | Manufacture of alloys |
-
1946
- 1946-07-17 US US684262A patent/US2452914A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2193363A (en) * | 1936-06-06 | 1940-03-12 | Perosa Corp | Process for obtaining beryllium and beryllium alloys |
| US2250687A (en) * | 1938-03-02 | 1941-07-29 | Walther H Duisberg | Manufacture of alloys |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2497529A (en) * | 1945-03-22 | 1950-02-14 | Magnesium Elektron Ltd | Process for production of magnesium base alloys containing zirconium |
| US2497530A (en) * | 1945-03-22 | 1950-02-14 | Magnesium Elektron Ltd | Master alloy for introducing zirconium into magnesium |
| US2497537A (en) * | 1946-05-17 | 1950-02-14 | Magnesium Elektron Ltd | Zirconium carrying alloying substance |
| US2604394A (en) * | 1949-07-04 | 1952-07-22 | Magnesium Elektron Ltd | Magnesium base alloys |
| US2911297A (en) * | 1956-05-05 | 1959-11-03 | Hugo Wachenfeld | Processes for the introduction of alloying constituents into metal melts |
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