US2924518A - Zirconium alloys - Google Patents
Zirconium alloys Download PDFInfo
- Publication number
- US2924518A US2924518A US746605A US74660558A US2924518A US 2924518 A US2924518 A US 2924518A US 746605 A US746605 A US 746605A US 74660558 A US74660558 A US 74660558A US 2924518 A US2924518 A US 2924518A
- Authority
- US
- United States
- Prior art keywords
- zirconium
- alloy
- alloys
- weight
- zircaloy
- 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
- 229910001093 Zr alloy Inorganic materials 0.000 title description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052726 zirconium Inorganic materials 0.000 claims description 13
- 239000012535 impurity Substances 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 description 25
- 239000000956 alloy Substances 0.000 description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PRVKLYVQRIDKIC-UHFFFAOYSA-N [Mo].[Cu].[Zr] Chemical compound [Mo].[Cu].[Zr] PRVKLYVQRIDKIC-UHFFFAOYSA-N 0.000 description 1
- QZLJNVMRJXHARQ-UHFFFAOYSA-N [Zr].[Cr].[Cu] Chemical compound [Zr].[Cr].[Cu] QZLJNVMRJXHARQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000000266 injurious effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005496 tempering Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
Definitions
- Zirconium alloys in accordance with the present invention contain 0.51.5% by weight of copper, and from 0.25-1.5% by weight of molybdenum or chromium, the
- Example 2Cu, 1.0%; M0, 1.5%; remainder Zr The following mechanical properties of the improved alloys in comparison with zirconium and Zircaloy-2 are as follows:
- V.P.N. Vickers Pyramid Number
- Alloy 3 30 300 3,000 secs. secs. secs. secs.
- Example 1 alloy was slightlyhardcr for the longest-period of load application, and slightly less hard for the shorter periods of 5 load application than Zircalo'y-Z.”
- Specimens of Example 1 alloy were about 20% better, and of Example 2 alloy about better than those of Zircaloy-2," the percentage elongation of specimens of Example l was about the same as that of Zircaloy-Z, while that of Example 2 was about two-thirds that of Zircaloy 2. This improvement was increased when the specimens were tested at 375 C.
- Example 1 and Example 2 are 0.012386 cm.- and 0.015126 cm.- respectively.
- the high temperature mechanical properties of zirconium-copper-molybdenum and zirconium-copper-chromium alloys mentioned above can be further improved by heat treatment, which consists of heating the alloy to a temperature of 850 C. to 950" C. and maintaining the temperature for a specified time before quenching to reduce the temperature of the alloy rapidly. This treatment may then be followed by a tempering treatment which consists of reheating the alloy for a specified time at a temperature below 850 C.
- the constituents of the alloy should be melted in a vacuum arc furnace.
- the alloys of the invention can be readily fabricated by conventional methods.
- Impurities in the base zirconium sponge should be kept to a minimum.
- the most deleterious impurities from the corrosion resistance point of view are. aluminium, silicon, hydrogen, xygenr i s n. a it ni m. l minium should be kept below 150 parts per million, whilst nitrogen and'titanium are not so injurious, and in the latter case, and titanium content may be as high as 1,000
- An alloy consisting of 0.5 to 1.5% by weight of copper, 0.25 to 1.5% by weight of a metal selected from the group consisting of chromium and molybdenum, and the remainder zirconium except for unavoidable impurities.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Furnace Charging Or Discharging (AREA)
- Conductive Materials (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
ZIRCONIUM ALLOYS Thomas Raine, Bramhall, and James Alan Robinson,
Bolton, England, assignors to Metropolitan-Vickers Electrical Company Limited, London, England, a
British company No Drawing. Appllcation July 7, 195a Serial No. 746,605
Claims priority, application Great Britain July 26, 1957 5 Claims. on. 75-111 This, invention relates ,to alloys suitable, inter alia, for use at high temperatures in an atmosphere of carbon dioxide.
Conditions arise, in the core of graphite moderated nuclear reactors in which carbon dioxide is used for cooling and heat extraction, where metallic parts are brought, under operating conditions, into contact with carbon dioxide at a high temperature. Normal structural materials, such as steel cannot be employed in these conditions because of their high neutron absorption.
Consideration has been given to the use of alloys of zirconium in such reactors. A known alloy of zirconium, Zircaloy-2, which contains l.3-l.6% tin, 0.070.2% iron, 0.050.15% chromium and 0.03-0.08% nickel, possesses good strength, and has a low neutron cross-section. But in the temperature range above 400 C. its resistance to corrosion by carbon dioxide is inadequate.
It has now been discovered, however, that when used in contact with carbon dioxide at temperatures up to 600 C. an alloy of zirconium with copper and molybdenum or chromium is both resistant to corrosion and has improved resistance to creep.
Zirconium alloys in accordance with the present invention contain 0.51.5% by weight of copper, and from 0.25-1.5% by weight of molybdenum or chromium, the
remainder consisting wholly of zirconium, except for unavoidable impurities which are normally found in the commercial material, known as sponge zirconium, which is preferably used as the source of zirconium in the alloy.
Two alloys which constitute preferred embodiments of the invention are:
Example 1Cu, 0.5%; M0, 0.5%; remainder Zr Example 2Cu, 1.0%; M0, 1.5%; remainder Zr The following mechanical properties of the improved alloys in comparison with zirconium and Zircaloy-2 are as follows:
Hardness tests at room temperature V.P.N. represents Vickers Pyramid Number.
These tests showed the improved hardness of the alloys of the invention over zirconium and Zircaloy-Z.
Hardness tests at a temperature of 500 C. with creasing times of load application and compared with 1 Zircaloy-Z showed the following results:
V.P.N.
Alloy 3 30 300 3,000 secs. secs. secs. secs.
Zircaloy2. 60 52 38 30 Example (2)- 66 61 59 55 The specimens of both alloys were annealed at 820 C. in vacuo prior to testing.
Tests made at 475 C. indicated that Example 1 alloy was slightlyhardcr for the longest-period of load application, and slightly less hard for the shorter periods of 5 load application than Zircalo'y-Z."
The tensile strength of the improved zirconium alloys of the invention at roomtemperature, after annealing at 820 C. showed increases over that of Zircaloy-Z. Specimens of Example 1 alloy were about 20% better, and of Example 2 alloy about better than those of Zircaloy-2," the percentage elongation of specimens of Example l was about the same as that of Zircaloy-Z, while that of Example 2 was about two-thirds that of Zircaloy 2. This improvement was increased when the specimens were tested at 375 C.
Tensile creep tests at 6,000 psi. the specimens being tested in an atmosphere of argon, showed the following results:
Temp. Time in hours to reach a of strain of- Alloy Condition Tag,
Zlrcaloy-2 Arsiggglgd at 450 800 1, 500 5, 300 6, 600 Do do 476 300 600 1, 040 2, 240 D0 n 500 275 480 810 Example (1) Aggg tld at 450 860 1, 960 5, 500 Example (2) do 475 500 900 1, 700 3,800
The increase in creep resistance of the improved alloys over that of Zircaloy-2 was greater the higher the percentage strain.
The reaction to corrosion by CO, is illustrated by results given below of tests at 700 C. and one atmosphere gas pressure.
Time to reach Post transition Alloy 50 mg./cm.1 Corrosion rate,
hours Zirconium--. 1, 200 50. 1x10- Z1rcaloy-2. 870x10 Example (1) 5, 000 11. 4x10- Example (2) 5, 000 9. 4X10- cm." relative to a cross-section in barns/atom of 0.20, then the corresponding eross-seetions of Example 1 and Example 2 are 0.012386 cm.- and 0.015126 cm.- respectively.
The high temperature mechanical properties of zirconium-copper-molybdenum and zirconium-copper-chromium alloys mentioned above can be further improved by heat treatment, which consists of heating the alloy to a temperature of 850 C. to 950" C. and maintaining the temperature for a specified time before quenching to reduce the temperature of the alloy rapidly. This treatment may then be followed by a tempering treatment which consists of reheating the alloy for a specified time at a temperature below 850 C.
Arising from the ability of zirconium to oxidise and to absorb atmospheric and other impurities readily at elevated temperatures, the constituents of the alloy should be melted in a vacuum arc furnace. Apart from this restriction the alloys of the invention can be readily fabricated by conventional methods.
Impurities in the base zirconium sponge should be kept to a minimum. The most deleterious impurities from the corrosion resistance point of view are. aluminium, silicon, hydrogen, xygenr i s n. a it ni m. l minium should be kept below 150 parts per million, whilst nitrogen and'titanium are not so injurious, and in the latter case, and titanium content may be as high as 1,000
. 4 parts per million without appreciably affecting the corrosion resistance of the alloys.
What we claim is:
1. An alloy consisting of 0.5 to 1.5% by weight of copper, 0.25 to 1.5% by weight of a metal selected from the group consisting of chromium and molybdenum, and the remainder zirconium except for unavoidable impurities.
2. An alloy as claimed in claim 1 and intended to be employed at a high temperature in contact with carbon dioxide, in which impurities, such as aluminium and titanium are restricted to the order of 100 parts per million, by weight.
3. An alloy as claimed in claim 1, in which the source of zirconium used in making'the alloy is that commercially known as sponge zirconium.
4. An alloy consisting of 0.5% by weight, of copper, 0.5% by weight, of molybdenum and the remainder zirconium except for unavoidable impurities.
5. An alloy of 1.0% by weight copper, 1.5% by weight of molybdenum, and the remainder zirconium except for unavoidable impurities.
References Cited in the file 015 this patent UNITED STATES PATENTS 2,705,674 Chubb Apr. 5, 1955
Claims (1)
1. AN ALLOY CONSISTING OF 0.5 TO 1.5% BY WEIGHT OF COPPER, 0.25 TO 1.5% BY WEIGHT OF A MERAL SELECTED FROM THE GROUP CONSISTING OF CHROMIUM AND MOLYBDENUM, AND THE REMAINDER ZIRCONIUM EXCEPT FOR UNAVOIDABLE IMPURITIES.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB23758/57A GB829668A (en) | 1957-07-26 | 1957-07-26 | Improvements relating to zirconium alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2924518A true US2924518A (en) | 1960-02-09 |
Family
ID=10200849
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US746605A Expired - Lifetime US2924518A (en) | 1957-07-26 | 1958-07-07 | Zirconium alloys |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US2924518A (en) |
| BE (1) | BE568934A (en) |
| DE (1) | DE1118976B (en) |
| FR (1) | FR1199996A (en) |
| GB (1) | GB829668A (en) |
| IT (1) | IT594672A (en) |
| NO (1) | NO95039A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3072478A (en) * | 1958-10-16 | 1963-01-08 | Associated Electrical Ind Rugb | Zirconium alloys |
| US3218162A (en) * | 1962-03-16 | 1965-11-16 | Ass Elect Ind | Process for making zirconium alloys |
| US3303025A (en) * | 1962-12-19 | 1967-02-07 | Ass Elect Ind | Zirconium alloys |
| US3645800A (en) * | 1965-12-17 | 1972-02-29 | Westinghouse Electric Corp | Method for producing wrought zirconium alloys |
| US5654993A (en) * | 1993-06-30 | 1997-08-05 | Abb Atom Ab | Fuel element for pressurized--water reactor with guide tubes finally heat-treated in two steps |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR1454541A (en) * | 1965-08-27 | 1966-02-11 | Commissariat Energie Atomique | Zirconium alloy |
| FR2334763A1 (en) * | 1975-12-12 | 1977-07-08 | Ugine Aciers | PROCESS FOR IMPROVING THE HOT RESISTANCE OF ZIRCONIUM AND ITS ALLOYS |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2705674A (en) * | 1954-02-18 | 1955-04-05 | Chubb Walston | Ternary zirconium alloys |
-
0
- IT IT594672D patent/IT594672A/it unknown
- NO NO95039D patent/NO95039A/no unknown
- BE BE568934D patent/BE568934A/xx unknown
-
1957
- 1957-07-26 GB GB23758/57A patent/GB829668A/en not_active Expired
-
1958
- 1958-07-07 US US746605A patent/US2924518A/en not_active Expired - Lifetime
- 1958-07-21 DE DEM38334A patent/DE1118976B/en active Pending
- 1958-07-24 FR FR1199996D patent/FR1199996A/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2705674A (en) * | 1954-02-18 | 1955-04-05 | Chubb Walston | Ternary zirconium alloys |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3072478A (en) * | 1958-10-16 | 1963-01-08 | Associated Electrical Ind Rugb | Zirconium alloys |
| US3218162A (en) * | 1962-03-16 | 1965-11-16 | Ass Elect Ind | Process for making zirconium alloys |
| US3303025A (en) * | 1962-12-19 | 1967-02-07 | Ass Elect Ind | Zirconium alloys |
| US3645800A (en) * | 1965-12-17 | 1972-02-29 | Westinghouse Electric Corp | Method for producing wrought zirconium alloys |
| US5654993A (en) * | 1993-06-30 | 1997-08-05 | Abb Atom Ab | Fuel element for pressurized--water reactor with guide tubes finally heat-treated in two steps |
| US5677937A (en) * | 1993-06-30 | 1997-10-14 | Abb Atom Ab | Fuel element for pressurized-water reactor with guide tubes finally heat-treated in two steps |
Also Published As
| Publication number | Publication date |
|---|---|
| IT594672A (en) | |
| FR1199996A (en) | 1959-12-17 |
| GB829668A (en) | 1960-03-02 |
| NO95039A (en) | |
| DE1118976B (en) | 1961-12-07 |
| BE568934A (en) |
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