US3464815A - Non-magnetic iron-nickel-chromium-molybdenum alloy,and watch springs obtained with this alloy - Google Patents
Non-magnetic iron-nickel-chromium-molybdenum alloy,and watch springs obtained with this alloy Download PDFInfo
- Publication number
- US3464815A US3464815A US647956A US3464815DA US3464815A US 3464815 A US3464815 A US 3464815A US 647956 A US647956 A US 647956A US 3464815D A US3464815D A US 3464815DA US 3464815 A US3464815 A US 3464815A
- Authority
- US
- United States
- Prior art keywords
- alloy
- nickel
- chromium
- molybdenum
- magnetic iron
- 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
- 229910045601 alloy Inorganic materials 0.000 title description 25
- 239000000956 alloy Substances 0.000 title description 25
- 229910001182 Mo alloy Inorganic materials 0.000 title description 3
- VZUPOJJVIYVMIT-UHFFFAOYSA-N [Mo].[Ni].[Cr].[Fe] Chemical compound [Mo].[Ni].[Cr].[Fe] VZUPOJJVIYVMIT-UHFFFAOYSA-N 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000004411 aluminium Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 239000011651 chromium Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 8
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011733 molybdenum Substances 0.000 description 8
- 229910052750 molybdenum Inorganic materials 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 239000005864 Sulphur Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 230000005291 magnetic effect Effects 0.000 description 5
- 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 5
- 239000000203 mixture Substances 0.000 description 5
- 229910000942 Elinvar Inorganic materials 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 229910001004 magnetic alloy Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 chromium carbides Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035945 sensitivity 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
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B17/00—Mechanisms for stabilising frequency
- G04B17/20—Compensation of mechanisms for stabilising frequency
- G04B17/22—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature
- G04B17/227—Compensation of mechanisms for stabilising frequency for the effect of variations of temperature composition and manufacture of the material used
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B43/00—Protecting clockworks by shields or other means against external influences, e.g. magnetic fields
- G04B43/007—Antimagnetic alloys
Definitions
- the heat coefiicient is a basic parameter characterizing the sensitivity of the spring to variations in ambient temperature.
- the other three parameters will not be described here, since they are not directly concerned with the invention.
- the heat coeflicient is dependent on the thermoelastic coefficient of the alloys used for the manufacture of the spring.
- the thermoelastic coefficient indicates the effect of temperature variations on the modulus of elasticity of the alloys.
- One of the aims in the manufacture of a watch spring is to obtain a zero heat coeflicient. This can be done by using an alloy having a zero thermoelastic coefficient under the operating conditions of the spring.
- Fe Remainder Durinval alloys are distinguished from Elinvar alloys in particular by their hardening mechanism.
- the mechanical characteristics of Elinvar are produced by appropriate heat treatment during which chromium carbides are precipitated, while titanium nickelides and aluminium nickelides are precipitated in the case of Durinval. This essential diiference in the hardening mechanisms of the two types of alloy is, of course, directly connected with differences in composition, which a comparison of the above two analyses will reveal.
- Durinval alloys like Elinvar alloys, have, of course, a substantially zero thermoelastic coefficient in the region of ambient temperature.
- This invention relates to a new group of alloys that have the usual features of conventional Durinval alloys, but are non-magnetic at ambient temperature.
- the invention relates to a non-magnetic alloy characterized in that it is composed of the following, by weight: 36.5 to 39.5% of nickel, 1.5 to 4.5% of chromium, 1.5 to 3% of molybdenum, 0.75 to 1.25% of aluminium and 2.3% of titanium, together with very small quantities of carbon, silicon, manganese, sulphur and phosphorus, the remainder being iron.
- the invention also relates to watch springs made of this alloy.
- composition by weight of an alloy according to the invention may be given as an example: carbon 0.005%, silicon 0.34%, manganese 0.16%, nickel 38.4%, chromium 3.37%, molybdenum 2%, titanium 2.46%, aluminium 0.96% and iron 52.29%, the remainder being sulphur and phosphorus.
- the Curie point of this alloy is below 18 and it is practically non-magnetic at ambient temperature, having a zero thermoelastic coefficient.
- Non-magnetic iron-nickel-chromiummolybdenum alloy characterized in that it is composed, by Weight, of 36.5 to 39.5% of nickel, 1.5 to 4.5% of chromium, 1.5 to 3% of molybdenum, 0.75 to 1.25% of aluminium and 2 to 3% of titanium, the remainder being iron, to gether with very small quantities of carbon, silicon, manganese, sulphur and phosphorus.
- a non-magnetic alloy as claimed in claim 1 characterized in that it is composed by Weight of 38.4% of nickel, 3.37% of chromium, 2% of molybdenum, 0.96%
- Watch springs characterized in that they are made of a non-magnetic iron-nickel-chromii1m-molybdenum alloy, composed, by weight, of 36.5 to 39.5% of nickel, 1.5 to 4.5% of chromium, 1.5 to 3% of molybdenum, 0.75 to 1.25% of aluminium and 2 to 3% of titanium, the remainder being iron, together with very small quantities of carbon, silicon, manganese, sulphur and phosphorus.
Landscapes
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Soft Magnetic Materials (AREA)
- Heat Treatment Of Steel (AREA)
Description
United States Patent 3,464,815 NON-MAGNETIC IRON-NICKEL-CHROMIUM- MOLYBDENUM ALLOY, AND WATCH SPRINGS OBTAINED WITH THIS ALLOY Xavier Wache, Sauvigny-les-Bois, Nievre, France, assignor t0 Socit Metallurgique dlmphy, Paris, France, a
French company No Drawing. Filed June 22, 1967, Ser. No. 647,956
Claims priority, application France, July 12, 1966, Int. Cl. C22c 39/20, 39/50 U.S. Cl. 75-124 3 Claims ABSTRACT OF THE DISCLOSURE Watch springs are characterized by four parameters well known to those who specialise in watch-making, namely the heat coefficient, isochronism factor, position distances and secondary error.
The heat coefiicient is a basic parameter characterizing the sensitivity of the spring to variations in ambient temperature. The other three parameters will not be described here, since they are not directly concerned with the invention.
The heat coeflicient is dependent on the thermoelastic coefficient of the alloys used for the manufacture of the spring. The thermoelastic coefficient indicates the effect of temperature variations on the modulus of elasticity of the alloys.
One of the aims in the manufacture of a watch spring is to obtain a zero heat coeflicient. This can be done by using an alloy having a zero thermoelastic coefficient under the operating conditions of the spring.
One of the solutions of this problem already proposed by the applicants is to make these springs of a type of alloy known as Elinvar, which is a trademark filed in the name of Socit Metallurgique d'Imphy.
The nominal composition of an alloy of this kind is as follows:
Percent C 0.7 Si 0.3 Mn 1.9 Ni 32 Cr 10 W 3.5 Fe Remainder Percent C Minimum Si Minimum Mn Minimum Ni 42 Percent Ti 2.5 A1 1 Fe Remainder Durinval alloys are distinguished from Elinvar alloys in particular by their hardening mechanism. The mechanical characteristics of Elinvar are produced by appropriate heat treatment during which chromium carbides are precipitated, while titanium nickelides and aluminium nickelides are precipitated in the case of Durinval. This essential diiference in the hardening mechanisms of the two types of alloy is, of course, directly connected with differences in composition, which a comparison of the above two analyses will reveal. Quite apart from their higher elastic limit, Durinval alloys, like Elinvar alloys, have, of course, a substantially zero thermoelastic coefficient in the region of ambient temperature.
But they cannot be used to make watch springs whose movement is not mechanical but electrical. For watch springs with electrical movements must be non-magnetic at ambient temperature, whereas Durinval alloys are highly magnetic under these conditions. Their Curie point, i.e. the temperature at which the alloy passes from the ferromagnetic to the paramagnetic state, is about This invention relates to a new group of alloys that have the usual features of conventional Durinval alloys, but are non-magnetic at ambient temperature.
The applicants have found that the Curie point of Durinval alloys can be greatly reduced by appropriate additions of molybdenum, while all the desired features, and in particular a zero thermoelastic coeflicient, are preserved in the resulting material by adjusting the contents of the other elements.
The invention relates to a non-magnetic alloy characterized in that it is composed of the following, by weight: 36.5 to 39.5% of nickel, 1.5 to 4.5% of chromium, 1.5 to 3% of molybdenum, 0.75 to 1.25% of aluminium and 2.3% of titanium, together with very small quantities of carbon, silicon, manganese, sulphur and phosphorus, the remainder being iron.
The invention also relates to watch springs made of this alloy.
The following composition by weight of an alloy according to the invention may be given as an example: carbon 0.005%, silicon 0.34%, manganese 0.16%, nickel 38.4%, chromium 3.37%, molybdenum 2%, titanium 2.46%, aluminium 0.96% and iron 52.29%, the remainder being sulphur and phosphorus. The Curie point of this alloy is below 18 and it is practically non-magnetic at ambient temperature, having a zero thermoelastic coefficient.
The research on which the invention is based has shown that the contents of the constituent elements of the alloy must be adjusted within the following limits to obtain a set of properties similar to those of the alloy mentioned above by way of example:
Percent Nickel 36.5-39.5 Chromium 1.5-4.5 Molybdenum 1.5-3 Aluminium 0.75-1.25 Titanium 2-3 The remainder is iron, carbon, silicon, manganese, sulphur and phosphorus in very small proportions.
To obtain the best results within the composition ranges indicated above, account must be taken of the sometimes contradictory effects on the Curie point of variations in the contents of the various elements. Within the composition range in question, additions of nickel raise the Curie point, while additions of chromium, molybdenum, titanium and aluminium lower it.
Account must also be taken of the efiect on the Curie point of the manner in which the alloy hardens during its treatment. The precipitation of titanium nickelides and aluminium nickelides makes the matrix of the alloy relatively poor in nickel, and is therefore accompanied by a lowering of the Curie point.
The invention is not, of course, limited by the details of the process that have just been described. These may be modified without going beyond the scope of the invention.
I claim 1. Non-magnetic iron-nickel-chromiummolybdenum alloy, characterized in that it is composed, by Weight, of 36.5 to 39.5% of nickel, 1.5 to 4.5% of chromium, 1.5 to 3% of molybdenum, 0.75 to 1.25% of aluminium and 2 to 3% of titanium, the remainder being iron, to gether with very small quantities of carbon, silicon, manganese, sulphur and phosphorus.
2. A non-magnetic alloy as claimed in claim 1, characterized in that it is composed by Weight of 38.4% of nickel, 3.37% of chromium, 2% of molybdenum, 0.96%
of aluminium, 2.46% of titanium, 52.29% of iron, 0.005% of carbon, 0.34% of silicon and 0.16% of manganese, the remainder being sulphur and phosphorus.
3. Watch springs, characterized in that they are made of a non-magnetic iron-nickel-chromii1m-molybdenum alloy, composed, by weight, of 36.5 to 39.5% of nickel, 1.5 to 4.5% of chromium, 1.5 to 3% of molybdenum, 0.75 to 1.25% of aluminium and 2 to 3% of titanium, the remainder being iron, together with very small quantities of carbon, silicon, manganese, sulphur and phosphorus.
References Cited UNITED STATES PATENTS 3,065,068 11/1962 Dyrkacz 75l28.8 3,243,287 3/1966 Lillys 75--128.8 3,300,347 1/1967 Kasza 75-124 HYLAND BIZOT, Primary Examiner US. Cl. X.-R. 75128
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR69163A FR1493033A (en) | 1966-07-12 | 1966-07-12 | Non-magnetic iron-nickel-chromium-molybdenum alloys and watch springs obtained with these alloys |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3464815A true US3464815A (en) | 1969-09-02 |
Family
ID=8613095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US647956A Expired - Lifetime US3464815A (en) | 1966-07-12 | 1967-06-22 | Non-magnetic iron-nickel-chromium-molybdenum alloy,and watch springs obtained with this alloy |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3464815A (en) |
| CH (2) | CH501954A (en) |
| DE (1) | DE1558642B2 (en) |
| FR (1) | FR1493033A (en) |
| GB (1) | GB1156574A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4911884A (en) * | 1989-01-30 | 1990-03-27 | General Electric Company | High strength non-magnetic alloy |
| US20070001139A1 (en) * | 2005-06-30 | 2007-01-04 | Walter Fleischer | Electrically actuatable valve |
| US20140003203A1 (en) * | 2012-06-28 | 2014-01-02 | Nivarox-Far S.A. | Mainspring for a timepiece |
| JP2017102110A (en) * | 2015-12-02 | 2017-06-08 | ニヴァロックス−ファー ソシエテ アノニム | Method for manufacturing balance spring for timepiece |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3065068A (en) * | 1962-03-01 | 1962-11-20 | Allegheny Ludlum Steel | Austenitic alloy |
| US3243287A (en) * | 1962-09-14 | 1966-03-29 | Crucible Steel Co America | Hot strength iron base alloys |
| US3300347A (en) * | 1964-05-07 | 1967-01-24 | Huck Mfg Co | Fastening device and method of making same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH217814A (en) * | 1937-06-02 | 1941-11-15 | Soc D Fabriques De Spiraux Reu | Process for the manufacture of balance springs for watches, chronometers, etc. |
-
1966
- 1966-07-12 FR FR69163A patent/FR1493033A/en not_active Expired
-
1967
- 1967-06-05 DE DE19671558642 patent/DE1558642B2/en not_active Withdrawn
- 1967-06-12 GB GB27004/67A patent/GB1156574A/en not_active Expired
- 1967-06-19 CH CH865767A patent/CH501954A/en not_active IP Right Cessation
- 1967-06-19 CH CH865767D patent/CH865767A4/xx unknown
- 1967-06-22 US US647956A patent/US3464815A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3065068A (en) * | 1962-03-01 | 1962-11-20 | Allegheny Ludlum Steel | Austenitic alloy |
| US3243287A (en) * | 1962-09-14 | 1966-03-29 | Crucible Steel Co America | Hot strength iron base alloys |
| US3300347A (en) * | 1964-05-07 | 1967-01-24 | Huck Mfg Co | Fastening device and method of making same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4911884A (en) * | 1989-01-30 | 1990-03-27 | General Electric Company | High strength non-magnetic alloy |
| US20070001139A1 (en) * | 2005-06-30 | 2007-01-04 | Walter Fleischer | Electrically actuatable valve |
| US20140003203A1 (en) * | 2012-06-28 | 2014-01-02 | Nivarox-Far S.A. | Mainspring for a timepiece |
| JP2017102110A (en) * | 2015-12-02 | 2017-06-08 | ニヴァロックス−ファー ソシエテ アノニム | Method for manufacturing balance spring for timepiece |
Also Published As
| Publication number | Publication date |
|---|---|
| FR1493033A (en) | 1967-08-25 |
| GB1156574A (en) | 1969-07-02 |
| CH865767A4 (en) | 1970-09-30 |
| DE1558642A1 (en) | 1971-05-06 |
| CH501954A (en) | 1970-09-30 |
| DE1558642B2 (en) | 1971-05-06 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: IMPHY S.A., 8, RUE DE LA ROCHEFOUCAULD, 75009 , FR Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CREUSOT-LOIRE;REEL/FRAME:003961/0485 Effective date: 19820318 |