CN1325687C - Ferritic steel alloy - Google Patents
Ferritic steel alloy Download PDFInfo
- Publication number
- CN1325687C CN1325687C CNB038236788A CN03823678A CN1325687C CN 1325687 C CN1325687 C CN 1325687C CN B038236788 A CNB038236788 A CN B038236788A CN 03823678 A CN03823678 A CN 03823678A CN 1325687 C CN1325687 C CN 1325687C
- Authority
- CN
- China
- Prior art keywords
- weight percent
- alloy
- steel
- steel alloy
- weight
- 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 - Fee Related
Links
Images
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
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
-
- 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
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- 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
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- 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
- C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
-
- 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
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
Abstract
Disclosed are steel alloys comprising no more than 1.00 percent by weight of silicon, 18.0 to 22.0 percent by weight of chromium, 1.80 to 2.50 percent by weight of molybdenum, 0.01 to 0.10 percent by weight of nitrogen, no more than 0.01 percent by weight of titanium, no more than 0.01 percent by weight of niobium, no more than 0.01 percent by weight of aluminum, the remainder being essentially iron. Said alloys are ferritic but polishable and have mechanical properties that nearly match those of the standard steel alloy no. 1.4521. The inventive steel alloys are processed into watch parts such as housing bottoms, housing shells, and faces, among others, such that watch housings can be produced, which also magnetically shield the clockwork.
Description
The field of the high-alloy stainless steel that the present invention relates in horological industry, use.
The wrist-watch great majority of now being worn are made by gold, stainless steel and titanium.Table starts from nineteen twenty-five with the exploitation of steel, and this moment, the Firth Vickers Special Steels Ltd. of Britain company was appointed as " DDQ " introducing market with the CrNi steel.Almost simultaneously, Krupp company has developed steel V2A, and still, because steel No.1.4301, this brings into use in the table industry is after 50 years.So,,, replaced steel " DDQ " by the austenitic stainless steel No.1.4435 that is Standard Steel now because the Swiss watch industry need improve erosion resistance in later 1980s.
Watchcase typically uses die-cut technology by the preparation of metal sheet and sheet material.In order to reach the final form that their need, according to the kind of watchcase, they must to a certain degree carry out the intensive cold extrusion, and according to the thickness of watchcase, carry out process annealing.For the situation (profiles) by cold rolling preparation watchband also is like this.The cold hardening behavior is very important to cold formation of lots.Generally speaking, the steel of this distortion of optimum is under the low yield strength value, and minimum cooling makes oneself sclerosis, improves the distortion grade simultaneously.In the as-annealed condition between block shaping period, the behavior of ferritic stainless steel alloy is similar to non-steel alloy.
In order to protect the influence that the parts of the clock mechanism of magnetic influence sensitivity is not subjected to high-intensity magnetic field, in titanium that some table producers mention in the above or the 1.4435 type Stainless Steel Watch Cases in conjunction with soft iron box (itself does not have magnetic shield performance this material).This soft iron box has the effect of diamagnetic protector, and it can not allow magnetic field penetration enter in the table.Therefore, in fact, can not be subjected to arrive by the protection table up to the magnetic field of 80000A/m; But must carry out suitable effort,, be attached to then in the actual watchcase, so the total thickness of wrist-watch greatly be improved because this soft iron box must be finished separately.
For the table steel, also need for example to be used for the polishability of the steel of watchcase, promptly it is to the suitability of preparation high gloss glazed surface.The austenitic stainless steel No.1.4435 that uses in the table industry can only satisfy this demand on limited degree at present.Ferritic stainless steel for example steel No.1.4521 can not the picture austenitic steel that works the polishing: almost exclusively stablize ferritic steel with titanium or Nb, separate out to prevent the Cr-carbide on grain boundary.But, so the titanium carbide of high rigidity or niobium carbide separate out, and destroyed the polishability of ferritic steel.By mechanical polishing, there is not to remove carbide particle that the size separate out is 5-10 μ m and as the outstanding outside of so-called pit, better glazed surface.So-called polishing vestige produces, that is, the precipitate of polishing thickener in the polishing shade of carbide particle, this is to disturb very much naked eyes.For the ferritic chromium steel that can polish,, be unpractical by adding Ti or Nb stabilized steel microtexture owing to negative influence to polishability.But, stablize microtexture without Ti or Nb, because velocity of diffusion, to such an extent as to the carbide of chromium separates out that to carry out so soon also be that inevitably the velocity of diffusion of the carbide of chromium is higher than about 2 orders of magnitude of velocity of diffusion of ferritic steel by short annealing from the solution annealing temperature on grain boundary.Chromium carbide forms hard inclusion in addition, and it damages the polishability of steel again.
The polishability of steel greatly is subjected to the influence of grain size.The polishing of macroparticle steel produces the effect that is known as orange peel, and this is unacceptable to glazed surface.Reason for this reason is in the performance difference of unordered particle (crystal) in different directions.If the grain size of measuring according to ASTM E 112 be lower than numerical value 4 (〉=80pm), human eye is the point-like particle by the plane of crystal of removing in various degree in polishing process as can be seen, it shows the outward appearance of orange peel.
In the technical specifications of table steel, another requirement is a good processing properties.According to the kind of watchcase, in the preparation process of watchcase, must have the operation of cold-forming on a large scale of process annealing step.In addition, boring and grinding are for example used in the preparation of watchband, also need alloy favorable mechanical processibility.
Good anti-corrosion in saline media, is another major requirement of table steel particularly.Direct and the skin contact of wrist-watch, and because soaking of perspire has special corrosion risk.The purity of steel has considerable influence to erosion resistance.Weakness on the coarse and linear nonmetal inclusion presentation surface of separating out, iron mold can produce at this, continues in the clear then.For this reason, in the art, steel comes remelting by esr (Electro-Slag-Remelting) method (ESR method) usually, according to DIN 65602, causes nonmetallic, corrosion to cultivate crystal grain (corrosion fostering particle) size and descend about about 2 units.
The chemistry and the mechanical property that are known that Steel Alloy can be controlled by adding metal and non-metallic element in alloy.
Every kind of independent alloying element and trace elements itself to the influence of machinery, chemistry and the magnetic property of steel and microtexture be known (relatively, for example at " Nichtrostende St hle-Eigenschaften; Verarbeitung; Anwendung; Normen " [Stainless Steels-Properties, Processing, Use, Standards] the 2.2nd chapter in the second edition, editor " Edelstahl-Vereinigung e.V. " Verlag Stahl-Eisen; And C.W.Wegst, VerlagStahlschl ü ssel, " the Stahlschl ü ssel " of Wegst GmbH the 18th edition, 1998, the 1 chapters).
If known alloying element and respectively they being joined in the alloy, they are briefly described below the influence of steel.
At first, chromium has passivation to steel, and therefore expression is used for all stainless main alloy element.
Molybdenum has improved erosion resistance and in the presence of halide-ions, to the stability of tubercular corrosion.
A lot of people think, but in polished steel, silicon is unwanted impurity, because it forms hard oxide compound inclusion.On the other hand, if alloy should be a soft magnetism, silicon is the alloying element that needs.
Nitrogen improves erosion resistance.Because the trend of yield strength and work hardening improves by adding N, the common strictness of the content of N is restricted to 0.2%.Think that adding N in the austenitic steel has greatly postponed M
23C
6The beginning of separating out (P.R.Levy, P.R., van Bennekom, A., Corrosion 51,911-921 (1995)).On the other hand, if desired be alloy with soft magnetic performance, the existence of nitrogen be problematic (referring to, " Ullmann ' s Encyclopaedia of Industrial Chemistry " the 5th edition for example, Volume A16, the 26th page, left hurdle, second section).
Manganese is austenite former.Therefore in ferritic steel, its existence is very unwanted.
The sulphur of trace is favourable to the machinability of steel, and they may be to the particular table parts, and for example the preparation of watchband is important.But a large amount of it has adverse influence for steel corrosion-resistant.
Though the adding of carbon has improved the hardness of steel,, on the other hand, it is very strong austenite former, and it has reduced machinability and polishability by separate out chromium carbide on grain boundary.Alloy has soft magnetic performance if desired, the existence of carbon be equally very debatable (referring to, " Ullmann ' s Encyclopedia of Industrial Chemistry " the 5th edition for example, Volume A16, the 26th page, left hurdle, second section).
For the soft magnetic performance of Steel Alloy, nickel needs as important alloying element (typically, 30 to 80 weight percents), still, on the other hand, because its performance as austenite former is very unwanted to ferritic steel.In addition, the anaphylaxis that contains the Ni alloy has been become serious medical care problem in industrial country.For example, in Europe, surpass 20% young women and surpass 6% young man and suffer damage because of the nickel allergy.This watchcase at wrist-watch is important, because these are placed directly on the skin.
Pure, non-alloy iron (soft iron) is favourable as soft magnetic material equally, still, known it does not have erosion resistance.
The bidimensional microtexture phasor of chromium nickel steel allows microtexture (austenite, δ-ferrite, martensite or its mixture) is roughly assessed, and will form the function of Cr content (being plotted among the figure on the x axle) and Ni content (being plotted among the figure on the y axle).By considering above element, can also enlarge this microtexture phasor; But only summary is considered other element, and estimates to form other nickel or chromium equivalent.With this form, be known that Schaeffler-figure.(A.L.Schaeffler：M.S.Thesis，Univ.of Wisconsin，June 1944；A.L.Schaeffler，The Welding Joumal 26/10，601-620(1947)；A.L.Schaeffler，Metal Progress vol.56 s.680A，B(1949))。Because the factor by the experience decision (compares, Briggs, J.Z., Parker, D., ClimaxMolybdenum Company, the the 6th to 7 page (1965)), carry out the amount of other element is converted into the amount of normal chromium and nickel by calculating, as the numerical value that obtains from experiment, so be impossible for the accurately predicting of the microtexture of concrete alloy.Particularly, from Schaeffler figure, can not reach a conclusion for a kind of erosion resistance of alloy or machinery and magnetic behavior.
To can also from graphics (Gr fen, H., Chem.Ing.Techn.54,108-119 page or leaf (1982)), obtaining according to a preliminary estimate of the pitting resistance of Cr/Mo steel.In the figure, as by the decision of current density/potential curve, will draw for the relative Cr content of sticking potential (X-axis) of the dependency of tubercular corrosion (Y-axis) beginning.Also molybdenum content is considered (the same, and Lorenz, K., Medawar, G., Thyssen-Forschung 1, the 97 to 108 pages (1969)) with the form of chromium equivalent.It is relevant to observe between sticking potential and Cr (Mo) content substantial linear.But this figure do not consider any other alloying element and fails whether it relates to Alfer with regard to it, or obtains conclusion with regard to their machinability, polishability and magnetic behavior.
Ding Yi effective total WS in the following manner:
WS＝％wt Cr+3.3×wt％Mo+16×wt％N，
It is an observed value that is used for roughly estimating the erosion resistance of steel.Because the perspire on the skin has more corrodibility than the blood of 0.9% salts contg, effective sum of the injection steel (implant steel) of table steel should be at least 26.
Provide the overview of the weight percent of 8 kinds of steel concrete, prior art (material number by them is specified) and their important alloying elements in the table 1.According to the applicant's knowledge, the steel No.1.4521 that mentions here is not the table steel.
Table 1
| 1.4521 DIN 10088 | 1.4523 steel-iron-L. | Sandvik (Richt) 1802 | Aichi (IST) YUS 190 | Aichi (IST) SUS 444 | NAR 445 | NARFC3 | NTK U-22 | |
| C | ≤0.025 | ≤0.030 | ≤0.03(C+N) | 0.004 | 0.025 | ≤0.020 | ≤0.025 | ≤0.025 |
| Si | ≤1.00 | ≤1.00 | 0.5 | 0.06 | 0.87 | ≤0.60 | ≤1.00 | ≤1.00 |
| Mn | ≤1.00 | ≤0.50 | 0.3 | 0.06 | 0.21 | ≤0.60 | ≤1.00 | ≤1.00 |
| P | ≤0.040 | ≤0.040 | -- | 0.025 | 0.032 | ≤0.040 | ≤0.040 | ≤0.040 |
| S | ≤0.015 | 0.15-0.35 | 0.3 | 0.008 | ≤0.002 | ≤0.010 | ≤0.005 | ≤0.030 |
| Cr | 17.0-20.0 | 17.5-19.0 | 18 | 18.8 | 17.8 | 19.0-21.0 | 19.0-22.0 | 21.0-23.0 |
| Mo | 1.80-2.50 | 2.00-2.50 | 2.3 | 1.86 | 2.07 | 1.70-2.30 | 0.75-1.25 | 1.75-2.50 |
| Ni | -- | -- | ≤0.20 | -- | 0.17 | -- | -- | -- |
| N | ≤0.03 | -- | -- | 0.009 3) | 0.025 3) | -- | -- | ≤0.025 |
| Al | -- | -- | -- | -- | 0.006 | -- | -- | -- |
| Ti | ≤0.08 1) | 0.30-0.80 2) | 0.6 | -- | 0.005 | -- | -- | -- |
| Nb | -- | -- | -- | 0.15 | 0.57 | -- | 0.15 | Ca.0.80 |
| Cu | -- | -- | -- | -- | 0.04 | -- | 0.08-0.30 | -- |
| Fe | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus | Surplus |
1)Ti=4 * (C+N)+0.15 to 0.80
2)Ti=0.30 to 0.80, wherein (C+N)≤0.40
3)N adds clearly, just impurity
The purpose of this invention is to provide a kind of ferritic steel that polishes, it has soft magnetic performance, wherein the risk with polishing defect is reduced to minimum, it has the mechanical property that can compare with steel No.1.4521, and, compare with steel No.1.4435 and to have erosion resistance identical or that improve for pitting corrosion resistance and anti-crack property.
This purpose is accomplished by a kind of like this Steel Alloy, described steel alloy comprise based on alloy at the most molybdenum, 0.01 to 0.10 weight percent of chromium, 1.80 to 2.50 weight percents of silicon, 18.0 to 22.0 weight percents of 1.00 weight percents nitrogen, at the most 0.01 weight percent titanium, at the most 0.01 weight percent niobium, the aluminium and the surplus of 0.01 weight percent are iron basically at the most.Preferred variable provides in the dependent claims.
Steel Alloy according to the present invention is a soft magnetism CrMoN-Steel Alloy.
Description of drawings
Fig. 1 represents a) according to Steel Alloy of the present invention and b) current density/potential curve figure of known Steel Alloy No.1.4435.4.0,40 ℃ of measuring condition: 3.2%NaCl, pH.The x axle: with respect to saturated calomel electrode (SCE) as reference electrode, the electromotive force of representing with mV; Y-axis: the logarithm of the current density of measurement.The potential values that show at two figure are the sticking potentials when tubercular corrosion (the strong growth of anodic current) begins.
In the application's scope, term " high alloy " has the implication of this area routine, and namely it indicates wherein that the amount sum of alloying element is 5 percentage by weights or above steel.
In the application's scope, term " ferrite " refers at least 98 volume % that exist in the alloy of the present invention preferably be at least 99.5 volume %, and particularly preferably 100 volume % iron exist with ferrite, wherein determine by carrying out with the metallography method.
In the application's scope, term " soft magnetism " is used for according to steel alloy of the present invention, and it produces the same with soft iron at least powerful magnetic screening action.
By in the pig iron or crude steel, adding the pure element of sufficient quantity, can in alloy of the present invention, add metal alloy elemental chromium and molybdenum according to traditional method.
According to the present invention, based on the alloy finished product, 18.0 to 22.0 weight percents are arranged, preferred 19.5 to 20.5 weight percents are preferably the chromium of about 20 weight percents especially.
According to the present invention, based on the alloy finished product, have an appointment 1.80 to about 2.50 weight percents, preferred about 1.90 to 2.10 weight percents are preferably the molybdenum of about 2 weight percents especially.
By molten steel alloy under nitrogen atmosphere, by nitrogen being blown in the melt or, can supplying with nitrogen by adding quantitative prealloy with high nitrogen-containing.According to the present invention, based on alloy, the content of nitrogen is about 0.01 to 0.10 weight percent based on alloy, and more preferably about 0.05 to about 0.10 weight percent, and is preferably about 0.05 weight percent especially.
Silicon can be used as SiO in alloy
2There is (for example, coming from top deoxidation).Move or the stirring steel melt by machinery in shielding gas, can reduce its content.So, since low density, SiO
2Assemble and rise to the slag surface.According to the present invention, the content of silicon is about 1 weight percent at the most based on alloy, is preferably about 0.7 to 0.9 weight percent, more preferably about 0.8 weight percent.
Result as fusion process, the carbon of significant quantity (4 to 4.5%) exists as the mixture in the pig iron, then, as being conventional in this area, by in steel melt, adding the ferriferous oxide (carbon is converted into carbon monoxide) of oxygen or sufficient quantity, this carbon content can be reduced to the level of substantial any needs.Preferably, according to the present invention, carbon back is at most 0.025 weight percent in alloy, especially preferably is at most 0.01 weight percent.
Sulphur is derived from fusion process (iron sulfide is contained in the iron ore), and mainly is that form with manganese sulfide exists in the pig iron.In alloy according to the present invention, the preferred amount that exists is at most 0.03 weight percent, more preferably is at most 0.002 weight percent.The mixture of CaO and MAGNESIUM METAL carries out desulfurization to melt by for example using, and can reach so low sulphur content.In another specific embodiments according to Steel Alloy of the present invention, described Steel Alloy has better machinability, and has an acceptable polishability, the upper limit of sulphur content can be 0.03 weight percent based on alloy (so-called IMA quality), be preferably about 0.015 to 0.03 weight percent, therefore can carry out the control that sulphur is added.The production of specific embodiment hereto, can utilize the adding of Ca-Si powder to melt metallurgy, the manganese sulfide that it is converted into hard aluminum oxide inclusion the mixed oxide compound of soft relatively CaSiAl type and forms fine dispersion, by it, the smear metal that forms during processing is broken, and has therefore prolonged the work-ing life of instrument.In check sulphur adds the erosion resistance that only slightly reduces this embodiment of Steel Alloy according to the present invention.
According to the present invention, based on the alloy finished product, about at the most 0.01 weight percent is arranged, the niobium of preferred about at the most 0.005 weight percent.Utilize suitable borings (avoiding containing the steel of niobium) by the present invention between melting period at Steel Alloy, can reach this amount.
According to the present invention,, preferably have about at the most 1.00 weight percents, more preferably the manganese of about at the most 0.40 weight percent based on the alloy finished product.
The phosphatic rock that exists in the comfortable at first iron ore of phosphorus or other phosphatic mineral.Between smelting period, phosphoric acid salt can be reduced to iron phosphide (mainly is Fe
2P) and can close and be present in the pig iron or the steel subsequently.According to the present invention, the preferred low phosphorus content of 0.04 weight percent and preferred 0.02 weight percent at the most can reduce during alloy preparation according to the present invention at the most, as in this area routine, for example by adding CaO between melting period, so that phosphorus ore containing is separated from slag at ore.
According to the present invention, the aluminium content of about at the most 0.01 weight percent and preferred about at the most 0.005 weight percent can reach, and precondition is that the deoxidation that needs in melting process is used not using aluminium under the condition of silicon or with AOD or VOD method and carried out (referring to following).
Based on the alloy finished product, preferably be at most 0.10 weight percent, more preferably be at most the nickel of 0.05 weight percent.
As conventional in this area,, preferably remove unnecessary carbon, silicon and phosphorus simultaneously by adding gaseous oxygen (being converted into oxide compound) and adding the CaO refining.Carry out refining by the mode of VOD (decarburization of vacuum oxygen (VacuumOxygen Decarburization)) or AOD (argon oxygen decarburization (Argon OxygenDecarburization)) (unnecessary oxygen is removed by the degassing in a vacuum or by with argon it being produced by boasting) then, can remove unnecessary oxygen with usual way.
(avoid containing the Ti smear metal by the control smear metal, as the known Ti steel No.1.4571 that contains of European scope) use, can be set to about at the most 0.01 weight percent by titanium content according to the present invention, be preferably about at the most 0.005 weight percent, be preferably about at the most 0.002 weight percent especially.As further step, avoid Ti impurity in the refractory lining nexine of the converter that can between melting period, use.
Scope in the application, term " being the surplus of iron basically " should refer to the residuals weight per-cent according to any one described alloy of claim 1 to 7, the weight percent that is surplus is not elementary composition by mentioned title in the corresponding claim, (typically reach at least 90 weight percents of surplus but almost exclusively be derived from iron, be preferably at least 95 weight percents, be preferably at least 99 weight percents or above degree especially).
The outer amount of element of deironing in the surplus that should select like this is so that Steel Alloy finished product according to the present invention is a ferrite.Be provided as initial basis by the Schaeffler figure that begins to mention,, calculate other element by Briggs and Parker by means of the equivalent of nickel and chromium to this.Under independent situation, according to the measuring method that begins to mention, checking by experiment, whether genuine yes or no is according to ferrite of the present invention can to determine the alloy that obtains.
Can prepare alloy of the present invention by standard method.By way of example, with reference to " Ullmann ' s Encyklop die der Technischen Chemie[Ullmann ' s Encyclopediaof Technical Chemistry] " the 4th edition, chapter 2 in " steel " part among the Verlag Chemie and the document of wherein mentioning.
In steel production process according to the present invention, preferably use AOD and VOD method to carry out refining operation in succession; Therefore the VOD refining can also be used for nitriding simultaneously.
For high quality steel, the ununiformity in microtexture causes the point of individual configurations composition to gather.This can cause microtexture form in and physical and mechanical property in undesirable variation.Therefore, preferably according to the present invention in the production process of Steel Alloy, as conventional in this area, the formation of the ununiformity of gathering and following for fear of the point of individual configurations composition, in forging the process of making,, more preferably from about anneal under 850 ℃ the temperature at about 800 to 900 ℃.For this reason, recommend the what is called " all thermal treatment " of hot rolling making sheet base or the warm up time before the prolongation hot rolling system.
At 750 to 850 ℃, annealing is about 0.5 to 2 hour under preferred about 800 ℃ temperature, water cooling then after forging or cold formation for alloy preferably according to the present invention.So, since diffusion process, balance (equilibriate) in the matrix of chromium concn in the zone of chromium nitride particle fine dispersion, that separate out.But, can suppress separating out of chromium nitride greatly by the optimization of nitrogen content.
According to Steel Alloy of the present invention can therefore the polishing of reproducibility ground be acceptable as the raw material that uses in the table industry by the ordinary method in the table industry.Under annealing temperature, there is the nitrogen that in alloy, adds with up to 0.1% quantity, it is preferred at Steel Alloy of the present invention, and perhaps dissolving is perhaps with the form of trickle chromium nitride of separating out, typically size is about 1 μ m, but therefore can not have a negative impact to polishability.
In the Steel Alloy of the present invention, particularly claim 3 to 7 those typically have following machinability (metal sheet, thickness are 6mm, hot rolling system, 800 ℃ of following annealing 30 minutes, at quenching-in water).
Yield strength R
P0.2420MPa
Tensile strength R
m603MPa
Elongation at break A
028%
Hardness HB 30 188
Therefore, can be comparable to the quality of Standard Steel No.1.4521 according to alloy of the present invention.
According to the present invention, replace niobium or titanium by in alloy, adding nitrogen, but eliminated the big relatively niobium carbide of destruction polishability or separating out of titanium carbide.In addition, suppressed separating out of the chromium carbide on the grain boundary.This takes place by separating out dynamic (dynamical) change, has produced separating out of the chromium nitride that replaces chromium carbide, and this is actively preferred.The solubleness of nitrogen surpasses under the situation of restriction in Steel Alloy, and diameter is about the chromium nitride particles of 1 μ m and littler very fine dispersion separates out, but since their fineness do not have a negative impact to polishing characteristic.
Since the titanium and the aluminium of low levels, thereby the content of relevant oxide compound is low in the alloy of the present invention, and the content of oxide compound can pass through test method M (ball oxide compound, DIN 50602) definition.By almost completely non-existent titanium and niobium, corresponding carbide does not almost completely have yet.On the other hand, add simultaneously with the outer residue alloying element of dechromisation by coordinating nitrogen, though the content of nitrogen (austenite former) has improved, the carbide that does not occur chromium is basically separated out, and alloy of the present invention remains ferrite.Therefore, the nonmetal oxide inclusion of Steel Alloy of the present invention or the purity level of carbide inclusion are adjusted to high level like this together, so that no longer need to melt again according to the ESU method that begins to mention; But, if desired, can melt again with Steel Alloy of the present invention.
On the meaning of the definition that begins to mention, Steel Alloy of the present invention is a soft magnetism.
Surpass their effective total amounts as beginning to define according to the preferred Steel Alloy of claim 3 to 7 of the present invention, the minimum value of the injection steel that needs in medical skill is 26.
Because good polishability and soft magnetic performance in the alloy of the present invention, these can be used for the magnetic shielding case member in the table industry preparation for example is used for wrist-watch or other clock and watch, and the magnetic shielding of wherein showing mechanism is important.According in the Steel Alloy of the present invention, particularly claim 7 those, can also be applicable to that preparation connects the parts that watchband is used.
Term " case member " comprises the shell of the general parts, particularly wrist-watch that use in the watchcase preparation in the application's scope, therefore for example at the bottom of the shell and housing.But term " case member " also comprises the surface in the application's scope.Term " case member " comprises the parts that appear in the telogenesis product, with and any blank and work in-process thereof, it is by further processing, optional use other materials or is further processed by the work in-process that alloy of the present invention and other materials are made, to prepare final parts.
Magnetic shielding watchcase of the present invention can by at the bottom of the shell, housing and surface composition, all according to Steel Alloy preparation of the present invention.Therefore, be used as material that parts use and diamagnetic shielding case simultaneously according to Steel Alloy of the present invention.Therefore, can cancel and remove the complicated other soft iron cover of preparation, its common enclosure the inside and its thickness that will cause showing that must be provided in the non magnetic CrNi steel increases.
Steel variant 1.4521 according to the present invention is suitable for using the powder metallurgy processing of MIM (metal jet casting (Metal Injection Moulding)) method unusually, particularly because can supply with the nitrogen content that the present invention needs during the pressing process (sintering) in nitrogen atmosphere no problemly.In hypergene product field, the MIM method itself is known.In order to prepare according to table parts of the present invention, will contain final quantity need element (these will be specified in claim 1 to 7 any one) but the Steel Alloy that do not contain enough nitrogen grinds, form powder and use liquid adhesive to suspend.This suspension is forced to for example put into mould by forcing machine, and the die cavity of mould has the shape with the case member of preparation.Then, evaporation tackiness agent, the powder residuum that preferably evaporation in a vacuum, and sintering keeps in mould.If the content of nitrogen begins inadequately in the powdered alloy, in sintering step, supply with to be fit to the nitrogen atmosphere of pressure so that during sintering alloy absorbed nitrogen also.By a series of tests, can determine the selection of the nitrogen of suitable pressure, to reach in the case member finished product according to nitrogen concentration of the present invention.
The preparation example
Provide an example that is used to prepare according to Steel Alloy of the present invention below:
A) the approximately fusing of 5t in the induction furnace
B) secondary metallurgy in the VOD converter
C) with slab form 1250 * 250 * 1270mm, continuous casting
D) chemical analysis
E) in box-type furnace, be preheated to about 1080 ℃ rolling temperature
F) begin to be rolling to the thickness of 120mm
G) grind on each face to slab
H) preheating in 1080 ℃ continuous furnace
I) roll the thickness of the ultimate demand that is rolling to 3-12mm on the platform at four-roller type
J) 750-850 ℃ of annealing down
K) at quenching-in water
1) de-scaling
M) test mechanical performance R
P0.2, R
m, A, Z
N) metallographic of grain size is measured
O) purity level determines
P) but the test polishability
Q) aligning
R) be cut into final size
S) emit
Claims (19)
1. high alloy Alfer, its comprise based on described alloy at the most molybdenum, 0.01 to 0.10 weight percent of chromium, 1.80 to 2.50 weight percents of silicon, 18.0 to 22.0 weight percents of 1.00 weight percents nitrogen, at the most 0.01 weight percent titanium, at the most 0.01 weight percent niobium, the aluminium and the surplus of 0.01 weight percent are iron basically at the most.
2. Steel Alloy according to claim 1, it comprises based on described alloy titanium, aluminium, niobium, manganese, the phosphorus and the carbon of 0.025 weight percent at the most of 0.04 weight percent at the most of 1.00 weight percents at the most of 0.005 weight percent at the most of 0.005 weight percent at the most of 0.005 weight percent at the most.
3. Steel Alloy according to claim 1 and 2, it comprises based on the molybdenum of the chromium of described alloy 19.5 to 20.5 weight percents, 1.90 to 2.10 weight percents and the nitrogen of 0.05 to 0.10 weight percent.
4. Steel Alloy according to claim 1 and 2, it comprises based on the nitrogen of the molybdenum of the chromium of the silicon of about 0.8 weight percent of described alloy, about 20 weight percents, about 2 weight percents, about 0.05 weight percent and the titanium of 0.002 weight percent at the most.
5. according to the described Steel Alloy of claim 3, it comprises based on the nitrogen of the molybdenum of the chromium of the silicon of about 0.8 weight percent of described alloy, about 20 weight percents, about 2 weight percents, about 0.05 weight percent and the titanium of 0.002 weight percent at the most.
6. Steel Alloy according to claim 1 and 2, it comprises based on the described alloy nickel of 0.10 weight percent at the most.
7. Steel Alloy according to claim 3, it comprises based on the described alloy nickel of 0.10 weight percent at the most.
8. Steel Alloy according to claim 4, it comprises based on the described alloy nickel of 0.10 weight percent at the most.
9. Steel Alloy according to claim 1 and 2, it comprises based on the described alloy sulphur of 0.03 weight percent at the most.
10. Steel Alloy according to claim 3, it comprises based on the described alloy sulphur of 0.03 weight percent at the most.
11. Steel Alloy according to claim 4, it comprises based on the described alloy sulphur of 0.03 weight percent at the most.
12. Steel Alloy according to claim 6, it comprises based on the described alloy sulphur of 0.03 weight percent at the most.
13. Steel Alloy according to claim 9, it comprises the sulphur based on described alloy 0.015 to 0.03 weight percent.
14. by the Housing for a meter parts of forming according to any one described Steel Alloy of claim 1 to 13.
15. according to the case member of claim 14, its form is at the bottom of the shell or the form of housing.
16. by the surface of forming according to any one described Steel Alloy of claim 1 to 13.
17. by the connection watchband parts of forming according to any one described Steel Alloy of claim 1 to 13.
18. according to the application of any one described Steel Alloy of claim 1 to 13 in the magnetic shielding of table.
19. the preparation method of Housing for a meter parts, it is characterized in that, suspend according to the Steel Alloy of any one powder type of claim 1 to 7 with liquid adhesive, and described Steel Alloy can be chosen wantonly and comprises low-level nitrogen, in suspension introducing and the corresponding mould of case member, the evaporation tackiness agent, and in mould the sintered powder residuum; Precondition is if the alloy of powder type comprises low-level nitrogen, then carries out sintering in nitrogen containing atmosphere.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH16592002 | 2002-10-04 | ||
| CH1659/02 | 2002-10-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1688734A CN1688734A (en) | 2005-10-26 |
| CN1325687C true CN1325687C (en) | 2007-07-11 |
Family
ID=32046629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038236788A Expired - Fee Related CN1325687C (en) | 2002-10-04 | 2003-09-30 | Ferritic steel alloy |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US20060130938A1 (en) |
| EP (1) | EP1546427B1 (en) |
| JP (1) | JP2006501368A (en) |
| CN (1) | CN1325687C (en) |
| AT (1) | ATE360103T1 (en) |
| AU (1) | AU2003264228A1 (en) |
| DE (1) | DE50307092D1 (en) |
| WO (1) | WO2004031430A1 (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007248397A (en) * | 2006-03-17 | 2007-09-27 | Seiko Epson Corp | Decoration and timepiece |
| JP5212602B2 (en) * | 2007-09-14 | 2013-06-19 | セイコーエプソン株式会社 | Device and housing material manufacturing method |
| EP2813906A1 (en) * | 2013-06-12 | 2014-12-17 | Nivarox-FAR S.A. | Part for clockwork |
| US10063074B2 (en) | 2016-04-01 | 2018-08-28 | Hewlett-Packard Development Company, L.P. | Electronic wearable device electrode pad with collection well |
| JP7413685B2 (en) | 2019-09-05 | 2024-01-16 | セイコーエプソン株式会社 | Metal materials, watch parts and watches |
| JP7404721B2 (en) | 2019-09-05 | 2023-12-26 | セイコーエプソン株式会社 | Metal materials, watch parts and watches |
| JP7272233B2 (en) | 2019-10-30 | 2023-05-12 | セイコーエプソン株式会社 | Watch parts and watches |
| JP7294074B2 (en) | 2019-11-11 | 2023-06-20 | セイコーエプソン株式会社 | Austenitized ferritic stainless steels, parts for watches and clocks |
| JP2021096076A (en) * | 2019-12-13 | 2021-06-24 | セイコーエプソン株式会社 | Watch exterior part, watch, and manufacturing method of watch exterior part |
| JP2021096079A (en) | 2019-12-13 | 2021-06-24 | セイコーエプソン株式会社 | Housing and apparatus |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11323502A (en) * | 1998-05-12 | 1999-11-26 | Sumitomo Metal Ind Ltd | Ferritic stainless steel excellent in workability and toughness and slab thereof |
| CN1241221A (en) * | 1997-08-05 | 2000-01-12 | 川崎制铁株式会社 | Ferritic stainless steel plate of high deep drawability and ridging resistance and method of mfg. same |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2848323A (en) * | 1955-02-28 | 1958-08-19 | Birmingham Small Arms Co Ltd | Ferritic steel for high temperature use |
| GB1359629A (en) * | 1971-10-26 | 1974-07-10 | Deutsche Edelstahlwerke Gmbh | Corrosion-resistant ferritic chrome steel |
| US3953201A (en) * | 1974-03-07 | 1976-04-27 | Allegheny Ludlum Industries, Inc. | Ferritic stainless steel |
| US4340424A (en) * | 1974-04-23 | 1982-07-20 | Daido Tokushuko Kabushiki Kaisha | Ferritic stainless steel having excellent machinability and local corrosion resistance |
| JPS5188413A (en) * | 1975-02-01 | 1976-08-03 | Kotaishokuseifueraitosutenresuko | |
| EP0379061B1 (en) * | 1989-01-18 | 1992-12-23 | Eta SA Fabriques d'Ebauches | Exterior cover part for a watch, and method for manufacturing the same |
| FR2705596B1 (en) * | 1993-05-24 | 1995-07-13 | Impac Technologies | Method of injection molding of slips and device for its implementation. |
| KR0169172B1 (en) * | 1994-02-15 | 1999-01-15 | 아키모토 유우미 | Fe-cr alloy |
| JPH07244172A (en) * | 1994-03-03 | 1995-09-19 | Seiko Instr Inc | Manufacture of watch component |
| JP3205162B2 (en) * | 1994-03-10 | 2001-09-04 | 新日本製鐵株式会社 | Ferritic stainless steel with excellent machinability and corrosion resistance |
| EP0964071A1 (en) * | 1998-06-12 | 1999-12-15 | Asulab S.A. | Ferritic stainless steel and exterior cover part for a watch made with such a steel |
-
2003
- 2003-03-30 US US10/529,325 patent/US20060130938A1/en not_active Abandoned
- 2003-09-30 AU AU2003264228A patent/AU2003264228A1/en not_active Abandoned
- 2003-09-30 WO PCT/CH2003/000651 patent/WO2004031430A1/en active IP Right Grant
- 2003-09-30 CN CNB038236788A patent/CN1325687C/en not_active Expired - Fee Related
- 2003-09-30 EP EP03798852A patent/EP1546427B1/en not_active Expired - Lifetime
- 2003-09-30 DE DE50307092T patent/DE50307092D1/en not_active Expired - Fee Related
- 2003-09-30 JP JP2004540449A patent/JP2006501368A/en not_active Abandoned
- 2003-09-30 AT AT03798852T patent/ATE360103T1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1241221A (en) * | 1997-08-05 | 2000-01-12 | 川崎制铁株式会社 | Ferritic stainless steel plate of high deep drawability and ridging resistance and method of mfg. same |
| JPH11323502A (en) * | 1998-05-12 | 1999-11-26 | Sumitomo Metal Ind Ltd | Ferritic stainless steel excellent in workability and toughness and slab thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1688734A (en) | 2005-10-26 |
| AU2003264228A1 (en) | 2004-04-23 |
| EP1546427B1 (en) | 2007-04-18 |
| WO2004031430A1 (en) | 2004-04-15 |
| EP1546427A1 (en) | 2005-06-29 |
| JP2006501368A (en) | 2006-01-12 |
| DE50307092D1 (en) | 2007-05-31 |
| US20060130938A1 (en) | 2006-06-22 |
| ATE360103T1 (en) | 2007-05-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sedriks | Corrosion of stainless steels | |
| CN107604250B (en) | A kind of heavy truck transmission gear 21MnCrMoS steel and its manufacturing method | |
| CN1325687C (en) | Ferritic steel alloy | |
| CN101528971B (en) | Hard alloys with dry composition | |
| JP5731500B2 (en) | Bearing steel | |
| JP6435297B2 (en) | Nickel free austenitic stainless steel | |
| US20100276038A1 (en) | Martensitic stainless steel, method for making parts from said steel and parts thus made | |
| CN108004487A (en) | A kind of high nitrogen is without magnetic austenitic stainless steel and its manufacture method | |
| CN102080188B (en) | CrNiMo series easily cut pinion steel and manufacturing method thereof | |
| CN101517116A (en) | Steel alloy, a holder or a holder detail for a plastic moulding tool, a tough hardened blank for a holder or holder detail, a process for producing a steel alloy | |
| JP4538966B2 (en) | High strength and high corrosion resistance nonmagnetic stainless steel | |
| WO2013159669A1 (en) | Stainless steel material and manufacturing method therefor | |
| CN102597290A (en) | Hot-rolled steel bar or wire rod | |
| CN103534377A (en) | Martensitic stainless steel plate for bicycle disc brake rotor and manufacturing method therefor | |
| CN107058906B (en) | Stainless steel, ball pen head STAINLESS STEEL WIRE and preparation method thereof | |
| CN108315643A (en) | A kind of free cutting stainless steel and preparation method thereof | |
| CN110438390A (en) | A kind of the petroleum pipeline valve body steel and its production method of the big specification pole material of Φ 280mm | |
| CN101596584B (en) | Compound centrifugal manufacturing method for sink roller or stabilizing roller | |
| CN108277432A (en) | A kind of cutlery martensite containing nitrogen stainless steel and its manufacturing method | |
| CN106062233A (en) | Stainless steel and a cutting tool body made of the stainless steel | |
| CN109477179A (en) | Steel for high-frequency quenching | |
| CN104245984A (en) | Method for producing mold steel, mold steel, method of producing pre-hardened mold material, and pre-hardened mold material | |
| CN103703150A (en) | Hot-work tool steel and a process for making a hot-work tool steel | |
| JP3486936B2 (en) | Material for watch exterior parts and watch exterior parts | |
| US5720829A (en) | Maraging type hot work implement or tool and method of manufacture thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |