JP4327601B2 - Precipitation hardening austenitic steel - Google Patents
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
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- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- 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
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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Abstract
Description
本発明は、オーステナイトステンレス鋼に関し、詳しくは適量のアルミニウムと多量のシリコンとを含有した高強度析出硬化型オーステナイトステンレス鋼に関し、その製品は中間熱処理無しに引抜きなどの冷間加工で断面減少させた製品であって、300℃〜500℃での最終熱処理によって強度が14%以上高まり、Md30値が−55〜−100であり、初期荷重1400Nで24時間の負荷試験における荷重低下が3.0%未満であり、例えば丸ワイヤや鋼ストリップ鋼などのバネ用および外科用や歯科用の器具などの医療機器に最適である。 The present invention relates to austenitic stainless steel, and more particularly, to a high-strength precipitation hardening austenitic stainless steel containing an appropriate amount of aluminum and a large amount of silicon, and the product is reduced in cross section by cold working such as drawing without intermediate heat treatment. It is a product, the strength is increased by 14% or more by the final heat treatment at 300 ° C. to 500 ° C., the M d30 value is −55 to −100, and the load decrease in the load test of 24 hours at an initial load of 1400 N is 3.0. For example, for springs such as round wire and steel strip steel and for medical devices such as surgical and dental instruments.
ステンレスバネ鋼の市場では、AISI302オーステナイトステンレスバネ鋼の冷間加工品が突出した地位にある。それは、良好な耐食性を備えていると同時に、優れたバネ材料の前提である高強度が冷間加工で得られるからである。冷間加工状態をベースに、単純な熱処理によって機械的性質を更に付加できる。AISI631鋼はアルミニウムを添加して、熱処理による強度上昇を増加させている。冷間加工の際に変態が起きて、焼鈍組織の主相であるオーステナイトが硬い加工誘起マルテンサイトになる。このように変形により急激に硬化すると、延性の低下も起きるので、製造工程において1回または数回の軟化焼鈍を行なう必要がある。その結果、製造コストが上昇するばかりでなく、材料に表面欠陥が生じ易くなる。AISI631鋼は、アルミニウムを添加したために、鋳造後の凝固時に組織内にフェライトが生じ易い。その結果形成されるオーステナイト・フェライト組織と比較的少ない合金量とによって急激な加工硬化が起き易いので、製造時の加工はできるだけ緩くしてクラック発生を避ける。代替材料として、AISI304鋼およびAISI316鋼がバネ鋼として用いられている。これらの鋼は、AISI302鋼およびAISI631鋼に比べて合金量が多く、炭素量が少ない。そのため加工度を大きくできる。ただし欠点は、最終的な製品のバネとしての性質がAISI302およびAISI631に比べて劣ることである。例えば、長期間に渡ってバネ強度を維持する能力を表す耐応力緩和性がその1つである。 In the stainless spring steel market, AISI 302 austenitic stainless spring steel cold work is in a prominent position. This is because high strength, which is a premise of an excellent spring material, can be obtained by cold working while having good corrosion resistance. Based on the cold working state, mechanical properties can be further added by a simple heat treatment. AISI 631 steel has aluminum added to increase the strength increase due to heat treatment. Transformation occurs during cold working, and austenite, the main phase of the annealed structure, becomes hard work-induced martensite. Thus, if it hardens | cures rapidly by a deformation | transformation, since a ductility fall will also occur, it is necessary to perform softening annealing once or several times in a manufacturing process. As a result, not only the manufacturing cost increases, but surface defects are likely to occur in the material. Since AISI 631 steel is added with aluminum, ferrite tends to form in the structure during solidification after casting. As a result, abrupt work hardening is likely to occur due to the austenite / ferrite structure formed and the relatively small amount of alloy, so the processing during manufacturing should be as loose as possible to avoid cracking. As an alternative material, AISI 304 steel and AISI 316 steel are used as spring steel. These steels have a larger amount of alloy and less carbon than AISI 302 steel and AISI 631 steel. Therefore, the degree of processing can be increased. However, the disadvantage is that the spring properties of the final product are inferior to those of AISI 302 and AISI 631. One example is stress relaxation resistance, which represents the ability to maintain spring strength over a long period of time.
US−A−6106639には、Cr−Ni−Cu鋼は前後に焼鈍を行なうと大きな断面減少が可能であることが記載されている。実験データによると断面減少(圧下率)ε=3.41(5.5mmから1mmへ)で強度1856MPaである。これは規格強度の標準値2050MPaと比肩される値である。US−A−6106639によれば、この標準値を満たす強度を得るには、熱処理が必要である。US−A−6106639の合金は、熱処理によって強度を高めるために銅を添加してある。 U.S. Pat. No. 6,106,639 describes that Cr—Ni—Cu steel can be greatly reduced in cross section when annealed back and forth. According to the experimental data, the cross-section reduction (rolling ratio) ε = 3.41 (from 5.5 mm to 1 mm) and the strength is 1856 MPa. This is a value comparable to the standard value 2050 MPa of the standard strength. According to U.S. Pat. No. 6,106,639, heat treatment is necessary to obtain a strength satisfying this standard value. In the alloy of US-A-6106639, copper is added to increase the strength by heat treatment.
US−A−6048416には、車両タイヤを改良するための高強度鋼ワイヤとしてCr−Ni−Cu鋼が記載されている。所望の特性を得るために、US−A−6048416の合金組成は、下記のいわゆるJM値:
JM=551−462×(C%+N%)−9.2×Si%−20×Mn%−13.7×Cr%−29×(Ni%+Cu%)−18.5×Mo%)
で表される安定区間が−55より大で−30より小でなくてはならない。この発明の合金は、累積対数加工率(ε=2*ln(S0/Sf))の最大値が4以下に限定されている。これは線引き加工の最大断面減少率に換算すると98%に相当する。US−A−6048416の合金は、析出硬化用元素としては銅のみを含有している。
US-A-6048416 describes Cr-Ni-Cu steel as a high strength steel wire for improving vehicle tires. In order to obtain the desired properties, the alloy composition of US-A-6048416 has the following so-called JM value:
JM = 551-462 × (C% + N%) − 9.2 × Si% −20 × Mn% −13.7 × Cr% −29 × (Ni% + Cu%) − 18.5 × Mo%)
The stability interval represented by must be greater than -55 and less than -30. In the alloy of the present invention, the maximum value of the cumulative log processing rate (ε = 2 * ln (S 0 / S f )) is limited to 4 or less. This corresponds to 98% in terms of the maximum cross-section reduction rate of the drawing process. The alloy of US-A-6048416 contains only copper as a precipitation hardening element.
本発明の目的は、適量のアルミニウムと多量のシリコンとを含有した高強度析出硬化型オーステナイトステンレス鋼であって、その製品は中間熱処理無しに引抜きなどの冷間加工で断面減少させた製品であって、300℃〜500℃での最終熱処理によって強度が14%以上高まり、Md30値が−55〜−100であり、荷重1400Nで24時間の負荷試験における荷重低下が3.0%未満であり、例えば丸ワイヤや鋼ストリップ鋼などのバネ用および外科用や歯科用の器具などの医療機器に最適である高強度析出硬化型オーステナイトステンレス鋼を提供することである。 An object of the present invention is a high-strength precipitation hardening austenitic stainless steel containing an appropriate amount of aluminum and a large amount of silicon, and the product is a product whose cross section is reduced by cold working such as drawing without intermediate heat treatment. The final heat treatment at 300 ° C. to 500 ° C. increases the strength by 14% or more, the M d30 value is −55 to −100, and the load drop in the load test of 24 hours at a load of 1400 N is less than 3.0%. It is to provide a high strength precipitation hardening austenitic stainless steel that is optimal for medical devices such as springs such as round wire and steel strip steel and surgical and dental instruments.
上記の目的は、本発明によれば、高強度オーステナイトステンレス鋼において、析出硬化型であって且つ下記の組成(wt%):
C :0を超え0.07以下
Si:0.5〜3.0
N :0を超え0.1以下
Cr:15.0〜20.0
Ni:7.0〜12.0
Al:0.25〜1.5
Cu:0〜4.0
Mn:0を超え3.0以下
Mo:0を超え2.0以下
Ti:0を超え1.0以下
残部:Feおよび通常の不純物および添加物
を有する高強度析出硬化型オーステナイトステンレス鋼によって達成される。
According to the present invention, the above-mentioned object is a high strength austenitic stainless steel, which is precipitation hardened and has the following composition (wt%):
C: more than 0 and 0.07 or less Si: 0.5-3.0
N: more than 0 and 0.1 or less Cr: 15.0-20.0
Ni: 7.0 to 12.0
Al: 0.25 to 1.5
Cu: 0 to 4.0
Mn: more than 0 and less than 3.0 Mo: more than 0 and less than 2.0 Ti: more than 0 and less than 1.0 Remainder: achieved by high strength precipitation hardening austenitic stainless steel with Fe and usual impurities and additives The
本発明鋼の合金元素の限定理由を説明する。 The reason for limiting the alloy elements of the steel of the present invention will be described.
炭素(C)はクロムと結合する傾向が強いため、結晶粒界にクロム炭化物が析出し、その周囲でクロムが枯渇する。そのため、炭素含有量が多いと耐食性が低下すると同時に脆化も起きて、線材(ワイヤ)をバネに成形する際に問題が生じる。したがって、炭素含有量はできる限り少なくすべきであり、0.0wt%は超えてしまうが、0.07wt%以下とし、望ましくは0.05wt%以下、最も望ましくは0.035wt%以下とする。 Since carbon (C) has a strong tendency to bond with chromium, chromium carbide precipitates at the grain boundary, and chromium is depleted around it. Therefore, if the carbon content is large, the corrosion resistance is lowered and at the same time embrittlement occurs, which causes a problem when a wire (wire) is formed into a spring. Therefore, the carbon content should be as low as possible and will exceed 0.0 wt%, but it should be 0.07 wt% or less, preferably 0.05 wt% or less, and most preferably 0.035 wt% or less.
シリコン(Si)はフェライト安定化元素であり、シリコン含有量が多すぎると2相組織になってしまう。そのためシリコン含有量は3.0wt%以下とする。しかし、シリコンには、冷間加工後の熱処理による強度増加を高める作用もある。そのためシリコン含有量は0.5wt%以上とすべきであり、範囲としては0.5〜3.0wt%、望ましくは0.5〜2.5wt%、最も望ましくは0.5〜1.5wt%とする。 Silicon (Si) is a ferrite stabilizing element, and if the silicon content is too high, it becomes a two-phase structure. Therefore, the silicon content is 3.0 wt% or less. However, silicon also has the effect of increasing the strength increase due to heat treatment after cold working. Therefore, the silicon content should be 0.5 wt% or more, and the range is 0.5 to 3.0 wt%, preferably 0.5 to 2.5 wt%, most preferably 0.5 to 1.5 wt%. And
窒素(N)はアルミニウムと窒化アルミニウムを形成して脆い望ましくない相を生ずる。更に、窒素は冷間加工時の加工硬化を促進するので本発明においては望ましくない。そのため窒素含有量はできる限り少なくすることが最も重要であり、0.1wt%以下とし、望ましくは0.05wt%以下とする。 Nitrogen (N) forms aluminum and aluminum nitride, creating a brittle and undesirable phase. Furthermore, nitrogen is undesirable in the present invention because it promotes work hardening during cold working. Therefore, it is most important to reduce the nitrogen content as much as possible, and it is 0.1 wt% or less, preferably 0.05 wt% or less.
クロム(Cr)は耐食性を付与する非常に重要な合金元素である。これはクロムによって鋼表面にCr2O3の不働体皮膜が形成されるからである。この不働体皮膜を生成させるには、Cr含有量を約12.0wt%以上とすることが必要であり、更にCrを増量すれば耐食性は高まる。Crのもう一つの利点は、オーステナイト組織を安定化して、冷間加工によるマルテンサイト変態を防止する作用があることである。しかし、Crはフェライト安定化元素なので、多すぎてはならない。そのため、本発明鋼においてCr含有量は15.0wt%以上、20.0wt%以下とし、望ましくは16.0〜19.0wt%とする。 Chromium (Cr) is a very important alloying element that imparts corrosion resistance. This is because a passive film of Cr 2 O 3 is formed on the steel surface by chromium. In order to produce this passive film, it is necessary to make the Cr content about 12.0 wt% or more. If the Cr content is further increased, the corrosion resistance is enhanced. Another advantage of Cr is that it has the effect of stabilizing the austenite structure and preventing martensitic transformation due to cold working. However, since Cr is a ferrite stabilizing element, it should not be too much. Therefore, the Cr content in the steel of the present invention is 15.0 wt% or more and 20.0 wt% or less, and preferably 16.0 to 19.0 wt%.
ニッケル(Ni)は含有量が十分であれば室温でオーステナイト組織を確保できる。また、Niを増量すると延性が高まる。しかし、Niは高価な合金元素であり、多量に存在すると加工硬化が遅れ、十分な強度が得られない。そのため、Ni含有量は7.0〜12.0wt%とし、望ましくは8.0〜11.0wt%、最も望ましくは9.0〜10.0wt%とする。 If the content of nickel (Ni) is sufficient, an austenite structure can be secured at room temperature. Moreover, ductility increases when the amount of Ni is increased. However, Ni is an expensive alloy element, and if it is present in a large amount, work hardening is delayed and sufficient strength cannot be obtained. Therefore, the Ni content is 7.0 to 12.0 wt%, preferably 8.0 to 11.0 wt%, and most preferably 9.0 to 10.0 wt%.
アルミニウム(Al)は本発明鋼の中心的な合金元素である。Alは析出硬化元素として添加して強度を高め、それにより耐応力緩和特性に効果を発揮する。冷間加工した線材を350〜500℃で析出硬化させると、βNiAlの析出物が生成して機械特性が高まるが、これは従来公知の材料とは異なる点である。これは線材をバネとして用いる場合に最も重要であり、耐応力緩和特性が非常に高い要求水準を満たさなくてはならない。Alの欠点はフェライト安定化元素であることであり、そのためにAl含有量は1.5wt%以下としなくてはならない。しかし、上述の観点から、Al含有量は0.25wt%以上とし、望ましくは0.4〜1.0wt%の範囲とする。 Aluminum (Al) is a central alloying element of the steel of the present invention. Al is added as a precipitation hardening element to increase the strength, thereby exerting an effect on stress relaxation resistance. When a cold-worked wire is precipitation hardened at 350 to 500 ° C., a precipitate of βNiAl is generated and mechanical properties are enhanced, which is different from a conventionally known material. This is most important when the wire is used as a spring, and the stress relaxation resistance must satisfy a very high requirement level. The disadvantage of Al is that it is a ferrite stabilizing element, and therefore the Al content must be 1.5 wt% or less. However, from the above viewpoint, the Al content is set to 0.25 wt% or more, and preferably in the range of 0.4 to 1.0 wt%.
銅(Cu)は2つの重要な性質を持つ合金元素である。1つ目はオーステナイト安定化元素であることであり、2つ目は加工硬化を低減して延性を高めることである。中間熱処理無しで強加工に耐えるためには、Cu含有量はできる限り多くしなくてはならない。しかし、Cu含有量を増加させると、望ましくない析出が起きて延性を低下させる危険性が出てくる。そのため、Cu含有量は0〜4.0wt%とし、望ましくは2.0〜3.5wt%、最も望ましくは2.4〜3.0wt%とする。 Copper (Cu) is an alloying element with two important properties. The first is to be an austenite stabilizing element, and the second is to reduce work hardening and increase ductility. In order to withstand strong processing without intermediate heat treatment, the Cu content must be increased as much as possible. However, increasing the Cu content raises the risk of undesirable precipitation and reduced ductility. Therefore, the Cu content is 0 to 4.0 wt%, preferably 2.0 to 3.5 wt%, and most preferably 2.4 to 3.0 wt%.
マンガン(Mn)はニッケルと同様の効果があり、オーステナイト生成元素であり、オーステナイトを安定化して冷間加工によるマルテンサイト変態を防止する。しかし、ニッケルとは異なり、マンガンは加工硬化を促進する。その結果、加工硬化が早まり、前後の焼鈍の間に行える最大加工率が小さくなる。そのため、マンガン含有量は0.0wt%を超え、3.0wt%以下、望ましくは1.0wt%以下とする。 Manganese (Mn) has the same effect as nickel and is an austenite-forming element, which stabilizes austenite and prevents martensitic transformation due to cold working. However, unlike nickel, manganese promotes work hardening. As a result, work hardening is accelerated and the maximum working rate that can be performed during the front and back annealing is reduced. Therefore, the manganese content is more than 0.0 wt%, 3.0 wt% or less, preferably 1.0 wt% or less.
モリブデン(Mo)はフェライト安定化元素であり、塩化物環境中での耐食性を著しく高める。周知のPRE(pitting corrosion equivalent:耐孔食当量)式によるとモリブデンはクロムの3倍効果的である。しかし、モリブデン含有量が多くなるとフェライト相が安定化する。更に、シグマ相などの金属間化合物が析出する危険性が高まる。そのため、モリブデン含有量は0.0wt%を超え、2.0wt%以下とする。 Molybdenum (Mo) is a ferrite stabilizing element that significantly enhances corrosion resistance in chloride environments. According to the well-known PRE (pitting corrosion equivalent) formula, molybdenum is three times more effective than chromium. However, when the molybdenum content is increased, the ferrite phase is stabilized. Furthermore, the risk of precipitation of intermetallic compounds such as a sigma phase increases. Therefore, the molybdenum content is more than 0.0 wt% and not more than 2.0 wt%.
チタン(Ti)はアルミニウムと同様に析出硬化元素であり、強度を高め、耐応力緩和特性を高めるために添加する。更に、チタンはシリコンと共に顕著な熱処理効果を発揮し、少量のチタン添加でも有効である。しかし、チタンは強力なフェライト安定化元素なので、含有量が多すぎてはいけない。そのため、チタン含有量は0.0wt%を超え、1.0wt%以下、望ましくは0.75wt%以下とする。 Titanium (Ti) is a precipitation hardening element like aluminum, and is added to increase strength and stress relaxation resistance. Further, titanium exhibits a remarkable heat treatment effect together with silicon, and is effective even when a small amount of titanium is added. However, since titanium is a strong ferrite stabilizing element, the content should not be too high. Therefore, the titanium content exceeds 0.0 wt% and is 1.0 wt% or less, preferably 0.75 wt% or less.
供試材を高周波炉で溶製した。得られたインゴットを全て全面研削した後に鍛造した。鍛造によりインゴットを103mm×103mm長さのスラブにした。加熱温度は1240〜1260℃の範囲内であった。昇温後の保持時間は1時間であった。全面研削後に超音波試験を行った。 The specimen was melted in a high frequency furnace. The obtained ingot was all ground and forged. The ingot was made into a slab having a length of 103 mm × 103 mm by forging. The heating temperature was in the range of 1240-1260 ° C. The holding time after raising the temperature was 1 hour. An ultrasonic test was performed after grinding the entire surface.
φ5.50mm〜φ5.60mmの線材を製造した。これは、スラブを1200℃〜1240℃に加熱し、最終寸法まで圧延することにより行った。この熱間圧延線材を従来の線引き機で冷間線引き加工した。 A wire rod having a diameter of φ5.50 mm to φ5.60 mm was manufactured. This was done by heating the slab to 1200 ° C to 1240 ° C and rolling to the final dimensions. This hot-rolled wire was cold drawn with a conventional drawing machine.
表1に、本発明鋼および比較鋼の供試材の化学組成(wt%)を示す。 Table 1 shows the chemical composition (wt%) of the test materials of the present invention steel and the comparative steel.
表2に、冷間線引き加工した状態およびその後に熱処理した状態の各鋼の強度を示す。表中で極限引張り強さは荷重−伸び線図の最大荷重に対応している。全ての鋼について、中間熱処理無しに累積対数加工率ε=3.95(断面減少率98%に相当)まで加工を行った。AISI302鋼はε=3.95まで冷間加工すると亀裂が発生するので、最終寸法に線引きする前の段階で焼鈍しなくてはならなかった。ともかく、全供試鋼とも同一直径の線材にした。
Table 2 shows the strength of each steel in the cold-drawn state and the heat-treated state thereafter. In the table, the ultimate tensile strength corresponds to the maximum load in the load-elongation diagram. All steels were processed to a cumulative log processing rate ε = 3.95 (corresponding to a cross-section reduction rate of 98%) without intermediate heat treatment. Since
熱処理はAISI302バネ鋼と同じ目的で行い機械的性質を高めた。これにより、幾つかの重要なバネ特性、例えば耐応力緩和特性について、従来鋼よりも顕著な効果があった。
Heat treatment was performed for the same purpose as
耐応力緩和特性を評価するために、巻き列を持たない円筒状弦巻きバネを作製した。表3に試験結果を示す。 In order to evaluate the stress relaxation resistance, a cylindrical chord spring having no winding row was produced. Table 3 shows the test results.
バネ力(F)および全バネサスペンション(ft)を室温にて力−荷重曲線から求めた。その後、バネ常数(C)および弾性係数(G)を式1および2により求めた。
Spring force (F) and total spring suspension ( ft ) were determined from the force-load curve at room temperature. Thereafter, the spring constant (C) and the elastic modulus (G) were obtained by
式1: C=(F*NV)/ft
式2: G=(8*F*NV *DM 3)/(ft*Dt 4)
応力緩和試験は、バネに一定荷重を負荷することにより行った。荷重の読み取りを最初の5分間は1分毎に行い、その後は読み取り回数を減らした。試験は全て24時間経過後に停止した。各溶製チャージについて、4水準の初期荷重について試験した。応力緩和を式3により算出し、結果を図1にまとめて示す。
Formula 1: C = (F * N V ) / ft
Equation 2: G = (8 * F * N V * D M 3) / (ft * D t 4)
The stress relaxation test was performed by applying a constant load to the spring. Load readings were taken every minute for the first 5 minutes, after which the number of readings was reduced. All tests were stopped after 24 hours. Each melt charge was tested for four levels of initial load. The stress relaxation is calculated by
式3: R=((F1−F2)/F1)*100
ここで、R=応力緩和(リラクセーション)
F1=初期荷重
F2=任意の時刻での荷重
図1に示すように、アルミニウム含有量の非常に少ないチャージ番号150725は、アルミニウムを合金元素として意図的に添加した鋼に比べて顕著な応力緩和を示した。また、本発明の合金はいずれもAISI302よりも耐応力緩和特性が同等以上であった。
Formula 3: R = ((F 1 −F 2 ) / F 1 ) * 100
Where R = stress relaxation (relaxation)
F 1 = Initial load
F 2 = Load at any time As shown in FIG. 1,
Md30/Noharaは、冷間加工率30%で鋼中のオーステナイトの50%がマルテンサイトに変態する温度である。この温度が高いほど組織が不安定であり(マルテンサイトになり易く)、必要な冷間変形量が多くなる。 M d30 / Nohara is a temperature at which 50% of austenite in the steel is transformed into martensite at a cold work rate of 30%. The higher the temperature, the more unstable the structure (is more likely to become martensite) and the required amount of cold deformation increases.
Md30/Noharaは下記式で算出される。 M d30 / Nohara is calculated by the following formula.
Md30/Nohara=551−462×(C+N)−9.2×Si−8.1×Mn−13.7×Cr−20×(Ni+Cu)−18.5×Mo−68×Nb−1.42×(ASTM結晶粒度番号−8)
表4に、試験チャージ1〜7についての結果を示す。本発明の組成を備えた鋼は、Md30値−55〜−100での熱処理の効果が最も著しく、また、中間熱処理無しで単に冷間加工した際の極限引張り強さの増加が最も大きかった。
M d30 /Nohara=551-462×(C+N)−9.2×Si−8.1×Mn−13.7×Cr-20×(Ni+Cu)−18.5×Mo−68×Nb−1.42 X (ASTM crystal grain size number -8)
Table 4 shows the results for test charges 1-7. The steel having the composition of the present invention had the most remarkable effect of heat treatment at M d30 value of −55 to −100, and the largest increase in ultimate tensile strength when simply cold worked without intermediate heat treatment. .
以下に、本発明の実施例を説明する。ただし、これは本発明を具体的に説明するのであって、本発明を限定するものではない。 Examples of the present invention will be described below. However, this is a specific description of the present invention and is not intended to limit the present invention.
本発明鋼に強い冷間加工を施した。種々の断面形状に成形可能であり、例えば、丸線材、楕円線材、型鋼、例えば矩形、三角形、その他の複雑形状が可能である。丸線材を平圧延することもできる。 The steel according to the present invention was subjected to strong cold working. It can be formed into various cross-sectional shapes, for example, round wire, elliptic wire, mold steel, such as rectangle, triangle, and other complex shapes. A round wire can be flat rolled.
実施例1:丸線材(丸ワイヤ)のバネ
前述したように、本発明鋼の線材を巻いてバネを作製した。これらのバネは、バネ特性として耐応力緩和特性すなわち長期間に渡るバネ力の維持特性が良好であり、典型的なバネ用途に適しており、例えば施錠用途すなわち施錠器具の機械部品、スプレー容器やペン特にボールペンのバネ、ポンプのバネ、織機のバネ、車両、電子工業、コンピュータおよびファインメカニクスのバネがある。
Example 1 Spring of Round Wire (Round Wire) As described above, a spring was prepared by winding a wire of the steel of the present invention. These springs have good stress relaxation characteristics, that is, long-term spring force maintenance characteristics as spring characteristics, and are suitable for typical spring applications, such as locking applications, that is, mechanical parts of locking devices, spray containers, There are pens, especially ballpoint pen springs, pump springs, loom springs, vehicles, electronics, computers and fine mechanics springs.
実施例2:条鋼(ストリップ)のバネ
純粋なトーションバネについては、トルクが定量的に求まる。トルクは下記式で表される。
Example 2: Steel bar (strip) spring For a pure torsion spring, the torque is determined quantitatively. Torque is expressed by the following formula.
M=(E*I*2*π(n−n0))/L
ここで、
M=バネのトルク
I=曲げの慣性モーメント(b*t3/12)
B=バネ条鋼の幅
T=バネ条鋼の厚さ
L=バネの伸び長さ
n0=自由バネの巻き数
n=作用巻き数
バネ形状を一定としたときにトルクを増加させるには、いわゆる逆巻きを行う。いわゆる「弾性」巻きは、作用方向とは逆向きに巻くことで行われる。この状態で熱処理を施した後、バネハウジング内で逆巻きにされる。いわゆる「クロスカーブ」巻きは、条鋼をジグザグに形成し、その後熱処理を施す。その後、バネをバネハウジング内へ逆向きに巻き込む。このようにすることにより、単純に巻いただけのバネに比べて、n0の値を小さく、更には負の値にもできる。図6を参照。本発明の合金は、熱処理で強度が顕著に増加するので、高いトルクと良好な耐応力緩和特性とを必要とするトーションバネ用として非常に適している。
M = (E * I * 2 * π (n−n 0 )) / L
here,
M = torque I = bending moment of inertia of the spring (b * t 3/12)
B = Spring strip width T = Spring strip thickness L = Spring length n 0 = Number of turns of the free spring n = Number of working turns To increase the torque when the spring shape is constant, so-called reverse winding I do. The so-called “elastic” winding is performed by winding in the direction opposite to the direction of action. After heat treatment is performed in this state, the coil is reversely wound in the spring housing. In so-called “cross curve” windings, the steel bar is formed in a zigzag and then heat treated. Thereafter, the spring is wound into the spring housing in the reverse direction. In this way, the value of n 0 can be made smaller and even a negative value compared to a simple spring. See FIG. Since the strength of the alloy of the present invention is remarkably increased by heat treatment, it is very suitable for a torsion spring that requires high torque and good stress relaxation characteristics.
実施例3:エキスパンダ線材
エキスパンダは一片の線材であり、波形成形したものを直列に接続して平坦のバネにする。このバネは、例えば、内燃機関のシリンダー内壁に負荷されるオイルスクレーパリングの圧力を調節するために用いる。自動車エンジン用の典型的なエキスパンダは2つのピストンリングの間に配置された波形線材である。このような波形リングの実例を図4に模式的に示す。
Example 3: Expander wire The expander is a piece of wire, and the corrugated ones are connected in series to form a flat spring. This spring is used, for example, to adjust the pressure of the oil scraper ring loaded on the cylinder inner wall of the internal combustion engine. A typical expander for an automobile engine is a corrugated wire placed between two piston rings. An example of such a wave ring is schematically shown in FIG.
現在のエンジン駆動車両の欠点は、車両に所望性能を発揮させるには多大なエネルギー消費を必要とすることである。エネルギー消費を低減する最も簡単な方法は、駆動装置内の摩擦を無くし、車両の総重量を減らすことである。ピストンコアはエンジンの摩擦の半分以上を占めている。そのため、リング、ピストン、シリンダー壁の材質と精度を改良することで風袋重量と軸受圧力を低下させようとする試みが行われている。エキスパンダはシリンダー壁に負荷されるオイルスクレーパリングの圧力を調整するバネであり、それによってオイル消費も、更にはエンジン内部の摩擦の一部をも調整する。エキスパンダ線材の荷重は、図5a〜5cに示すように力Fで構成される。 A drawback of current engine-driven vehicles is that they require significant energy consumption in order for the vehicle to achieve the desired performance. The simplest way to reduce energy consumption is to eliminate friction in the drive and reduce the total weight of the vehicle. The piston core accounts for more than half of the engine friction. Therefore, attempts have been made to reduce the tare weight and bearing pressure by improving the material and accuracy of the ring, piston, and cylinder wall. The expander is a spring that adjusts the pressure of the oil scraper ring loaded on the cylinder wall, thereby adjusting oil consumption and part of the friction inside the engine. The load of the expander wire is constituted by a force F as shown in FIGS.
平坦なバネの場合は、荷重は最大荷重背面に対して角度90°で負荷され、下記の関係が適用される。 In the case of a flat spring, the load is applied at an angle of 90 ° with respect to the maximum load back surface, and the following relationship applies.
σmax: バネ背面に負荷される最大許容荷重
F: ピストン直径に対するエキスパンダ線材の長さによって決まる荷重力
T: 線材の厚さ
B: 線材の幅
E: 線材の弾性係数
s: サスペンション移動距離、エキスパンダの変形量
R: 個々のバネ要素の曲げ半径
(1) σmax=6FR/BT2
(2) s=42R3F/EBT3
(3) (1)と(2)を組み合わせて:
B=42R3T/EsT3=6FR/σmaxT2 ⇒ T=7R2σmax/Es
式(3)は、所望特性を得るのに必要な線材厚さがエキスパンダのデザインに依存することを示している。材料の許容引張り力が増加すると、曲げ半径は小さくて済み、これはサイズの小さいリングを製造できる点で重要である。環境上の規制が強まるのに伴ってエンジンの小型化に対する要請が高まっており、製造できるリングサイズを小さくすることの重要性が高まっている。
σ max: Maximum allowable load applied to the back of the spring F: Load force determined by the length of the expander wire relative to the piston diameter T: Wire thickness B: Wire width E: Elastic modulus of wire s: Suspension travel distance, Expander deformation amount R: Bending radius of each spring element (1) σmax = 6FR / BT 2
(2) s = 42R 3 F / EBT 3
(3) Combining (1) and (2):
B = 42R 3 T / EsT 3 = 6FR / σmax T 2 ⇒ T = 7R 2 σmax / Es
Equation (3) shows that the wire thickness necessary to obtain the desired properties depends on the design of the expander. Increasing the allowable pulling force of the material requires a smaller bend radius, which is important in that small size rings can be produced. As environmental regulations become stronger, there is an increasing demand for smaller engines, and the importance of reducing the ring size that can be manufactured is increasing.
エキスパンディングリングの高強度化によるもう一つの利点は、下記のエネルギー的な観点から考えられる。 Another advantage of increasing the strength of the expanding ring can be considered from the following energy viewpoint.
A: 弾性エネルギー
K: 材料用途による常数
E: 弾性係数
V: バネの実効体積(バネとして作用する材料の量)
σ: 負荷される引張応力
(4) A=VK(σ2/E)
式(4)は、弾性係数が決まれば、弾性エネルギーは、体積、材料用途、最大負荷引張応力の関数となることを示している。一般に最大負荷引張応力が増加すると材料用途常数が増加し、その組み合わせにより所要材料体積が大きく影響される。したがって、一定レベルの弾性エネルギーを得るための体積増加による許容引張応力を減ずることができる。
A: Elastic energy K: Constant depending on material application E: Elastic modulus V: Effective volume of spring (amount of material acting as spring)
σ: Applied tensile stress (4) A = VK (σ 2 / E)
Equation (4) shows that once the elastic modulus is determined, the elastic energy is a function of volume, material application, and maximum load tensile stress. Generally, when the maximum load tensile stress increases, the material application constant increases, and the required material volume is greatly influenced by the combination. Therefore, the allowable tensile stress due to the volume increase for obtaining a certain level of elastic energy can be reduced.
複雑な形のエキスパンディングリングの形成は、柔らかい材料でのみ可能である。ステンレス鋼を用いる最大の理由はその加工性である。しかし、エキスパンダとしての機能の観点からは、引張降伏点および極限引張強さは少なくとも全てのバネ用途で重要である。従来、両方の要請を満たすことはできなかった。本発明鋼を用いることにより、材料を柔らかい状態で成形し、最終形状にしてから熱処理して、析出硬化により所望のバネ特性を付与できる。 The formation of complex shaped expanding rings is possible only with soft materials. The biggest reason for using stainless steel is its workability. However, from a functional standpoint as an expander, the tensile yield point and ultimate tensile strength are important in at least all spring applications. Traditionally, both requests could not be met. By using the steel of the present invention, the material can be molded in a soft state, heat-treated after being made into a final shape, and desired spring characteristics can be imparted by precipitation hardening.
実施例4: 平坦な線材
この形態は、予備成形なしで力に対抗しなくてはならないので、耐応力緩和特性が最も求められる用途に特に適している。最適な具体例としては、ウィンドスクリーンワイパー用の線材があり、出発材料の打ち抜き加工性が良好で、最終製品の耐応力緩和特性が優れている必要がある。
Example 4: Flat wire This form is particularly suitable for applications where stress relaxation resistance is most required because it must resist forces without preforming. As an optimal example, there is a wire for a windscreen wiper, and it is necessary that the starting material has good punchability and the final product has excellent stress relaxation resistance.
実施例5: 医療用途の丸および平坦な線材(ワイヤ)および条鋼(ストリップ)
本発明鋼で作製された線材は医療用途にも有用であり、例えば根管用ファイルなどのファイル類、神経摘出用鉗子など、外科用縫合針としても用いられる。本発明鋼の平坦な圧延線材は歯科用および外科用の器具を製造するのに適している。
Example 5: Round and flat wire (wire) and strip (strip) for medical use
The wire made of the steel of the present invention is also useful for medical applications, and is also used as a surgical suture needle such as a file for a root canal file or a forceps for nephrectomy. The flat rolled wire of the steel according to the invention is suitable for producing dental and surgical instruments.
これらの用途はいずれも複雑な形状のものであり、研削、曲げ、捻りなどの加工を行った後に最終的に熱処理を施すことにより、高い破断強度と良好な延性とを兼ね備えた機械特性を付与される。 All of these applications have complicated shapes, and after final processing such as grinding, bending, and twisting, mechanical properties that combine high fracture strength and good ductility are imparted. Is done.
Claims (10)
C :0を超え0.07以下
Si:0.5〜3.0
N :0を超え0.1以下
Cr:15.0〜20.0
Ni:9.0〜12.0
Al:0.25〜1.5
Cu:2.4〜3.0
Mn:0を超え3.0以下
Mo:0を超え2.0以下
残部:Feおよび不可避的不純物を有し、
冷間加工により中間熱処理無しに99%以上の加工率で加工可能であり、300℃〜500℃での最終熱処理によって強度が14%以上増加することを特徴とする高強度析出硬化型オーステナイトステンレス鋼。In high-strength austenitic stainless steel, the steel is precipitation hardened and has the following composition (wt%):
C: more than 0 and 0.07 or less Si: 0.5-3.0
N: more than 0 and 0.1 or less Cr: 15.0-20.0
Ni: 9.0 to 12.0
Al: 0.25 to 1.5
Cu: 2.4 to 3.0
Mn: more than 0 and 3.0 or less Mo: more than 0 and 2.0 or less Remainder: Fe and unavoidable impurities
High-strength precipitation hardened austenitic stainless steel that can be processed at a processing rate of 99% or more by cold working without intermediate heat treatment, and the strength increases by 14% or more by the final heat treatment at 300 ° C. to 500 ° C. .
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SE0104192A SE526881C2 (en) | 2001-12-11 | 2001-12-11 | Secretion curable austenitic alloy, use of the alloy and preparation of a product of the alloy |
PCT/SE2002/002300 WO2003056053A1 (en) | 2001-12-11 | 2002-12-11 | Precipitation hardenable austenitic steel |
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JP2003556567A Expired - Fee Related JP4327601B2 (en) | 2001-12-11 | 2002-12-11 | Precipitation hardening austenitic steel |
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US (2) | US20050126661A1 (en) |
EP (1) | EP1472383B1 (en) |
JP (1) | JP4327601B2 (en) |
KR (1) | KR100966068B1 (en) |
AT (1) | ATE360104T1 (en) |
AU (2) | AU2002360028A1 (en) |
BR (1) | BR0214816B1 (en) |
DE (1) | DE60219693T2 (en) |
SE (1) | SE526881C2 (en) |
WO (2) | WO2003056053A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013146876A1 (en) | 2012-03-29 | 2013-10-03 | 新日鐵住金ステンレス株式会社 | High-strength stainless steel wire having excellent heat deformation resistance, high-strength spring, and method for manufacturing same |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060266439A1 (en) * | 2002-07-15 | 2006-11-30 | Maziasz Philip J | Heat and corrosion resistant cast austenitic stainless steel alloy with improved high temperature strength |
DE102005024029B3 (en) * | 2005-05-23 | 2007-01-04 | Technische Universität Bergakademie Freiberg | Austenitic lightweight steel and its use |
SI2136089T1 (en) * | 2008-06-16 | 2011-02-28 | Gally S P A | Self-locking nut |
IT1396294B1 (en) * | 2009-10-05 | 2012-11-16 | Gally S P A | SELF-LOCKING NUTS |
KR101420782B1 (en) * | 2013-12-30 | 2014-07-17 | 광일토건환경 주식회사 | The processing method covering construction of the rod surface |
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CN105483502A (en) * | 2015-12-03 | 2016-04-13 | 浙江腾龙精线有限公司 | Production method for spring wire |
CN108977727A (en) * | 2018-06-29 | 2018-12-11 | 柳州市横阳机械有限公司 | The preparation method of stainless steel wire |
CN112941423A (en) * | 2019-11-26 | 2021-06-11 | 上海微创医疗器械(集团)有限公司 | Medical alloy and stent |
CN114959423B (en) * | 2022-06-07 | 2023-04-14 | 甘肃酒钢集团宏兴钢铁股份有限公司 | Smelting method of high-silicon titanium-containing austenitic stainless steel |
Family Cites Families (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2553330A (en) * | 1950-11-07 | 1951-05-15 | Carpenter Steel Co | Hot workable alloy |
US3282684A (en) * | 1963-07-31 | 1966-11-01 | Armco Steel Corp | Stainless steel and articles |
US3282686A (en) * | 1965-02-01 | 1966-11-01 | Armco Steel Corp | Stainless steel and articles |
US3362813A (en) * | 1964-09-15 | 1968-01-09 | Carpenter Steel Co | Austenitic stainless steel alloy |
US3357868A (en) * | 1964-11-17 | 1967-12-12 | Armco Steel Corp | Stainless steel and method |
US3376780A (en) * | 1966-09-19 | 1968-04-09 | Armco Steel Corp | Stainless steel, products and method |
US3408178A (en) * | 1967-06-27 | 1968-10-29 | Carpenter Steel Co | Age hardenable stainless steel alloy |
US3957545A (en) * | 1970-07-28 | 1976-05-18 | Nippon Kokan Kabushiki Kaisha | Austenitic heat resisting steel containing chromium and nickel |
JPS5129854B2 (en) * | 1973-04-21 | 1976-08-27 | ||
US3969109A (en) * | 1974-08-12 | 1976-07-13 | Armco Steel Corporation | Oxidation and sulfidation resistant austenitic stainless steel |
SE419102C (en) * | 1974-08-26 | 1985-12-23 | Avesta Ab | APPLICATION OF A CHROME NICKEL NUMBER WITH AUSTENITIC STRUCTURE FOR CONSTRUCTIONS REQUIRING HIGH EXTREME CRIME RESISTANCE AT CONSTANT TEMPERATURE UP TO 1200? 59C |
US4102225A (en) * | 1976-11-17 | 1978-07-25 | The International Nickel Company, Inc. | Low chromium oxidation resistant austenitic stainless steel |
US4218268A (en) * | 1977-06-30 | 1980-08-19 | Kubota Ltd. | High corrosion resistant and high strength medium Cr and low Ni stainless cast steel |
JPS54120223A (en) * | 1978-03-11 | 1979-09-18 | Kawasaki Steel Co | Production of stainless steel spring material with fatigue resistance |
JPS59162254A (en) * | 1983-03-01 | 1984-09-13 | Takeshi Masumoto | Fe alloy material of superior workability |
JPS6036649A (en) * | 1983-08-05 | 1985-02-25 | Nisshin Steel Co Ltd | Precipitation hardening martensitic stainless steel with superior toughness |
ES2044905T3 (en) * | 1986-12-30 | 1994-01-16 | Nisshin Steel Co Ltd | PROCESS FOR THE PRODUCTION OF A CHROME STAINLESS STEEL BELT OF A DOUBLE STRUCTURE THAT HAS A HIGH STRENGTH AND EXTENSION AS WELL AS A BETTER FLAT ANISTROPY. |
TW290592B (en) * | 1993-07-08 | 1996-11-11 | Asahi Seiko Co Ltd | |
US5496421A (en) * | 1993-10-22 | 1996-03-05 | Nkk Corporation | High-strength martensitic stainless steel and method for making the same |
DE4498699B4 (en) * | 1993-11-09 | 2005-04-07 | Nisshin Steel Co., Ltd. | Use of a stainless steel with excellent corrosion resistance to molten salts |
JPH07138704A (en) * | 1993-11-12 | 1995-05-30 | Nisshin Steel Co Ltd | High strength and high ductility dual-phase stainless steel and its production |
US5411513A (en) * | 1994-02-24 | 1995-05-02 | Danek Medical, Inc. | Transmission mechanism for a surgical cutting instrument |
JPH08104953A (en) * | 1994-08-11 | 1996-04-23 | Nisshin Steel Co Ltd | Austenitic stainless steel having antibacterial property |
US5686044A (en) * | 1995-03-31 | 1997-11-11 | Nippon Yakin Kogyo Co., Ltd. | Austenitic stainless steels for press forming |
US5681528A (en) * | 1995-09-25 | 1997-10-28 | Crs Holdings, Inc. | High-strength, notch-ductile precipitation-hardening stainless steel alloy |
MY118759A (en) * | 1995-12-15 | 2005-01-31 | Nisshin Steel Co Ltd | Use of a stainless steel as an anti-microbial member in a sanitary environment |
JP4173609B2 (en) * | 1999-09-16 | 2008-10-29 | 日新製鋼株式会社 | Austenitic stainless steel and steel plate for press forming with excellent formability and hot workability |
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2001
- 2001-12-11 SE SE0104192A patent/SE526881C2/en not_active IP Right Cessation
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2002
- 2002-12-11 JP JP2003556567A patent/JP4327601B2/en not_active Expired - Fee Related
- 2002-12-11 KR KR1020047008951A patent/KR100966068B1/en not_active IP Right Cessation
- 2002-12-11 US US10/496,491 patent/US20050126661A1/en not_active Abandoned
- 2002-12-11 AT AT02792137T patent/ATE360104T1/en not_active IP Right Cessation
- 2002-12-11 AU AU2002360028A patent/AU2002360028A1/en not_active Abandoned
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- 2002-12-11 WO PCT/SE2002/002300 patent/WO2003056053A1/en active IP Right Grant
- 2002-12-11 DE DE60219693T patent/DE60219693T2/en not_active Expired - Lifetime
- 2002-12-11 WO PCT/SE2002/002299 patent/WO2003056052A1/en not_active Application Discontinuation
- 2002-12-11 EP EP02792137A patent/EP1472383B1/en not_active Expired - Lifetime
- 2002-12-11 AU AU2002358375A patent/AU2002358375A1/en not_active Abandoned
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013146876A1 (en) | 2012-03-29 | 2013-10-03 | 新日鐵住金ステンレス株式会社 | High-strength stainless steel wire having excellent heat deformation resistance, high-strength spring, and method for manufacturing same |
CN104136645A (en) * | 2012-03-29 | 2014-11-05 | 新日铁住金不锈钢株式会社 | High-strength stainless steel wire having excellent heat deformation resistance, high-strength spring, and method for manufacturing same |
CN104136645B (en) * | 2012-03-29 | 2016-06-29 | 新日铁住金不锈钢株式会社 | The excellent high-strength stainless steel wire of resistance to heat distorsion, high-strength spring and manufacture method thereof |
Also Published As
Publication number | Publication date |
---|---|
DE60219693T2 (en) | 2007-12-27 |
SE526881C2 (en) | 2005-11-15 |
US20050126661A1 (en) | 2005-06-16 |
AU2002358375A1 (en) | 2003-07-15 |
SE0104192D0 (en) | 2001-12-11 |
SE0104192L (en) | 2003-06-12 |
ATE360104T1 (en) | 2007-05-15 |
WO2003056052A1 (en) | 2003-07-10 |
WO2003056053A1 (en) | 2003-07-10 |
BR0214816A (en) | 2004-08-31 |
JP2005513273A (en) | 2005-05-12 |
WO2003056053B1 (en) | 2004-04-08 |
AU2002360028A1 (en) | 2003-07-15 |
EP1472383A2 (en) | 2004-11-03 |
US20070041863A1 (en) | 2007-02-22 |
KR100966068B1 (en) | 2010-06-28 |
BR0214816B1 (en) | 2011-02-08 |
DE60219693D1 (en) | 2007-05-31 |
EP1472383B1 (en) | 2007-04-18 |
KR20040061028A (en) | 2004-07-06 |
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