JP2002510030A - Heat exchanger tube, method of manufacturing heat exchanger tube, and condenser - Google Patents
Heat exchanger tube, method of manufacturing heat exchanger tube, and condenserInfo
- Publication number
- JP2002510030A JP2002510030A JP2000541472A JP2000541472A JP2002510030A JP 2002510030 A JP2002510030 A JP 2002510030A JP 2000541472 A JP2000541472 A JP 2000541472A JP 2000541472 A JP2000541472 A JP 2000541472A JP 2002510030 A JP2002510030 A JP 2002510030A
- Authority
- JP
- Japan
- Prior art keywords
- heat exchanger
- exchanger tube
- surface layer
- chromium
- coating material
- 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.)
- Granted
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F19/00—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers
- F28F19/02—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings
- F28F19/06—Preventing the formation of deposits or corrosion, e.g. by using filters or scrapers by using coatings, e.g. vitreous or enamel coatings of metal
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28B—STEAM OR VAPOUR CONDENSERS
- F28B1/00—Condensers in which the steam or vapour is separate from the cooling medium by walls, e.g. surface condenser
- F28B1/02—Condensers in which the steam or vapour is separate from the cooling medium by walls, e.g. surface condenser using water or other liquid as the cooling medium
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
Abstract
(57)【要約】 外側の表面層（２）と、この外側の表面層により囲まれる内側の表面層（３）とを備え、これらの表面層が互いに固定結合されている、特に復水器（１０）用の熱交換器管（１）において、一方の表面層が高耐食性の被覆材料（４）からなり、他方の表面層がそれより低い耐食性の基材（５）からなる。この発明は、さらに、この熱交換器管の製造方法及び復水器に関する。 (57) Abstract: A condenser comprising an outer surface layer (2) and an inner surface layer (3) surrounded by the outer surface layer, wherein the surface layers are fixedly connected to each other, in particular, a condenser. In the heat exchanger tube (1) for (10), one surface layer is made of a high corrosion resistant coating material (4), and the other surface layer is made of a lower corrosion resistant base material (5). The present invention further relates to a method for manufacturing the heat exchanger tube and a condenser.
Description
【０００１】 この発明は、外側の表面層と、この外側の表面層に囲まれている内側の表面層
とを備えた、特に復水器用の熱交換器管に関する。The present invention relates to a heat exchanger tube, particularly for a condenser, having an outer surface layer and an inner surface layer surrounded by the outer surface layer.
【０００２】 熱交換器管は、媒体の熱を他の媒体に伝達するいろいろな種類の熱交換器にお
いて使用される。これにより、例えば媒体を蒸発するまで加熱したり、媒体を凝
縮するまで冷却したりすることができる。フィシャー企業グループの情報誌「管
技術の今日」、７／９５、には、「Ｄ１Ｌ−最新の管コンセプトの新しい公式」
なる論文で、排ガス設備、特に排ガス曲管用の二重壁管が記載されている。この
二重壁管は特殊鋼で作られ、これにより平滑で、流れ状態のよい管内面が得られ
る。この二重壁管を製造するために、２つのスリット帯板を連続プロセスで圧延
形成し、その突き合わせ端でレーザ溶接により溶接する。このようにして製造し
た二重壁管は、従来公知の二重壁管のように、共通の溶接継ぎ目で互いに結合さ
れた２つの管壁からなっている。かくして製造した二重壁管においては、ただ１
つの接続を溶接継ぎ目により行っているので、内管と外管の分かれ目において音
響の伝達を有効に遮断し、その結果このような二重壁管で有効な音響絶縁を行え
ることが示されている。[0002] Heat exchanger tubes are used in various types of heat exchangers that transfer the heat of a medium to another medium. Thereby, for example, the medium can be heated until it evaporates or the medium can be cooled until it condenses. "D1L-a new formula for the latest tube concept" in the Fischer Corporate Group's information magazine "Today in Tube Technology", 7/95.
In a dissertation, a double wall pipe for exhaust gas installations, in particular for bent exhaust pipes, is described. This double-walled tube is made of special steel, which results in a smooth, well-flowing tube inner surface. To produce this double-walled tube, two slit strips are roll formed in a continuous process and are welded at their butt ends by laser welding. The double-walled pipe produced in this way consists of two pipe walls which are connected to one another by a common weld seam, as is the case for the double-walled pipes known in the prior art. In a double-walled tube manufactured in this way, only one
Since the two connections are made by welding seams, it has been shown that sound transmission can be effectively cut off at the junction between the inner and outer tubes, resulting in effective acoustic insulation with such a double-walled tube .
【０００３】 ヨーロッパ特許第０６１９４６６号明細書には、蒸気復水器として説明された
熱交換器が示されている。この熱交換器は蒸気タービン用の長方形構造の表面復
水器である。この復水器は、この場合、排出蒸気短管を介して蒸気タービンに接
続され、これを介して蒸気が復水器の首部に流入する。この復水器は熱交換器管
の束を備え、その外側を全長にわたり蒸気が流れる。熱交換器管の内部は冷却水
が貫流する。熱交換器管の各束は、熱交換器管に対し垂直に配置された支え板に
より幾つかの区分に分割されている。[0003] EP 0619466 shows a heat exchanger described as a steam condenser. This heat exchanger is a rectangular surface condenser for a steam turbine. This condenser is in this case connected to a steam turbine via a short steam discharge pipe, through which steam flows into the neck of the condenser. The condenser comprises a bundle of heat exchanger tubes through which steam flows over its entire length. Cooling water flows through the inside of the heat exchanger tube. Each bundle of heat exchanger tubes is divided into several sections by support plates arranged perpendicular to the heat exchanger tubes.
【０００４】 オーストリー特許第ＡＴ３５０２８６号明細書は、例えば自動車用の、アルミ
ニウムラジエータ形の熱交換器管を開示している。この熱交換器管は、２つの異
なるアルミニウム合金を互いに圧延固定した複合管である。これにおいては、異
なるアルミニウム合金のそれぞれ２つの薄板が互いに圧延固定されている。この
ように圧延固定された帯板は、その継ぎ目を溶接することにより円管に形成され
る。この熱交換器管は、内面に耐食性のアルミニウム合金（被膜、メッキ）を、
外面にこれより遙かに厚い、基材としてのアルミニウム合金を備えている。内面
被膜の材料は、この場合、水を含む環境において、例えば自動車のラジエータに
おいて不凍液に起因して、基材に対し陽極性である。これによって、もし被膜に
局部的に孔があくと、相対的に大きな陽極（被膜）と小さな陰極とにより発生す
る電流が基材に孔の空くのを阻止し、これをそれ以上破壊しないように陰極的に
保護する作用を持つことになる。[0004] Austrian Patent AT 350286 discloses a heat exchanger tube of the aluminum radiator type, for example for motor vehicles. This heat exchanger tube is a composite tube in which two different aluminum alloys are rolled and fixed to each other. In this case, two thin plates of different aluminum alloys are each rolled and fixed to one another. The strip fixed by rolling in this manner is formed into a circular pipe by welding the joint. This heat exchanger tube is made of a corrosion-resistant aluminum alloy (coating, plating) on the inner surface,
The outer surface is provided with a much thicker aluminum alloy as the substrate. The material of the inner coating is in this case anodic to the substrate in a water-containing environment, for example due to antifreeze in the radiator of a motor vehicle. This prevents the current generated by the relatively large anode (coating) and the small cathode from puncturing the substrate if the coating is locally punctured, so that it is not destroyed further. It has the effect of protecting the cathode.
【０００５】 フランス特許出願第２３８９８６３号明細書には、冷蔵庫或いは暖房装置に使
用される、複合材からなる熱交換器管が記載されている。この熱交換器管は、こ
の場合、アルミニウム合金からなる管状の基材を備え、この基材は内側もまた外
側も、別のアルミニウム・シリコン合金で被膜されている。[0005] French patent application 2,389,863 describes a heat exchanger tube made of composite material for use in refrigerators or heating devices. The heat exchanger tube in this case comprises a tubular substrate made of an aluminum alloy, which substrate is coated both inside and outside with another aluminum-silicon alloy.
【０００６】 この発明の課題は、高い耐食性を持つ熱交換器管を提供することにある。この
発明のその他の課題は、このような熱交換器管の製造方法並びにこのような熱交
換器管を使用した復水器を提供することにある。An object of the present invention is to provide a heat exchanger tube having high corrosion resistance. Another object of the present invention is to provide a method for manufacturing such a heat exchanger tube and a condenser using such a heat exchanger tube.
【０００７】 この発明によれば、最初に挙げた課題は、外側の表面層と、この外側の表面層
によって囲まれている内側の表面層とを備えた、特に復水器用の熱交換器管にお
いて、これらの表面層が互いに固く結合され、一方の表面層が高耐食性の被覆材
料からなり、他方の表面層がそれより低い耐食性の基材からなり、この低耐食性
の基材が１０重量％以上のクロム成分を含むクロム鋼及び／又はこの被覆材料が
２０重量％以上のクロム成分を含む非腐食性クロム鋼或いはチタン、タンタル又
はジルコニウム合金であることによって解決される。According to the present invention, the first object is to provide a heat exchanger tube, particularly for a condenser, having an outer surface layer and an inner surface layer surrounded by the outer surface layer. Wherein the surface layers are firmly bonded to each other, one surface layer comprises a high corrosion resistant coating material, the other surface layer comprises a lower corrosion resistant substrate, and the low corrosion resistant substrate comprises 10% by weight. The problem is solved by the chromium steel containing the above chromium component and / or the coating material is a non-corrosive chromium steel or a titanium, tantalum or zirconium alloy containing not less than 20% by weight of the chromium component.
【０００８】 この発明は、この場合、熱交換器管が、良熱伝導性の他に、特に腐食性の水、
例えば海水、汽水或いは汚染河川水に接触するときに、特に含有塩分、有機性含
有物質或いは水又は他の媒体の化学的処理に基づき、高い耐食性を要求されると
いう認識に基づいている。高い熱伝導性と、これに伴う高い熱交換性とは、特に
熱交換器管の壁厚を薄くすることにより達成できる。例えば、非腐食性の鋼或い
はチタンからなる熱交換器管用の材料においては、高耐食性を達成し、薄壁構成
により同時に高い熱交換性を達成することが可能であり、しかも、銅合金からな
る熱交換器管とは異なり、長期にわたって使用しても殆ど壁厚の減少が起こらな
い。特に、著しい耐食性の材料（物質）、例えばモリブデンを含む、非腐食性の
ＣｒＮｉ鋼、チタン、ジルコニウム及びタンタル合金の場合には、材料及び製造
コストが高いので壁厚を減らすことは大きなコスト節減に繋がる。勿論、この場
合、製造性、加工性及び負荷強度に関しては限界があるので、例えば基材が一定
の厚さを下回ると、管を製造するためにその製造プロセスが明らかに高騰し、こ
のような熱交換器管の組立は、特に損傷の危険が増大することを考えると、より
難しくなる。さらに、このような材料は熱交換器管を、例えば復水器或いは熱交
換器の管底に固定する際に問題になる。というのは、管底において管を広げるこ
とによって接着強度及び密封性が小さくなるからである。このことは、特に、例
えばスーパーオーステナイト、スーパージュプレックス或いはスーパーフェライ
トのような高耐食性である非腐食性鋼が、その合金組成により高い強度を持って
いるので、これらの非腐食性鋼が低合金化、低強度の鋼板からなる管底において
、特に薄い管壁厚さ及びルート間隔において、充分に固着し、密封することがで
きないことに起因する。高耐食性の材料或いはチタンからなるこのような熱交換
器管においては、従って、これらを被覆された管底に溶接することが必要になる
。しかしこのためには、極めて時間がかかる。その上、高耐食性の材料からなる
このような管の振動強度は小さく、かかる薄壁の熱交換器管の振動を抑制するた
めに使用される支え板の数が大きくならざるを得ず、これに伴ない熱交換器、特
に復水器の製造における構造的経費が高騰する。According to the invention, the heat exchanger tubes, in addition to the good thermal conductivity, have, in particular, corrosive water,
It is based on the recognition that high corrosion resistance is required, for example, when coming into contact with seawater, brackish water or polluted river water, especially due to the chemical treatment of the salt content, organic content or water or other media. High thermal conductivity and consequently high heat exchange can be achieved, in particular, by reducing the wall thickness of the heat exchanger tubes. For example, in a material for a heat exchanger tube made of non-corrosive steel or titanium, it is possible to achieve high corrosion resistance and at the same time achieve a high heat exchange property by a thin-walled structure, and furthermore, it is made of a copper alloy. Unlike heat exchanger tubes, there is little wall thickness reduction over long periods of use. Particularly in the case of non-corrosive CrNi steels, titanium, zirconium and tantalum alloys, which contain significantly corrosion-resistant materials, for example molybdenum, the high material and production costs make reducing the wall thickness a significant cost saving. Connect. Of course, in this case, there is a limit in terms of manufacturability, workability and load strength, so that, for example, if the base material falls below a certain thickness, the manufacturing process for manufacturing the tube will obviously increase, and such a process will increase. Assembly of the heat exchanger tubes becomes more difficult, especially given the increased risk of damage. Furthermore, such materials are problematic when fixing the heat exchanger tubes, for example, to the condenser or to the bottom of the heat exchanger tubes. This is because spreading the tube at the bottom of the tube reduces the adhesive strength and the sealability. This is especially true because non-corrosive steels, such as super austenitic, super-duplex or super ferrite, which have high corrosion resistance have a higher strength due to their alloy composition. This is due to the fact that it cannot be sufficiently fixed and sealed at the bottom of a tube made of a low-strength steel plate, particularly at a small tube wall thickness and a route interval. In such heat exchanger tubes made of highly corrosion resistant materials or titanium, it is therefore necessary to weld them to the coated tube bottom. However, this takes a very long time. In addition, the vibration strength of such tubes made of highly corrosion resistant materials is low, and the number of support plates used to suppress the vibration of such thin-walled heat exchanger tubes must be increased. As a result, the structural costs in the production of heat exchangers, especially condensers, increase.
【０００９】 高耐食性の材料と、それより耐食性の低い材料とからなる複合材を備えたこの
発明による熱交換器管により、比較的強度が高く、高耐食性の被覆材料と、低合
金化、低強度の基材とを備え、管底においても簡単に固定ができまた薄い壁厚に
おいても振動強度の優れた熱交換器管が得られる。熱交換器管の要求に応じ、外
側の表面層或いは内側の表面層のいずれかに高耐食性の被覆材料を備えることが
できる。例えば熱交換器管の内部を腐食作用を持つ媒体、例えば塩分を含む水が
貫流する場合、内側の表面層を高耐食性の被覆材料とする。これに対し、熱交換
器管の外側を腐食性の媒体が環流するときには、外側の表面層を高耐食性の被覆
材料とする。[0009] The heat exchanger tube according to the present invention, comprising a composite of a material having high corrosion resistance and a material having lower corrosion resistance, provides a coating material having relatively high strength and high corrosion resistance, and a low alloying and low alloying material. A heat exchanger tube which has a strong base material, can be easily fixed even at the bottom of the tube, and has excellent vibration strength even with a small wall thickness. Depending on the requirements of the heat exchanger tube, either the outer surface layer or the inner surface layer can be provided with a highly corrosion resistant coating material. For example, when a medium having a corrosive action, for example, water containing salt, flows through the inside of the heat exchanger tube, the inner surface layer is made of a highly corrosion-resistant coating material. On the other hand, when the corrosive medium circulates outside the heat exchanger tubes, the outer surface layer is made of a highly corrosion-resistant coating material.
【００１０】 この熱交換器管は特に薄壁状に形成するのがよく、これにより内部に流れる媒
体と管壁の回りを流れる媒体との間の良好な熱伝達が行える。この壁厚は、その
場合、０．３〜２ｍｍの間、特に蒸気タービンの復水器用の熱交換器管として適
用する場合には約０．５ｍｍの範囲にあるのがよい。[0010] The heat exchanger tube is particularly preferably formed in a thin-walled form, so that a good heat transfer between the medium flowing inside and the medium flowing around the tube wall can be achieved. This wall thickness may then be in the range between 0.3 and 2 mm, especially about 0.5 mm when applied as a heat exchanger tube for a steam turbine condenser.
【００１１】 被覆材料からなる表面層の部分の厚さは、基材からなる表面層の部分の厚さよ
り薄いのがよい。特に、基材の部分の厚さは被覆材料の部分の厚さの１．５倍で
あるのがよい。これにより腐食性の媒体が接触する熱交換器管の表面における腐
食に対する保護が得られ、同時に基材の特性が、基材の強度が小さく、従って、
変形性が良いことにより、管底における熱交換器管の振動安定性及び容易な固定
に貢献する。The thickness of the portion of the surface layer made of the coating material is preferably smaller than the thickness of the portion of the surface layer made of the base material. In particular, the thickness of the part of the substrate may be 1.5 times the thickness of the part of the coating material. This provides protection against corrosion at the surface of the heat exchanger tube where the corrosive medium comes into contact, while at the same time the properties of the substrate reduce the strength of the substrate, thus
Good deformability contributes to vibration stability and easy fixing of the heat exchanger tube at the bottom of the tube.
【００１２】 被覆材料からなる表面層の部分の厚さは０．１〜０．５ｍｍの間、特に約０．
２ｍｍであるのがよい。基材からなる表面層の部分の厚さは０．２〜１．５ｍｍ
の間、特に約０．３ｍｍであるのがよい。The thickness of the part of the surface layer made of the coating material is between 0.1 and 0.5 mm, in particular about 0.
It is preferably 2 mm. The thickness of the portion of the surface layer composed of the base material is 0.2 to 1.5 mm
, Especially about 0.3 mm.
【００１３】 腐食性の媒体に曝される被覆材料は、高合金鋼、特にスーパーフェライト、ス
ーパージュプレックス或いはスーパーオーステナイトであるのがよい。これらの
合金鋼は、重量比にて以下の合金成分を含むのがよい。 スーパーフェライト：２７〜３１％のクロム、１〜５％のニッケル及び２〜５
％のモリブデン、特に約２９％のクロム。 スーパージュプレックス：２３〜２７％のクロム、４〜８％のニッケル、２〜
５％のモリブデン並びに０．１％以上の窒素、特に約２５％のクロム、５〜８％
のニッケル及び３〜５％のモリブデン。 スーパーオーステナイト：２０〜２５％のクロム、２０〜２５％のニッケル、
３〜７％のモリブデン、並びに０．２％以上の窒素。[0013] The coating material exposed to the corrosive medium may be a high alloy steel, especially super ferrite, super duplex or super austenite. These alloy steels preferably contain the following alloy components by weight. Superferrite: 27-31% chromium, 1-5% nickel and 2-5
% Molybdenum, especially about 29% chromium. Super duplex: 23-27% chromium, 4-8% nickel, 2-
5% molybdenum and 0.1% or more nitrogen, especially about 25% chromium, 5-8%
Nickel and 3-5% molybdenum. Super austenite: 20-25% chromium, 20-25% nickel,
3-7% molybdenum, and 0.2% or more nitrogen.
【００１４】 基材は、重量比にて１０〜１７％のクロムを含んだフェライトクロム鋼とする
のがよい。この基材は、また、重量比にて１６〜２０％のクロム及び６〜１０％
のニッケル、特に約１８％のクロム及び約８％のニッケルとすることもできる。The substrate is preferably a ferritic chromium steel containing 10 to 17% by weight of chromium. The substrate also contains 16-20% chromium and 6-10% by weight.
Nickel, especially about 18% chromium and about 8% nickel.
【００１５】 特に、この複合材は、スーパーフェライトとフェライト、スーパージュプレッ
クスとフェライト、スーパージュプレックスとオーステナイト或いはスーパーオ
ーステナイトとオーステナイトとのような、被覆材料と基材との組合せからなる
こともできる。また、熱交換器管の使用領域に応じて、他の組合せ、例えばスー
パージュプレックスとジュプレックス或いはスーパーオーステナイトとジュプレ
ックスのような組合せも使用することができる。In particular, the composite can also consist of a combination of a coating material and a substrate, such as superferrite and ferrite, superduplex and ferrite, superduplex and austenite or superaustenite and austenite. Also, other combinations, such as super duplex and duplex or super austenitic and duplex, may be used depending on the area of use of the heat exchanger tubes.
【００１６】 この熱交換器管は、特に複合材料の帯板を湾曲して管を形成し、その継ぎ目を
溶接して製造するのがよい。この場合、この継ぎ目の範囲における外表面と内表
面において、基材の被覆材料への混合或いはその逆の混合は起こらない。これに
より、腐食性媒体が接触する表面に、高耐食性の被覆材料がそれに応じた純度と
厚さで存在し、その結果継ぎ目には、腐食性媒体にさらされる全表面におけると
同等の耐食性が与えられる。従って、溶接継ぎ目によって許容できない程度に耐
食性が損なわれるのを回避できる。The heat exchanger tube is preferably manufactured by bending a strip of composite material to form a tube and welding the seams. In this case, no mixing of the substrate with the coating material or vice versa occurs on the outer and inner surfaces in the region of this seam. This ensures that the surface in contact with the corrosive medium has a high corrosion-resistant coating material of corresponding purity and thickness, so that the seam has the same corrosion resistance as on all surfaces exposed to the corrosive medium. Can be Therefore, it is possible to prevent the corrosion resistance from being impaired to an unacceptable degree by the welding seam.
【００１７】 この発明によれば、外側の表面層と、この外側の表面層により囲まれた内側の
表面層とを備えた熱交換器管の製造方法において、低合金基材、即ち１０重量％
以上のクロム成分を含むクロム鋼が高耐食性の被覆材料で被覆される。適当な低
合金基材の上に、この場合、２０重量％以上のクロム成分を含む非耐食性のクロ
ム鋼或いはチタン、タンタル或いはジルコニウム合金からなる高耐食性の被覆材
料が被着される。このように被覆された基材から薄厚の帯板が作られ、この帯板
から熱交換器管が湾曲されて、継ぎ目に沿って僅かな熱侵入で溶接が行われる。
最小の熱侵入と冷却速度の大きい溶接方法、例えばレーザ溶接或いは電子ビーム
溶接を使用することにより、溶接継ぎ目の範囲において腐食性媒体が接触する表
面にまで広がって、基材が被覆材料に混合することがない。この被覆材料の被覆
は、公知の被覆方法、例えば圧延、溶接及び溶射被覆により行うことができる。
圧延及び溶接被膜の場合、被覆材料及び基材に充分な延性が必要とされるが、溶
射被覆法では硬い、耐磨耗性の被覆材料でも処理可能である。冷間或いは熱間圧
延によれば大きな板状の基材も被覆することができる。溶射被覆法によれば、チ
タン合金を含む鋼板も被覆することができる。According to the present invention, in a method for manufacturing a heat exchanger tube including an outer surface layer and an inner surface layer surrounded by the outer surface layer, a low alloy base material, that is, 10% by weight is used.
The chromium steel containing the above chromium component is coated with a coating material having high corrosion resistance. On a suitable low-alloy substrate, a non-corrosive chromium steel with a chromium content of more than 20% by weight or a highly corrosion-resistant coating material of a titanium, tantalum or zirconium alloy is applied. A thin strip is produced from the substrate coated in this way, from which the heat exchanger tubes are bent and welded along the seam with little heat penetration.
By using a welding method with a minimum heat penetration and a high cooling rate, such as laser welding or electron beam welding, the substrate is mixed with the coating material in the area of the welding seam, extending to the surface where the corrosive medium contacts. Nothing. The coating of the coating material can be performed by known coating methods such as rolling, welding and spray coating.
In the case of rolled and welded coatings, sufficient ductility is required for the coating material and the substrate, but the thermal spray coating method can process even hard, wear-resistant coating materials. According to the cold or hot rolling, a large plate-shaped substrate can be coated. According to the thermal spray coating method, a steel sheet containing a titanium alloy can also be coated.
【００１８】 圧延被覆法を適用する場合には、先ず、広幅の帯板を作る。その場合、冷間或
いは熱間圧延の際の異なる合金成分により起きる、異なる変形抵抗を考慮して製
作する。この広幅の帯板から、次に、幅の狭い帯板を作り、この帯板を管に成形
し、少ない熱侵入で継ぎ目の範囲を溶接する。溶接の際に、基材が被覆材と著し
く混合する溶接法、特にシールドアーク溶接法に較べて、レーザ溶接或いは電子
ビーム溶接においては、基材と被覆材料との混合がない、最高の純度のかつ精密
な溶接継ぎ目が得られる。電子ビーム溶接は、深い、狭い溶接継ぎ目を、しかも
極めて狭い熱作用領域、従って複合材に対して最小の熱作用で、作ることを可能
とする。その上、熱侵入が少ないことにより、歪みや応力発生も小さくなり、精
密溶接を行うことができる。同様に、水素、酸素或いは窒素を供給する必要がな
いので、特に反応性の金属において、純粋なかつ脆性破壊のない、溶接継ぎ目の
形成が可能である。高いエネルギー密度は、その上、大きな溶接速度も、また非
常に薄い部分の微細溶接をも可能にする。高温溶融金属や、熱侵入の少ないこと
により非常に異なる溶融点を持つ材料も溶接できる。同様な利点は、レーザ溶接
によっても実現できる。なお、レーザ溶接は特に１ｍｍ以下の板厚に対して適し
ているので、凡そ０．５ｍｍの板厚を持つ薄壁の管においてレーザ溶接が好適に
使用される。非消耗性のタングステン電極を用い、特に高合金鋼の溶接に適用さ
れる、保護ガス雰囲気下でのタングステン不活性ガス（ＷＩＧ）溶接のような、
従来のシールドアーク溶接方法に比較して高いエネルギー密度及びビームによる
溶融溶接は、それ故、複合材からなる熱交換器管の製造に適している。When the rolling coating method is applied, first, a wide strip is produced. In that case, it is manufactured in consideration of different deformation resistances caused by different alloy components at the time of cold or hot rolling. From this wide strip, a narrow strip is then made, which is formed into a tube and the area of the seam is welded with little heat penetration. In laser welding or electron beam welding, there is no mixing of the base material and the coating material, compared to the welding method in which the base material is significantly mixed with the coating material, especially shielded arc welding. And a precise welding seam can be obtained. Electron beam welding makes it possible to produce deep, narrow welding seams, but with a very small thermal action zone and thus minimal thermal action on the composite. In addition, since there is little heat penetration, distortion and stress generation are also small, and precision welding can be performed. Similarly, since there is no need to supply hydrogen, oxygen or nitrogen, it is possible to form a pure and brittle fracture-free weld seam, especially in reactive metals. The high energy density also allows for high welding speeds, as well as fine welding of very thin parts. High temperature molten metals and materials with very different melting points due to less heat penetration can also be welded. Similar advantages can be achieved by laser welding. Since laser welding is particularly suitable for a plate thickness of 1 mm or less, laser welding is suitably used for a thin-walled tube having a plate thickness of approximately 0.5 mm. Using non-consumable tungsten electrodes, such as tungsten inert gas (WIG) welding under protective gas atmosphere, especially applied to welding of high alloy steel
The high energy density and beam fusion welding compared to conventional shielded arc welding methods are therefore suitable for the manufacture of composite heat exchanger tubes.
【００１９】 復水器に向けられた課題は、この発明によれば、外側の表面層と内側の表面層
とを備えた複合材からなる複数の熱交換器管を備え、この複合材が高耐食性の被
覆材料と低耐食性の基材とからなる、特に蒸気タービン用の復水器により解決さ
れる。被覆材料は、熱交換器管の外側の表面層が腐食性の媒体に接触するときに
は、高耐食性の被覆材料を形成する。熱交換器管の内面が腐食性の媒体に接触す
るときには、被覆材料は内側の表面層を形成する。冷却水、例えば河川、湖沼或
いは海から取り入れられる冷却水が貫流する復水器の熱交換器管においては、そ
れに応じて、内側の表面層が被覆材料から形成される。これによって、熱交換器
管の耐食性が向上し、他方では基材からなる外側の表面層により高い振動安定性
並びに復水器の管底における良好な固定が行える。According to the present invention, a problem directed to a condenser includes a plurality of heat exchanger tubes made of a composite material having an outer surface layer and an inner surface layer, and the composite material has a high height. The problem is solved by a condenser comprising a corrosion-resistant coating material and a low-corrosion-resistant substrate, in particular for a steam turbine. The coating material forms a highly corrosion resistant coating material when the outer surface layer of the heat exchanger tube contacts a corrosive medium. When the inner surface of the heat exchanger tube comes into contact with a corrosive medium, the coating material forms an inner surface layer. In the heat exchanger tubes of the condenser through which cooling water, for example cooling water from rivers, lakes or the sea, flows, the inner surface layer is correspondingly formed from the coating material. Thereby, the corrosion resistance of the heat exchanger tubes is improved, while on the other hand the outer surface layer consisting of the substrate provides high vibration stability and good fixing at the tube bottom of the condenser.
【００２０】 この発明による熱交換器管並びに復水器を、図面に示す実施例で詳細に説明す
る。各図において使用する記号は、一貫して同じ部分を示す。A heat exchanger tube and a condenser according to the present invention will be described in detail with reference to an embodiment shown in the drawings. The symbols used in each figure indicate the same parts throughout.
【００２１】 図１には帯板７が斜視図で示されている。この帯板７は低合金及び低強度の鋼
板からなる基材５を備え、この上に被覆方法、特に圧延被覆法を使用して、高耐
食性の、高合金鋼が被着されている。帯板７は０．５ｍｍの範囲の板厚１５を持
っている。基材５は板厚１７を持ち、これはメッキ材料４の板厚１６より厚い。
約０．５ｍｍの板厚１５を持つ熱交換器管１（図２参照）において、基材５の板
厚１５は約０．３ｍｍであり、被覆材料４の板厚１６は約０．２ｍｍである。FIG. 1 shows the strip 7 in a perspective view. The strip 7 comprises a substrate 5 made of a low-alloy and low-strength steel plate, on which a high corrosion-resistant, high-alloy steel is applied using a coating method, in particular a rolling coating method. The strip 7 has a thickness 15 in the range of 0.5 mm. The substrate 5 has a thickness 17 which is greater than the thickness 16 of the plating material 4.
In the heat exchanger tube 1 having a thickness 15 of about 0.5 mm (see FIG. 2), the thickness 15 of the base material 5 is about 0.3 mm, and the thickness 16 of the coating material 4 is about 0.2 mm. is there.
【００２２】 図２には熱交換器管１が斜視図で示されている。この熱交換器管１は帯板７（
図１参照）から形成されている。この熱交換器管１は、継ぎ目６に沿って電子ビ
ーム溶接或いはレーザビーム溶接により溶接されている。熱交換器管１は、内側
の表面層３に被覆材料４を、そして外側の表面層３に基材５を備えている。熱交
換器管１を継ぎ目６に沿って電子ビーム溶接或いはレーザビーム溶接を使用して
溶接することにより、外表面８と内表面９とのいずれにおいても、基材が被覆材
料と混合することはない。この結果継ぎ目６に沿って必要な材料特性、即ち、腐
食性媒体が接触する表面における高耐食性及び特に復水器の底面における固定の
ための小さい強度が保証される。腐食性媒体、例えば冷却水は、熱交換器管１を
内側から貫流する。FIG. 2 shows the heat exchanger tube 1 in a perspective view. This heat exchanger tube 1 has a strip 7 (
1 (see FIG. 1). The heat exchanger tube 1 is welded along the joint 6 by electron beam welding or laser beam welding. The heat exchanger tube 1 comprises a coating material 4 on an inner surface layer 3 and a substrate 5 on an outer surface layer 3. By welding the heat exchanger tube 1 along the seam 6 using electron beam welding or laser beam welding, the substrate mixes with the coating material on both the outer surface 8 and the inner surface 9. Absent. This guarantees the necessary material properties along the seam 6, i.e. high corrosion resistance at the surface where the corrosive medium comes into contact and low strength, especially for fixing at the bottom of the condenser. A corrosive medium, for example cooling water, flows through the heat exchanger tube 1 from the inside.
【００２３】 図３は、復水器１０の一部を縦断面で示す。この復水器１０は多数の熱交換器
管１を備え、図では分かりやすくするために、その中の４個だけを示している。
熱交換器管１は、復水器１０の管底１１に固定されている。熱交換器管１は、さ
らに、熱交換器の図示されていない両端において支え板１２により支えられてい
る。基材４と被覆材料５とからなる複合材を使用したことに伴う熱交換器管１の
振動安定性により、支え板１２の数は少数に保たれる。熱交換器管１には冷却媒
体１３、特に水が貫流する。その外表面８（図２参照）には、図示しいない蒸気
タービンから蒸気１４がその回りを流れ、この蒸気１４は熱交換器管１（復水器
管）において凝縮し、復水器１０から放出される。冷却媒体１３は、例えば河川
、湖沼或いは海から供給される場合、冷却媒体１３は熱交換器管１を高度に腐食
させるおそれがある。これは、高耐食性である被覆材料４によって明らかに減少
し、もしそうでなくても、阻止される。管底１１の範囲の内部で管１を圧延する
ことによって、管１が拡張し、それに伴って基材４の変形が起こる。これにより
管底１１において管１の良好な固定が行われる。FIG. 3 shows a part of the condenser 10 in a longitudinal section. The condenser 10 has a number of heat exchanger tubes 1 of which only four are shown for clarity.
The heat exchanger tube 1 is fixed to the tube bottom 11 of the condenser 10. The heat exchanger tube 1 is further supported by support plates 12 at both ends, not shown, of the heat exchanger. Due to the vibration stability of the heat exchanger tube 1 associated with the use of the composite material composed of the base material 4 and the coating material 5, the number of the support plates 12 is kept small. The cooling medium 13, in particular water, flows through the heat exchanger tube 1. On its outer surface 8 (see FIG. 2), steam 14 flows from a steam turbine (not shown), which condenses in the heat exchanger tube 1 (condenser tube) and from the condenser 10 Released. When the cooling medium 13 is supplied from, for example, a river, a lake, or the sea, the cooling medium 13 may highly corrode the heat exchanger tube 1. This is clearly reduced by the coating material 4, which is highly resistant to corrosion, and is prevented if not. By rolling the tube 1 within the area of the tube bottom 11, the tube 1 expands and the deformation of the substrate 4 occurs accordingly. As a result, the tube 1 is fixed well at the tube bottom 11.
【図１】 複合材からなる帯板を斜視図で示す。FIG. 1 shows a perspective view of a strip made of a composite material.
【図２】 複合材からなる帯板で構成された熱交換器管を斜視図で示す。FIG. 2 is a perspective view showing a heat exchanger tube constituted by a strip made of a composite material.
【図３】 復水器の一部を縦断面で示す。FIG. 3 shows a part of the condenser in a longitudinal section.
【符号の説明】 １ 熱交換器管 ２ 外側の表面層 ３ 内側の表面層 ４ 被覆材料 ５ 基材 ６ 継ぎ目 ７ 帯板 ８ 外表面 ９ 内表面 １０ 復水器 １１ 管底 １２ 支え板 １３ 冷却媒体（水） １４ 蒸気 １５ 板厚 １６、１７ 部分の板厚[Description of Signs] 1 Heat exchanger tube 2 Outer surface layer 3 Inner surface layer 4 Coating material 5 Base material 6 Seam 7 Strip plate 8 Outer surface 9 Inner surface 10 Condenser 11 Tube bottom 12 Support plate 13 Cooling medium (Wed) 14 Steam 15 Sheet thickness 16, 17 part thickness
Claims (13)
る内側の表面層（３）とを備え、これらの表面層（２、３）が互いに固く結合さ
れ、一方の表面層（２、３）が高耐食性の被覆材料（４）からなり、他方の表面
層（３、２）がそれより低い耐食性の基材（５）からなり、 この低耐食性の基材（５）が１０重量％以上のクロム成分を含むクロム鋼であり
及び／又は この被覆材料（４）が２０重量％以上のクロム成分を含む耐食性クロム鋼或いは
チタン、タンタル又はジルコニウム合金である 特に復水器（１０）用の熱交換器管。An outer surface layer (2) and an inner surface layer (3) surrounded by the outer surface layer (2), wherein the surface layers (2, 3) are hardened together. Bonded, one surface layer (2, 3) consisting of a coating material (4) with high corrosion resistance and the other surface layer (3, 2) consisting of a substrate (5) with lower corrosion resistance; The base material (5) is a chromium steel containing 10% by weight or more of chromium component and / or the coating material (4) is a corrosion-resistant chrome steel containing 20% by weight or more of chromium component or a titanium, tantalum or zirconium alloy. There are heat exchanger tubes, especially for the condenser (10).
いる請求項１記載の熱交換器管。2. The heat exchanger tube according to claim 1, wherein the heat exchanger tube is formed as a thin wall having a plate thickness (15) of between 0.3 and 2 mm.
基材（５）からなる表面層（３、２）の板厚（１７）より薄い、特に約５０％だ
け薄い請求項１又は２記載の熱交換器管。3. The thickness (16) of the surface layer (2, 3) made of the coating material (4) is:
3. A heat exchanger tube according to claim 1, wherein the thickness of the surface layer (3, 2) of the substrate (5) is smaller than the plate thickness (17).
．１〜０．３ｍｍの間、特に約０．２ｍｍである請求項３記載の熱交換器管。4. The thickness (16) of the surface layer (2, 3) made of the coating material (4) is zero.
. 4. The heat exchanger tube according to claim 3, which is between 1 and 0.3 mm, in particular about 0.2 mm.
〜１．５ｍｍの間、特に約０．３ｍｍである請求項３又は４記載の熱交換器管。5. The surface layer (3, 2) composed of the substrate (5) has a thickness (17) of 0.2.
Heat exchanger tube according to claim 3 or 4, wherein the heat exchanger tube is between about 1.5 mm and about 0.3 mm.
％のニッケル及び２〜４％のモリブデンを含むスーパーフェライトである請求項
１から５の１つに記載の熱交換器管。6. The coating material (4) comprises 27 to 31% by weight of chromium, 1 to 5%.
Heat exchanger tube according to one of claims 1 to 5, which is a superferrite containing 5% nickel and 2-4% molybdenum.
％のニッケル及び２〜５％のモリブデン並びに０．１％以上の窒素を含むスーパ
ージュプレックスである請求項１から６の１つに記載の熱交換器管。7. A coating material (4) comprising 23 to 27% by weight of chromium, 4 to 8%.
Heat exchanger tube according to one of claims 1 to 6, which is a superduplex containing 5% nickel and 2-5% molybdenum and 0.1% or more nitrogen.
２５％のニッケル、３〜７％のモリブデン並びに０．２％以上の窒素を含むスー
パーオーステナイトである請求項１ないし７の１つに記載の熱交換器管。8. A coating material (4) comprising 20 to 25% by weight of chromium, 20 to 20% by weight.
8. The heat exchanger tube according to claim 1, which is a super-austenite containing 25% nickel, 3-7% molybdenum and 0.2% or more nitrogen.
トクロム鋼である請求項５又は６記載の熱交換器管。9. The heat exchanger tube according to claim 5, wherein the base material (5) is a ferritic chrome steel containing 10 to 17% by weight of chromium.
％のニッケル、特に１８％のクロム及び８％のニッケルを含むオーステナイトク
ロム鋼である請求項６又は７記載の熱交換器管。10. The base material (5) comprises 16 to 20% by weight of chromium and 6 to 10%.
Heat exchanger tube according to claim 6 or 7, which is an austenitic chromium steel containing 8% nickel, 18% chromium and 8% nickel.
溶接されている熱交換器管（１）において、この継ぎ目（６）に沿ってこの外表
面（８）と内表面（９）のそれぞれの周囲にそれぞれ被覆材料（４）或いは基材
（５）だけが存在している請求項１ないし１０の１つに記載の熱交換器管。11. In a heat exchanger tube (1) having an outer surface (8) and an inner surface (9) and being welded along a seam (6), said outer surface along said seam (6). 11. The heat exchanger tube according to claim 1, wherein only the coating material (4) or the substrate (5) is present around each of (8) and the inner surface (9).
いる内側の表面層（３）とを備えた熱交換器管（１）の製造方法において、 ａ）低合金の基材（５）を高耐食性の被覆材料（４）で被覆し、その際低合金の
基材（５）として重量比にて１０％以上のクロム成分を含むクロム鋼及び／又は
高耐食性の被覆材料（４）として２０％以上のクロム成分を含む非腐食性クロム
鋼、チタン、タンタル或いはジルコニウム合金を使用し、 ｂ）これから薄壁状の帯板（７）を作り、次いで ｃ）この帯板（７）を湾曲させて熱交換器管（１）を形成し、継ぎ目（６）に沿
った少ない熱侵入で、特にレーザ溶接により溶接する 熱交換器管の製造方法。12. A method for manufacturing a heat exchanger tube (1) comprising an outer surface layer (2) and an inner surface layer (3) surrounded by the outer surface layer (2). a) A low-alloy base material (5) is coated with a coating material (4) having high corrosion resistance, wherein the low-alloy base material (5) includes a chromium steel containing 10% or more by weight of a chromium component and / or Or using a non-corrosive chromium steel, titanium, tantalum or zirconium alloy containing 20% or more of chromium as a coating material (4) having high corrosion resistance; b) forming a thin-walled strip (7) therefrom; c) A method of manufacturing a heat exchanger tube in which the strip (7) is bent to form a heat exchanger tube (1) and welded with a small heat penetration along the seam (6), in particular by laser welding.
囲まれている内側の表面層（３）とを備えた多数の熱交換器管（１）を備え、こ
れらの表面層（２、３）が互いに固く結合され、一方の表面層（２、３）が高耐
食性の被覆材料（４）からなり、他方の表面層（３、２）がそれより低い耐食性
の基材（５）からなる、特に蒸気タービン用の復水器。13. A number of heat exchanger tubes (1) each having an outer surface layer (2) and an inner surface layer (3) surrounded by the outer surface layer (2). The surface layers (2, 3) are firmly bonded to one another, one of the surface layers (2, 3) being made of a highly corrosion-resistant coating material (4) and the other surface layer (3, 2) being lower. A condenser comprising a corrosion-resistant substrate (5), especially for steam turbines.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19813771 | 1998-03-27 | ||
| DE19813771.0 | 1998-03-27 | ||
| PCT/DE1999/000714 WO1999050610A1 (en) | 1998-03-27 | 1999-03-15 | Heat exchanger tube, method for the production of a heat exchanger tube and capacitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2002510030A true JP2002510030A (en) | 2002-04-02 |
| JP4276382B2 JP4276382B2 (en) | 2009-06-10 |
Family
ID=7862686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000541472A Expired - Fee Related JP4276382B2 (en) | 1998-03-27 | 1999-03-15 | Heat exchanger tube, heat exchanger tube manufacturing method and condenser |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP1066494A1 (en) |
| JP (1) | JP4276382B2 (en) |
| KR (1) | KR20010034712A (en) |
| CN (1) | CN1139782C (en) |
| WO (1) | WO1999050610A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004069102A (en) * | 2002-08-02 | 2004-03-04 | Mitsuro Takahama | Double cylinder type heat exchanger |
| KR101131846B1 (en) * | 2009-12-09 | 2012-03-30 | 주식회사 다산 | Manufacturing method of Cu/Ti bi-metal tube |
| WO2018131112A1 (en) * | 2017-01-12 | 2018-07-19 | 三菱電機株式会社 | Twisted tube heat exchanger and manufacturing method for twisted tube heat exchangers |
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| US6318094B1 (en) | 2000-08-11 | 2001-11-20 | Paul Mueller Company | Bimetallic tube in a heat exchanger of an ice making machine |
| US7660740B2 (en) | 2000-10-16 | 2010-02-09 | Ebay Inc. | Method and system for listing items globally and regionally, and customized listing according to currency or shipping area |
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| DE102004056619B4 (en) * | 2004-03-09 | 2007-06-06 | BRÜNDERMANN, Georg | Process for the production of a heat exchanger partition with an armor and heat exchanger partition |
| EP1722917A1 (en) * | 2004-03-09 | 2006-11-22 | Bründermann, Georg | Method for producing a heat exchanger partition with an armor-plating, and a heat exchanger partition |
| US20090266529A1 (en) * | 2005-04-18 | 2009-10-29 | Giovanni Jahier | Protected Carbon Steel Pipe for Fire Tube Heat Exchange Devices, Particularly Boilers |
| US20090173485A1 (en) * | 2007-11-30 | 2009-07-09 | Ranga Nadig | Fin tube assembly for air cooled heat exchanger and method of manufacturing the same |
| EP2161095A1 (en) * | 2008-09-05 | 2010-03-10 | ALSTOM Technology Ltd | Method of surface treatment of a turbine component |
| US10620010B2 (en) | 2015-02-05 | 2020-04-14 | Moovit App Global Ltd | Public and ordered transportation trip planning |
| WO2019049498A1 (en) | 2017-09-11 | 2019-03-14 | ソニーセミコンダクタソリューションズ株式会社 | Semiconductor integrated circuit |
| AU2018347410B2 (en) * | 2017-10-13 | 2024-06-13 | Haynes International, Inc. | Solar tower system containing molten chloride salts |
| CN117187700A (en) | 2019-07-05 | 2023-12-08 | 斯塔米卡邦有限公司 | Ferritic steel component in urea plant |
| CN110579131A (en) * | 2019-09-20 | 2019-12-17 | 江阴市亚龙换热设备有限公司 | highly corrosion-resistant heat exchanger |
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|---|---|---|---|---|
| US3809155A (en) | 1972-02-02 | 1974-05-07 | Olin Corp | Erosion-corrosion resistant aluminum radiator clad tubing |
| FR2389863B1 (en) | 1977-05-06 | 1982-06-25 | Chausson Usines Sa | |
| JPS57120002A (en) * | 1981-01-19 | 1982-07-26 | Sumitomo Metal Ind | Double tube for boiler |
| JPS59176596A (en) * | 1983-03-25 | 1984-10-05 | Babcock Hitachi Kk | Tube for heat exchanger |
| JPS59176501A (en) * | 1983-03-28 | 1984-10-05 | 株式会社日立製作所 | Boiler tube |
| JPS61227152A (en) * | 1985-03-29 | 1986-10-09 | Sumitomo Metal Ind Ltd | Surface covered heat resisting steel pipe for boiler for recovering black liquor |
| JPH028336A (en) * | 1988-06-28 | 1990-01-11 | Jgc Corp | Carbon deposition-resistant two-layer pipe |
| JPH05118772A (en) * | 1990-12-01 | 1993-05-14 | Toshiba Corp | Seawater cooling condenser |
| DE4311118A1 (en) | 1993-04-05 | 1994-10-06 | Abb Management Ag | Steam condenser |
| EP0619179A1 (en) * | 1993-04-06 | 1994-10-12 | Nippon Steel Corporation | Wear resisting steel for welded pipes, and manufacturing process |
| JPH07159056A (en) * | 1993-12-08 | 1995-06-20 | Toshiba Corp | Condenser |
-
1999
- 1999-03-15 KR KR1020007010730A patent/KR20010034712A/en not_active Application Discontinuation
- 1999-03-15 CN CNB998046973A patent/CN1139782C/en not_active Expired - Fee Related
- 1999-03-15 JP JP2000541472A patent/JP4276382B2/en not_active Expired - Fee Related
- 1999-03-15 EP EP99919076A patent/EP1066494A1/en not_active Withdrawn
- 1999-03-15 WO PCT/DE1999/000714 patent/WO1999050610A1/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004069102A (en) * | 2002-08-02 | 2004-03-04 | Mitsuro Takahama | Double cylinder type heat exchanger |
| KR101131846B1 (en) * | 2009-12-09 | 2012-03-30 | 주식회사 다산 | Manufacturing method of Cu/Ti bi-metal tube |
| WO2018131112A1 (en) * | 2017-01-12 | 2018-07-19 | 三菱電機株式会社 | Twisted tube heat exchanger and manufacturing method for twisted tube heat exchangers |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4276382B2 (en) | 2009-06-10 |
| EP1066494A1 (en) | 2001-01-10 |
| KR20010034712A (en) | 2001-04-25 |
| CN1139782C (en) | 2004-02-25 |
| WO1999050610A1 (en) | 1999-10-07 |
| CN1295663A (en) | 2001-05-16 |
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