TW200806814A

TW200806814A - A anti-oxidation method of utilizing decay electron

Info

Publication number: TW200806814A
Application number: TW95126615A
Authority: TW
Inventors: Chung-Pin Liao
Original assignee: Univ Nat Formosa
Priority date: 2006-07-21
Filing date: 2006-07-21
Publication date: 2008-02-01

Abstract

This invention utilizes beta sources with long half-life (in the order of 100 years, also meaning an extremely small decay constant) and low energy (much lower than the MeV level of many radioactive substances), such as nickel-63, to provide a cathode protection method that is non-anode, passive, durable (for instance hundreds of years), and versatile. This method may be applied to a wide range of materials (including metals, non-metals, and composite materials) under various conditions and readily to achieve anti-corrosion (anti-oxidation) purpose.

Description

200806814 九、發明說明：【發明所屬之技術領域】本發明係有關於防鏽及抗氧化，尤其有關於於一新颖、經濟的防鐘及抗氧化措施之方法。【先前技術】200806814 IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION The present invention relates to rust and oxidation resistance, and more particularly to a novel, economical anti-clock and anti-oxidation measure. [Prior Art]

腐姓，隨著時間的流逝’對於許多由金屬或非金屬製造的物體而言一向是其品質與結構完整性的莫大威脅，尤其是在對某一物體特別不利的（或，腐钱的）特殊環境下。雖然在不同的狀況下腐蚀似以許多不同的面貌出現，然而’它背後的物理基本上只是廣義的氧化作用。例如：接近海厗線的鐵橋和海面上的鑽油平台在此潮澄多鹽（且電化學腐蝕性）的環境下都很容易生銹（即··被羥基離子(〇jr) 氧化為鐵鏽：Fe(OH)2和Fe(OH)3)，即使它們都已經在防鏽漆的保護之下。類似的，即使都曾作過防鏽處理，海軍船艦、貨輪、油輪、渡輪等都會隨著時間流逝而漸漸腐蝕。在我們日常生活周圍的東西也都不免生銹，例如，車子、鐵鎚、圓鍬、冰箱、地下鐵管（被〇ίΓ離子、微生物等氧，），甚至患者體内的人工移植物（大致被含氯之諸化合物氧化）。尤其當它們表面的保護塗料被刮傷所移除，或著孔 =現象已經開始時，情況更將變得特別的糟。對鐵製品而 L個第用的防鏽作法是在其表面電鐘一層比鐵更容易被氧化的金屬（亦即，更且、苦 / 例如辞，而造成的產品 ==鐵）’或者將之製成合金（例如補鋼的目的。然而’儘管採取這樣高代價的措施，當中的^ 5 200806814 份至終仍將在該更具活性的金屬層被犧牲耗盡之後開始生銹。另外’金屬也可被氧以外的元素氧化，例如，鐵會在一個充滿硫化物的環境中腐钱（或者，電化學氧化)而至終滿佈硫化鐵（iron sulfides)的腐爛損毀。相似的情況也困擾著其他的重要金屬，例如，鋁、銅，以及它們的合金。事實上，除了金屬以外，甚至非金屬類，諸如陶瓷（ceramics，在本發明中為方便故將之歸於非金屬類，如氮化硼（boronnitride)，石墨（graphite))、有機化合物、以及聚合物（P〇lymers，例如橡膠（rubber))，都會在當匕其中的某個或數個分子群或金屬成份被外在的氧化劑（oxidizing agents)氧化之後逐日退化或分解。例 ’ 如，特別在溫度提南時，將聚合物曝露於氧氣的環境下會 • 因此而改變它的聚合結構。比如在橡膠中，氧原子會提供額外的交聯（cross-Unking)造成該橡膠變硬或者疲乏 (fatigue)(見 Ege，Seyhan，Organic Chemistry 4th ed·， φ PP· 1057-1058, Houghton Mifflin Co., New York, 1999)- 在高溫時情況將變得更糟。儘管其所造成的是一個在技術上與經濟上難以解決的問題，氧化性腐蝕（oxidative corrosion)本身的一般基礎概念卻是頗為單純的。亦即，任何的氧化反應都牽扯到搶電子的行為。第1圖以電化學電池來說明氧化性腐蝕是如何作用的（見’例如 ’ Lawrence H. Van Vlack，Elements of Materials Science and Engineering，Section 13-5, Addison-Wesley，Reading，MA，USA，1985)。在陽極 6 200806814 ( )1的這邊，在其金屬成份Μ因失去電子而變成正離子之際，（_卩：氧錄雜反應）： Μ° - r + m e- ⑴ —陽極物貝的表面開始惡化。為了讓這個反應持續進灯’上述的電子與金屬離子都必須從陽極1移除，否則，逆向反應將變得顯著而最後動H平衡將建立。請注意，陰極2通系由較不具活性的金屬，亦即比之陽極金屬μ較不具放出電子能力的金屬構成。在陰極2發生的反應可以象徵性的表示為X + n e — r，其中χ可以是來自陽極或環境的原子或離子。卿，上述陽極丨釋躺電子，經由金屬連接19 _陰極2，而在陰極2這邊由-非金屬元素Ν 接受，或被已移動到陰極2的金屬離子Mm+接收（因之，在一腐蝕過程中陰極消耗並享用電子）·· N° + n e~ Nn~ ⑵ 或，ίΓ + m e- — Μ0 ⑶ 公式（1)中的金屬離子經由溶解在周遭的環境（如：電解液），或者額外地，與非金屬離子Νη-結合，而在陰極上形成表面沈積（surface d印osit)。因此，總體而言，該陽極金屬Μ由於這樣的電化學氧化反應而遭漸漸腐餘。一個絕佳的範例是在一滴水（或其他沈積）下面的鐵會在水滴的周圍開始腐蝕。換言之，當圍繞陽極和陰極的環境存在著差異時’ 一種稱為濃度（差異）電池(c〇ncentrati〇n cell)的電化學電池便會產生。如第2圖所描述的，當鏽、微生物、或水的沈積3遮住了下方的鐵17表面時，便會使 200806814 其無法與空氣中的氧接觸（此情況稱為氧叙餓（〇Xygen starvation))。結果，陽極反應Fe〜Fe2+ + 2e_在這個低氧區（low-oxygen region) 4裡展開，導致金屬開始腐蝕，並在該沈積3的邊界’即在陰極的氧豐足區(high—胃_ region) 5之内，逐漸形成鐵鏽18。氧豐足區5之内的陰極反應為：〇2 + 2 H2O + 4 e_ — 4 Olf 以及 Fe2+ + 2 0ΙΓ -Fe(0H)2 Donald R. Askeland, The Science and Engineering of Materials, pp. 792, PWS-KENT ⑩ Publishing， Boston， MA， 1989)。樹ί電化學電池理麵推演自來的知識，各種不同的防腐蝕對策陸續的出現。它們當中的一個是原電 • (职1vanic，有直譯"伽凡尼”）（或陰極）保護，其係由設絲所祕護的產品變成陰極來達成。這又可分為利用原電池（galvanic ceU)及外加電壓或電流（impresse/、 voltage or current)的兩個不同作法。對别者而言’當不同的兩種金屬接觸在-起時，在一給定的環境條件下，-種特殊的電化學電池稱 _vaniCcell)便因之產生。在其中，於表一之電動 (emf，electromotive force)系列中佔較高位置（即· 陽極性）的金屬便成為陽極，而另一個金屬則成為陰極。例如’在-片鍍鋅的鐵上面，鋅塗佈係作為以保護底下，即使是在触未全鳄蓋住^ 面的情形下亦是如此（如：_傷而使鐵裸露的鐵是扮演陰極的角色，故不會腐兹。但是，像』: 8 200806814 裡’被裸露的鐵表面只要有沈積，例如一個水滴，也會因為形成前述的濃度電池而開始生銹（見第2圖）。此外，一俟犧牲金屬被耗盡，它所提供的陰極保護便會消失，因此例行的更新犧牲陽極將是必要的。同樣的，不鏽鋼（stainless steels)是，，不鏽”的，因為它的表面已經被更具陽極性的鉻（Cr，chr〇mium)所鈍化（passivated)，後者當接觸氧時形成氧化物薄膜。但是，假如其應用環境中具化學還原性且不具有氧，這一層被動膜便會被摧毁。沒有了這層保護，鋼變得具化學活性因而所有帶絡的鋼都將迅速腐钕（見Lawrence H. Van Vlack, Elements of Materials Science and Engineering, pp· 539， Addison-Wesley， Reading， MA， USA， 1985)。實際上，因為這樣的緣故，不少試圖改進的工夫都花在不鏽鋼、以及其他用被動膜保護的金屬上面。例如，Cuemanet al· (US Patent 5, 000, 979，March 19，1991)便提出一塗佈金屬基座（substrate)的特殊製程試圖使該金屬基座得以抵抗惡劣的環境。表一：幾個選定元素之電化學電動勢乂emf)系列* _____金屬與非金屬__ 陽極性 U — Li+ + e- K — r + e-The rotten surname, as time goes by, has always been a great threat to its quality and structural integrity for many objects made of metal or non-metal, especially when it is particularly detrimental to an object (or rotted money). Under special circumstances. Although corrosion appears to appear in many different ways under different conditions, the physics behind it is basically a generalized oxidation. For example, iron bridges close to the sea otter line and oil rigs on the sea surface are prone to rust in this sloppy (and electrochemically corrosive) environment (ie, oxidized by hydroxyl ions (〇jr) to Rust: Fe(OH)2 and Fe(OH)3), even though they are already under the protection of anti-rust paint. Similarly, even if they have been rust-proof, naval ships, freighters, tankers, ferries, etc. will gradually corrode over time. The things around our daily life are also rusting, for example, cars, hammers, round urns, refrigerators, underground iron pipes (such as Γ Γ ions, microorganisms, etc.), and even artificial grafts in patients (roughly Oxidized by chlorine-containing compounds). Especially when the protective coating on their surface is removed by scratching, or when the hole = phenomenon has begun, the situation will become even worse. The first rust prevention method for iron products is that the metal clock on the surface of the electric clock is more susceptible to oxidation than iron (that is, the product is more and more bitter / for example, the product == iron) or The alloy is made (for example, for steel purposes. However) despite the costly measures, the ^ 5 200806814 parts will eventually rust after the more active metal layer is sacrificed and exhausted. Metals can also be oxidized by elements other than oxygen. For example, iron can be rotted (or electrochemically oxidized) in a sulphide-rich environment to the rot of iron sulfides. It is troubled by other important metals, such as aluminum, copper, and their alloys. In fact, in addition to metals, even non-metals, such as ceramics, are classified as non-metallic in the present invention for convenience, such as Boron nitride, graphite, organic compounds, and polymers (P〇lymers, such as rubber), are all in one or several molecular groups or metal components. It is degraded or decomposed day by day after being oxidized by external oxidizing agents. For example, especially when the temperature is raised, the polymer is exposed to the oxygen environment. Therefore, its polymerization structure is changed. For example, in rubber. The oxygen atom will provide additional cross-Unking to cause the rubber to harden or fatigue (see Ege, Seyhan, Organic Chemistry 4th ed·, φ PP· 1057-1058, Houghton Mifflin Co., New York) , 1999) - The situation will get worse at high temperatures. Although it is a technically and economically difficult problem, the general basic concept of oxidative corrosion itself is quite simple. That is, any oxidation reaction involves the act of stealing electrons. Figure 1 shows an electrochemical cell to explain how oxidative corrosion works (see 'for example' Lawrence H. Van Vlack, Elements of Materials Science and Engineering, Section 13-5, Addison-Wesley, Reading, MA, USA, 1985). On the anode 6 200806814 ( )1, the metal component becomes positive due to the loss of electrons. At the time of the ion, (_卩: oxygen recording reaction): Μ° - r + m e- (1) - the surface of the anode object begins to deteriorate. In order for this reaction to continue into the lamp, the above electrons and metal ions must be from the anode. 1 removed, otherwise, the reverse reaction will become significant and the final moving H balance will be established. Note that the cathode 2 is made of a less active metal, that is, a metal that is less electron-emitting than the anode metal μ. The reaction occurring at the cathode 2 can be represented graphically as X + n e - r, where χ can be an atom or ion from the anode or the environment. Qing, the above anode is released from the electrons, via the metal connection 19 _ cathode 2, and on the cathode 2 side is received by the -nonmetal element , or by the metal ion Mm+ that has moved to the cathode 2 (since, in a corrosion During the process, the cathode consumes and enjoys electrons. ··· N° + ne~ Nn~ (2) or, ίΓ + m e- — Μ0 (3) The metal ions in formula (1) are dissolved in the surrounding environment (eg electrolyte), or Additionally, it combines with the non-metal ion Νη-, while forming a surface deposit on the cathode. Therefore, in general, the anode metal ruthenium is gradually rotted due to such an electrochemical oxidation reaction. An excellent example is that iron under a drop of water (or other deposit) will begin to corrode around the water droplets. In other words, when there is a difference in the environment surrounding the anode and the cathode, an electrochemical cell called a concentration (differential) cell is produced. As depicted in Figure 2, when rust, microbes, or water deposits 3 obscure the surface of the underlying iron 17, it will make 200806814 unable to contact the oxygen in the air (this condition is called oxygen hunger (〇 Xygen starvation)). As a result, the anode reaction Fe~Fe2+ + 2e_ is unfolded in this low-oxygen region 4, causing the metal to begin to corrode, and at the boundary of the deposition 3, that is, in the oxygen-rich region of the cathode (high-stomach_ Within the region 5, rust 18 is gradually formed. The cathodic reaction within the oxygen-rich foot zone 5 is: 〇2 + 2 H2O + 4 e_ — 4 Olf and Fe2+ + 2 0ΙΓ -Fe(0H)2 Donald R. Askeland, The Science and Engineering of Materials, pp. 792, PWS -KENT 10 Publishing, Boston, MA, 1989). The tree ί electrochemical cell surface deducts the knowledge of the future, and various anti-corrosion measures have emerged one after another. One of them is the original electricity • (1vanic, there is a literal translation " Gavigny) (or cathode) protection, which is achieved by the product of the secret of the silk set to become the cathode. This can be divided into the use of primary batteries ( Galvanic ceU) and two different methods of applying voltage or current (impresse/, voltage or current). For others, 'when two different metals are in contact, at a given environmental condition, - A special type of electrochemical cell is called _vaniCcell), in which the metal occupying a higher position (ie, anodic) in the electric (emf, electromotive force) series of Table 1 becomes the anode, and the other The metal becomes the cathode. For example, 'on the galvanized iron, the zinc coating is used to protect the bottom, even if it is covered with a full crocodile (such as: _ injury and iron) The bare iron plays the role of a cathode, so it will not rot. However, as in the case: 8 200806814, as long as there is deposition on the surface of the exposed iron, such as a water droplet, it will start to rust because of the formation of the aforementioned concentration battery. See Figure 2). As soon as the sacrificial metal is exhausted, the cathodic protection it provides will disappear, so routinely updating the sacrificial anode will be necessary. Similarly, stainless steels are, stainless, because of its The surface has been passivated by a more anodic chromium (Cr, chr〇mium) which forms an oxide film when exposed to oxygen. However, if the application environment is chemically reducing and does not have oxygen, this layer The passive membrane is destroyed. Without this protection, the steel becomes chemically active and all the steel with the belt will rot quickly (see Lawrence H. Van Vlack, Elements of Materials Science and Engineering, pp. 539, Addison) -Wesley, Reading, MA, USA, 1985). In fact, for this reason, many attempts to improve are spent on stainless steel and other metals protected by passive membranes. For example, Cuemanet al· (US Patent 5 , 000, 979, March 19, 1991) proposes a special process of coating a metal substrate to try to make the metal base resistant to harsh environments. Table 1: Several Selected Electrochemical Electromotive Forces 乂emf) Series * _____ Metals and Nonmetals __ Anodes U — Li+ + e- K — r + e-

Na -> Na+ + e'Na -> Na+ + e'

Mg Mg+ + e'Mg Mg+ + e'

Al — Al3+ + 3e_ 200806814Al — Al3+ + 3e_ 200806814

Ti — Ti2+ + 2e_Ti — Ti2+ + 2e_

Mn — Mn2+ 十 2e_Mn — Mn2+ ten 2e_

Zn — Zn2+ + 2eZn — Zn2+ + 2e

Cr ^Cr2+ + 2e_Cr ^Cr2+ + 2e_

Fe — Fe2+ + 2e_Fe — Fe2+ + 2e_

Ni Ni2+ + 2eNi Ni2+ + 2e

Sn — Sn2+ + 2e-Sn — Sn2+ + 2e-

Pb Pb2+ +2e_ H2 — 2H+ + 2e-Cu—Cu2+ + 2e_ 4(0H ) O2 + 2H2〇 + 4e-Fe2+ — Fe3+ + e-Ag—Ag+ + e_Pb Pb2+ +2e_ H2 — 2H+ + 2e-Cu—Cu2+ + 2e_ 4(0H ) O2 + 2H2〇 + 4e-Fe2+ — Fe3+ + e-Ag—Ag+ + e_

Pt Pt4+ + 4e" 2H2O O2 + 4H+ + 4e' 極性_—— Au -> Au3+ + 3e~ ^ *在25°C, —大氣壓及丨M離子濃度之下。假若離子/辰度不疋1 M，則必須使用Nernst公式（見前述文獻) 來決定新排序。至於在外加電壓（或電流）的作法裡，一個小的直流 (DC)電壓（例如取自一個一般3—5伏特的電池）在欲保濩的產品上維持一個負電位（相對環境中的一個參考接地點（reference ground))，使成陰極。對於报多的應用場合，包括埋藏在地底下的設備（如：天然氣管路）和汽車 200806814 ^ 賴’這樣的作法有效的達到了防鏽的效果。甚至，—此本已遭鐵_始攻擊的區域也相為所提供的帶負電_ 瞻1£輯如復。_，這_財軒瓣點。首先，即便^需的陽極電流一般不大，但為了維持這樣的陰極保護’有必要常態、定期的更新或保修電源。當所面對的是 -個具高度雜（舰氧化）性的環境時，因為必須持續的消耗大的陽極電流’這樣—來，的更新或保修需要便會成為重大的缺點^次，這種作法需要一個實體的陽極，而它自己也因會雜喊要定_換。再者，這樣的陰極保護細餘，除非所觸陽極尺稍大。第三點，由陽極所放出的所謂迷散電流（straycurrent)會導致對 • 鄰近設備的不良干擾進而造成其腐钱。換句話說，由陽極 ‘ 端流出來的直流電在其最終抵達陰極（即··以陰極法保護的產品）之前的各個迷散路徑上，會額外的將鄰近的其他 -— 設備變為次等陽極（secondary anodes )因而使他們開始 φ 腐蝕。最後一點，在實際工程應用上，直流電源的極性因失誤而被反接是-件常常發生的事，這樣的話，反而會導致所欲防鏽的產品更加速的腐蝕生銹。、最近’一項新的、"被動的”外加電壓作法被提出來並加以展示，其係由以二氧化鈦（titanium 〇xide (Ti〇2)) 太陽能面板收集陽光來提供陰極保護法所需的電壓（見Pt Pt4+ + 4e" 2H2O O2 + 4H+ + 4e' Polarity _—— Au -> Au3+ + 3e~ ^ * at 25 ° C, under atmospheric pressure and 丨M ion concentration. If the ion/length is less than 1 M, then the Nernst formula (see above) must be used to determine the new order. As for the applied voltage (or current), a small direct current (DC) voltage (for example, taken from a typical 3-5 volt battery) maintains a negative potential on the product to be protected (relative to one in the environment). Refer to the ground (reference ground) to make the cathode. For the application of the newspaper, including the equipment buried under the ground (such as: natural gas pipeline) and the car 200806814 ^ Lai's effective rust-proof effect. Even, the area that has been attacked by the iron _ is also provided with a negative charge. _, this _ 财轩瓣点. First, even if the required anode current is generally small, it is necessary to maintain the normal, periodic update or warranty power supply in order to maintain such cathode protection. When faced with a highly heterogeneous (ship oxidizing) environment, because of the need to continuously consume large anode currents, the update or warranty requirements will become a major disadvantage. The practice requires an anode of the entity, and it itself has to be fixed because of the screaming. Moreover, such cathodic protection is fine unless the anode scale is slightly larger. Third, the so-called stray current emitted by the anode can cause undesirable interference to nearby devices and cause it to rot. In other words, the direct current flowing from the anode 'end will additionally infer the neighboring other equipment to the inferior path before it finally reaches the cathode (ie, the product protected by the cathode method). The secondary anodes thus cause them to begin φ corrosion. Finally, in practical engineering applications, the polarity of the DC power supply is reversed due to mistakes. This often causes things to happen, which in turn leads to more accelerated corrosion and rusting of the desired rust-proof product. Recently, a new, "passive" applied voltage method was proposed and demonstrated, which is required to provide cathodic protection by collecting sunlight from titanium dioxide (Titanium 〇xide (Ti〇2)) solar panels. Voltage (see

Park H· etal·，J· Phys· Chem· B，106，4775-4781， 2002)。第3圖展示它的一個建議應用，其中，一個地面上的光陽極（photoanode) 6 (覆蓋於一 IT0 (銦錫氧化物） 11 200806814 破璃16 (即透光導電板）保護-個地下鋼鐵結構9。雖二:有電’同消除器7) 電池或其他電源8,這樣的作:==仍需要使用源更新或保修的需求。已經大幅的放見了定期的電 ^ ’值得注意的是，前述的作法需要—個持績的電流（在1〇 “A的勃旦&、七穴而 i = 9 m ^ 里、、及）來維持所需的外加電壓。 =疋口為，g在沒有日晒之紫外光作用下，—個鐵陽極 2域陰極的電化學電池自然形成，硫#中的. =意也;T:所可能暗示予'、，）。由贿魏轉極雜反舰轉，亦即使鐵 =陰極（鱗域祕護法），—她#大㈣子流必須由讓太陽的紫外光照射二氧化鈦面板來提供（見前述文、獻）。因此，_顯的，要在較大的產品上實施此種"被動" 外加電壓保5蔓法’意味著必須使用較大的太陽能面板。因此之故，相_經濟考量與實際顧上料與否的問題都會^繼出籠。更何況，如在提出公式⑴時所提到的，此^案也需要電祕關（hQlesseavenger)來維持這個太陽能陰鱗護反應麟續妨。就這點而言，這個"被動 η防腐蝕作法的有效性將隨著在電洞驅除劑中金屬離子濃度的變化而隨時變化。無可避免的，這些都將增加此前案在實際應用上額外的複雜度，使得這個太陽能陰極保護作法無法適用於需要能變通、適合多用途的(versatile)情況。更有甚者’正如同其他習知的陰極保護前案，亦即除了上述指出的缺點外，它也不能免於濃度電池的威脅，後 12 200806814 者要在產(如·鐵）上有不均勻的沈積物時便會發生進而開始腐姓效應。回顧人類的歷史，龐大的資源與腦力一直都未停的被投注於防鏽與抗氧化的諸多措施上，包含油漆、合金的使用、以及對有機化合物和不同配方的食品所用的各式添加料，更不用談各式的塗佈、製造與應用的細節。然而，至今的成效似乎總離令人滿意尚有一段距離。【發明内容】 • 本發明的第-個目的係提供一個被動（passive)以及夕用途（versatile)的方法以普遍容易地在廣泛的情況下，在多種物質上達成長久抗腐蝕的目的。本發明的第二個目的是提供一個具經濟價值、能防止廣義氧化、甚至具還原能耐的方法，其並且能容易的被應用在金屬與非金屬之上。本發明的第二個目的為提供一個被動(passive)與普遍谷易採用（robust)的防鏽法，其係可直接應用在已完成的奈米產品上。本發明的再一個目的是提供一個創新的外加電壓抗腐钱法’其中並不需要電源、陽極、電洞消除劑、以及陽極與陰極間的金屬連接。本發明的最後一個目的係提供一個新穎的陰極保護法，其並不會引致由迷散電流造成的鄰近設備腐蝕。上述諸目的之達成皆有賴於提供一個創新的陰極保護法’其中為了將產品置於負電位（即成為陰極）所需的外 13 200806814 加電壓係由具長半衰_貝靖源（beta emitters)，如鎳一63，所維持，而並非由外加的電源供應。作為鎳 (nickel ’Νι)的一個同位素（is〇t〇pe)，鎳—肋是一個具 100年半衰期（half-life)的純貝它（即：帶能量的電子）射源’其中半衰期（half-life)是指一定量（重量）的放射性同位素（radioisotGpe)在勒形成穩定核(对牆 nucleus)的過程中，當其放射活性（radi〇activity)衰減至-選定初始值的—半所需要的_。從前述原電池 (galvanic cell ’或譯"伽凡尼"電池）峨點，現在的貝它射源正是以比鐘更高的電活性（即：更高的放出電子的能力，見表一）在發揮原來的犧牲陽極的功能，因之並不像傳統的外加電壓作法需要—個物輯極。事實上，由鐵 -63所射出的貝他粒子（即電子）個個帶有約的本均能量’因此，是飛過去，而非僅是流過去，到達所欲保護的產品上。所以，欲完成陰極保護所需的外加電屋在本發明中是由_極少數的貝它雜（見實麵丨巾之計算以被動的方式（即··無外加電源）達成u 變過程（beta decay process)為： 2sNi63 -> 2qCu63 + e~ (4) 中衰變產物銅-63是一個穩定核，亦即其不會再進 4丁哀變。此外，在習知的鋅（陽極）—鐵（陰極）_ 法中（亦即：利用表一中的陽極性金屬作為犧牲陽極），録離子（Zn)峨妓在钉 200806814 個平衡值。當因為有刮傷轉致底下的鐵裸露出來時，此 -平衡態便被大幅的改變，制是t裸露的鐵表面又有鹽水的沈積峨濃度差異魏自然形成時。亦即，在後者的情況下，由於在此間天然的電洞驅除劑僅為鋅電鍍上方的空氣與靜止不_油漆，触職剌傷區域之具保護鐵作用的犧牲陽極反應zn 4紀+化並不足以有效的映蔽 Fe — Fe + 2e的鐵腐蝕反應。與此相較的，在本發明的馨方法中，電洞驅除劑是不需要的，因為鎳一63只是自發 (spontaneously)而有效率的透過貝他粒子放射來逐漸^ 變成電中性的穩定核銅一63 (見公式（4))，並不會留下正電荷需要處理。另外’由於在氧叙餓區域（〇xygen stan^ationregion) 40 (見第4圖）中本來的陽極反應化 —Fe + 2e會被埋藏於鐵表面的塗佈或者在鐵2〇本身中的貝他射源所放出的大量電子所阻礙，甚至逆轉，因而也能有效的避免如第2圖所描述的濃度電池形成過程（第4 ⑩ 圖中尚有··沈積10、含鎳~63的鐵20、和氧豐足區域 (oxygen-rich region·)。就這點而言，比之現存的各種陰極保護法，本發明由於能強力的阻礙及逆轉本來的陽極腐蝕反應，因而更能提供一個將初始鏽（initial—phase rust)還原的有效措施。在達到抗微生物目的上，除了可以直接對付由這些微生物系統所帶來的氧化作用以外，本發明的方法也可以轉而對上述諸微生物系統本身扮演抗代謝物 (anti-metabolite)的角色。如今人們已熟知，高等動物與 15 200806814 β 低等微生物的生化維生機制有一大比例是相似的，例如，重要有機化合物的合成’像阿米諾酸（amino acids)與維生素，以及為了營養供應所作的對各種化合物的繁複氧化一還原過程（見，例如：Solomons，T. W. Graham， Fundamentals of Organic Chemistry, 5th Ed，pp. 878-881，John—Wiley & Sons，New York, 1997)。本發明的方法具有被動與抗氧化的特性，亦即利用埋藏在油漆、包裝、合金等内之貝他射源，如鎳一63，能自然的阻礙這 ® 些諸如細菌等微生物系統内的重要維生氧化反應，而最終將這些微生物從所欲保護的產品上驅離。至少有數種具長半衰期的貝他射源可供本發明的方法採用。除了前述的鎳一63 (Ni-63，半衰期1〇〇年，66 keV 貝他粒子）以外，尚有例如：鎘一 113(Cd-113,半衰期13.7 年，590 keV貝他粒子），以及鉻一99 (Tc-99，半衰期2· 13 xl〇5年，293 keV 貝他粒子)（見，例如，chart of Nuclides， ⑩ General Elec^ic Company, 1984)。鎳一63 可以很直接的透過2sNi62(n，9〇祕严反應來得到，例如，以由核子反應爐導引出來的熱中子轟擊穩定核鎳一62 (自然豐度（natural abundance) : 3· 59 %，熱中子吸收截面：ΐ4· 5 邦（barn)， 1邦=10 24 cm2)。上述的核反應係採用通用的表示式 A(a,b)B，其中乾原子核"a”被拋射粒子（或輻射線），,a" 轟擊後質變為原子核以及釋出粒子（或輻射）"b"。另外，V代表熱中子（具約〇· 025 eV能量），而” r”代表伽瑪射線（gammaray)。類似地，鎘一 113也可由對穩定核鎘 16 200806814 ’ —112 (Cd—112 ’自然豐度：24· 13 %，熱中子吸收截面： 2· 2邦）進行(〇，τ)反應來得到。至於錨一99，由對翻一 98 (Mo-98，自然豐度：24· 13 %，熱中子吸收截面·· 〇· 132 邦）進行核種轉變至少有兩條途徑可得到。一個是透過 42Mo (p，7 )43Tc反應，其中p代表質子（即氫離子）；另一個則是透由42Mo98(n，7〇4逼〇99反應，以及接著一個約邸小時半衰期的衰變（以上見，例如，Chart 〇f Nuclides， • General Electric Company， 1984)。由鎳~63所射出、個個攜帶約661^7動能的貝他粒子 (即電子）’由於能量太低甚至無法穿透人體皮膚最外面的一層，因之並不會對人類構成任何輻射的威脅。更何況，， =於在本發明的方法中’這些貝他射源變成是諸如油漆（待施加於不同產品上）、包裝、生醫材料、合金（如：電銲用的共熔相（eutectics)銲料）、陶瓷、或聚合物等物質的一部份，因此這些電子更進一步的被該物質中的其他原子 • 及分子慢化（slowed d〇wn)而再度降低能量。尤其是，我們僅需要極少量的錄—63便足以實現本發明的新顆陰極保護法（見實施例1中之計算）。即便是在一些特殊的情況中可能需要使用較大量的鎳—63，這樣的情況也大半會是相關於極具腐蝕性而較偏遠的場合，因而通常也不至於對人們的居住環境構成麟。事實上，對於像上财特殊情況，即使採用其他較高能量的貝他射源也可能是頗為可行的。生產與應用放射性同位素，包括具相對低能量的貝他射源，都必須遵照相關核能管制單位所制定的安全規範。 17 200806814 在我國為原子能委員會，在美國為核能管制署（Nuclear Regulatory Commission (NRC))，在國際上則為國際原子能總署（International Atomic Energy Agency (IAEA))。通常，在鎳一63的使用上，超過約5 x 104Bq (或，1· 35 #Park H. et al., J. Phys Chem. B, 106, 4775-4781, 2002). Figure 3 shows a suggested application, in which a photoanode on the ground 6 (covered on an IT0 (indium tin oxide) 11 200806814 broken glass 16 (ie, light-transmissive conductive plate) protection - an underground steel Structure 9. Although two: there is an electric 'with canceller 7' battery or other power supply 8, such a work: == still need to use the source update or warranty requirements. It has been widely seen that the regular electricity ^ 'It is worth noting that the above-mentioned approach requires a current of performance (in 1 〇 "A's Bodan &, seven points and i = 9 m ^, and ) to maintain the required applied voltage. = 疋 mouth is, g in the absence of sunlight, the electrochemical cell of the iron anode 2 domain cathode naturally formed, sulfur #. = meaning also; T: It may be implied by ',,). From bribery to extremely anti-ship rotation, even if iron = cathode (scale secret method), - her #大(四) substream must be provided by the sun's ultraviolet light illuminating the titanium dioxide panel (See the above article, offer). Therefore, _ obvious, to implement this type of "passive" on a larger product, "applied voltage protection 5 vine method" means that a larger solar panel must be used. Therefore, Phase _ economic considerations and actual considerations or not will be followed. Not to mention, as mentioned in formula (1), this case also requires the electric secret (hQlesseavenger) to maintain this solar yin Responding to the continuation of the ruling. In this regard, this "passive η anti-corrosion practice has Sex will change with the change of metal ion concentration in the hole repellent. Inevitably, these will increase the additional complexity of the previous case in practical applications, making this solar cathodic protection method unsuitable for the need. Flexible, suitable for multi-purpose (versatile) situation. What's more, just like other conventional cathodic protection cases, that is, in addition to the above-mentioned shortcomings, it is not immune to the threat of concentration battery, after 12 200806814 When there are uneven deposits on the production (such as · iron), it will start to start the rot effect. Reviewing the history of mankind, huge resources and brain power have been bet on rust and oxidation resistance. In terms of measures, including the use of paints, alloys, and various additives for organic compounds and foods of different formulas, not to mention the details of coating, manufacturing and application. However, the results so far seem to be always There is still a distance between people's satisfaction. [Summary] The first object of the present invention is to provide a passive and versatile The invention aims to achieve long-term corrosion resistance on a wide variety of substances in a wide range of conditions. The second object of the present invention is to provide a method which is economical, can prevent generalized oxidation, and even has a reduction ability, and It can be easily applied on metal and non-metal. The second object of the present invention is to provide a passive and universal rust-proof method, which can be directly applied to the completed 奈A further object of the present invention is to provide an innovative applied voltage anti-corrosion method which does not require a power source, an anode, a hole eliminator, and a metal connection between the anode and the cathode. A novel cathodic protection method is provided which does not cause corrosion of adjacent equipment caused by faint current. The above objectives are all achieved by providing an innovative cathodic protection method, which is required for the product to be placed at a negative potential (ie, becomes a cathode). 13 200806814 The voltage system consists of a long half-fade_beta emitters ), such as Ni-63, is maintained and not supplied by an external power source. As an isotope of nickel (nickel 'Νι), a nickel-rib is a 100-year half-life pure beta (ie, electron with energy) source's half-life ( Half-life refers to a certain amount (weight) of radioisotope (radioisotGpe) in the process of forming a stable nucleus (for wall nucleus), when its radioactivity (radi 〇 activity) decays to - the initial value - half needs_. From the aforementioned galvanic cell 'or galvanic cell', the current beta source is a higher electrical activity than the clock (ie: higher ability to emit electrons, see Table 1) is playing the role of the original sacrificial anode, so it is not like the traditional applied voltage method. In fact, the beta particles (i.e., electrons) emitted by the iron-63 have a mean energy of about ‘and therefore fly over, not just flow past, to the product to be protected. Therefore, the external power house required to complete the cathodic protection is in the present invention by a very small number of beta hybrids (see the calculation of the solid wipes in a passive manner (ie, without an external power supply) to achieve a u-change process ( The beta decay process is: 2sNi63 -> 2qCu63 + e~ (4) The decay product copper-63 is a stable core, ie it will not change further. In addition, in the conventional zinc (anode) - Iron (cathode) _ In the middle of the process (that is, using the anodic metal in Table 1 as the sacrificial anode), the recorded ion (Zn) 峨妓 is at the equilibrium value of the pin 200806814. When the iron is exposed due to the scratch When it comes out, this-equilibrium state is greatly changed. The system is the difference between the exposed iron surface of the t-exposed iron and the sediment concentration of the salt. When the latter is formed naturally, that is, in the latter case, due to the natural hole excavation here. The agent is only the air above the zinc plating and the static non-paint. The sacrificial anode reaction with protective iron action in the contact injury area is not enough to effectively reflect the iron corrosion reaction of Fe-Fe + 2e. In contrast, in the fragrant method of the present invention, the hole The removal agent is not required because the nickel-63 is only spontaneous and efficiently passes through the beta-particle radiation to gradually become electrically neutral, stable nuclear copper-63 (see formula (4)), and will not remain. The positive charge needs to be treated. In addition, due to the anodic reaction in the oxygen stagnation region (see Figure 4), the original anode reaction - Fe + 2e will be buried in the iron surface coating or in iron 2 The large amount of electrons emitted by the beta source in itself is hindered or even reversed, so that the formation process of the concentration battery as described in Fig. 2 can be effectively avoided (there is still deposition in Fig. 4). The iron 20 containing nickel ~ 63, and the oxygen-rich region (oxygen-rich region). In this regard, the present invention is capable of strongly hindering and reversing the original anodic corrosion reaction, compared to various existing cathodic protection methods. Therefore, it is more effective to provide an effective measure for reducing the initial-phase rust. In addition to being able to directly deal with the oxidation caused by these microbial systems, the method of the present invention can also be transferred. The above-mentioned microbial systems themselves play the role of anti-metabolites. It is now well known that higher animals are similar to a large proportion of the biochemical biosynthesis mechanisms of 15 200806814 β lower microorganisms, for example, the synthesis of important organic compounds. 'Amino acid and vitamins, as well as complex oxidation-reduction processes for various compounds for nutrient supply (see, for example: Solomons, TW Graham, Fundamentals of Organic Chemistry, 5th Ed, pp. 878- 881, John-Wiley & Sons, New York, 1997). The method of the present invention has the characteristics of passive and anti-oxidation, that is, the use of a beta-ray source buried in paint, packaging, alloy, etc., such as nickel-63, can naturally hinder the importance of such a microbial system such as bacteria. The vitamins are oxidized and eventually these microorganisms are driven away from the product to be protected. At least a number of beta injection sources having a long half-life can be employed in the method of the present invention. In addition to the aforementioned nickel-63 (Ni-63, half-life of 1 year, 66 keV beta particles), there are, for example, cadmium-113 (Cd-113, half-life 13.7 years, 590 keV beta particles), and chromium One 99 (Tc-99, half-life 2·13 xl 〇 5 years, 293 keV beta particles) (see, for example, chart of Nuclides, 10 General Elec^ic Company, 1984). Nickel-63 can be obtained directly through the 2sNi62 (n, 9 〇 secret reaction, for example, by the thermal neutron bombardment guided by the nuclear reactor to stabilize the nuclear nickel-62 (natural abundance: 3· 59 %, thermal neutron absorption cross section: ΐ4·5 邦 (barn), 1 邦=10 24 cm2). The above nuclear reaction system uses the general expression A(b,b)B, in which the dry nucleus "a" is ejected Particles (or radiation), a" after bombardment, become metanuclear and release particles (or radiation) "b" In addition, V stands for thermal neutron (with about 〇 025 eV energy), and "r" stands for gamma Similarly, cadmium-113 can also be carried out on stable nuclear cadmium 16 200806814 '-112 (Cd-112 'natural abundance: 24.3%, thermal neutron absorption cross section: 2.2 state) (〇 , τ) reaction to obtain. As for anchor 99, there are at least two ways to carry out nuclear transformation by turning 98 (Mo-98, natural abundance: 24.3%, thermal neutron absorption cross section · · · · · · · · · Available. One is through 42Mo (p,7)43Tc reaction, where p represents proton (ie hydrogen ion); One is through the 42Mo98 (n, 7〇4 forced 99 reaction, and followed by a decay of about half-life of the hour (see, for example, Chart Nuf Nuclides, • General Electric Company, 1984). From nickel to 63 Shooting, each of the beta particles (ie, electrons) carrying about 661^7 kinetic energy 'because the energy is too low to penetrate the outermost layer of human skin, it does not pose any radiation threat to humans. Moreover, In the method of the present invention, 'these beta sources become such as paint (to be applied to different products), packaging, biomedical materials, alloys (eg, eutectics solder for electric welding), a part of a substance such as ceramics or a polymer, so that these electrons are further slowed down by other atoms and molecules in the substance. In particular, we only need a very small amount. Recording - 63 is sufficient to implement the new cathodic protection method of the present invention (see calculation in Example 1). Even in some special cases, it may be necessary to use a larger amount of nickel-63. Most of the time, it will be related to extremely corrosive and remote occasions, so it usually does not constitute a lining for people's living environment. In fact, for the special case of Shangcai, even other high-energy beta mobile sources are used. It may be quite feasible. The production and application of radioisotopes, including beta-ray sources with relatively low energy, must comply with the safety regulations established by the relevant nuclear energy control unit. 17 200806814 The Atomic Energy Commission in China, the Nuclear Regulatory Commission (NRC) in the United States, and the International Atomic Energy Agency (IAEA) in the international arena. Usually, in the use of nickel-63, more than about 5 x 104Bq (or, 1. 35 #

Ci’ 其中 ICi (居里）= 3.7xl01Gdisintegration/s(^pCi’ where ICi (Curie) = 3.7xl01Gdisintegration/s(^p

Bq，亦即Becquerel))的制定臨界量則必須擁有這些單位的營運管制執照。反過來說，對一個產品，或積集的一堆產品，當其所含的鎳一63放射活性（radioactivity)低於上述的臨界值，則原則上便只要維持記錄並報告相關管制單位就可以逕行營運。在底下的實施例中將可以知道本發明的方法可以很容易的在遵循上述安全規範下加以實現 (見實施例1中之計算）。【實施方式】為使貴委員對本發明之特徵、目的及功效，有更加深入之瞭解與認同，兹列舉較佳實施例並配合圖式說明如后：底下提出幾個本發明的實施例。 1·以含貝他射源的油漆或塗料保護鑄鐵和鋼對許多工業而言’鑄鐵（east irGns)與鋼（S細is) 兩者都是非常重要的基礎材料。然而它們也都—直面臨著嚴峻的生_題。因此，每年單是花在對它們作各種防鐘努力的經費便在世界各地都佔了國民生產毛額（GNPS)的可觀比例’儘管問題健存在。在此實施例中，本發明的方法以下_方式實現’脚將具有長半衰期的貝他射源 18 200806814Bq, also known as Becquerel)), must have an operational control license for these units. Conversely, for a product, or a collection of products, when the nickel-63 radioactivity is lower than the above-mentioned critical value, in principle, as long as the record is maintained and the relevant regulatory unit is reported. Running. It will be appreciated in the following embodiments that the method of the present invention can be readily implemented following the above-described safety regulations (see calculations in Example 1). [Embodiment] For a better understanding and recognition of the features, objects, and advantages of the present invention, the preferred embodiments and the accompanying drawings are illustrated as follows: Several embodiments of the invention are set forth below. 1. Protecting cast iron and steel with paint or paint containing a beta source For many industries, both cast iron (east irGns) and steel (S thin is) are very important base materials. However, they are also facing a serious problem. Therefore, the annual expenditure on all kinds of anti-clock efforts for them has accounted for a considerable proportion of gross national product (GNPS) in all parts of the world, although the problem persists. In this embodiment, the method of the present invention achieves the following: a footstep source with a long half-life 18 200806814

置=漆或_ ’而後再將之施加於由鑄鐵或鋼所製成的產品表面。換言之，現在’由於這些產品_收從這樣的油漆或塗卿㈣電子而帶有負電位，致使—個新賴、被動、而且耐久的外加電壓陰極保護在這些產品上建立。第5 圖描述一個例子，其中鐵結構係由帶鎳-63的油漆80所保護，而油義之上的額外塗你12〇則可視需要選或不施加。請注意，所有的舰電子⑽皆由的油漆80所射出。 ^ 63 底下將以個估异來展示：以本發明的方法來提供建立陰極保護法所需的負電位是件容易而直接的事。取二個具有大的半徑R的圓形鐵盤作例子。如果它上面的面電荷 f 度（^surface charge density)是σ (= Q/A，Q 為總電荷，Α是該鐵盤面積），則電位沿著垂直於鐵盤面（ζ = 〇) 之中央ζ軸的方向作變化（見Haus，HermanA.，Place = paint or _ ' and then apply it to the surface of the product made of cast iron or steel. In other words, nowadays, because of the negative potential of these products, such as the paint or the coating (4) electrons, a new, passive, and durable applied voltage cathodic protection is established on these products. Figure 5 depicts an example in which the iron structure is protected by a paint 80 with a nickel-63, and an additional 12 coats above the oily one may or may not be applied. Please note that all ship electronics (10) are shot by paint 80. ^ 63 Bottom will be shown by an estimate: it is easy and straightforward to provide the negative potential required to establish cathodic protection by the method of the present invention. Take two circular iron plates with a large radius R as an example. If the surface charge density above it is σ (= Q/A, Q is the total charge, Α is the area of the iron plate), then the potential is along the center perpendicular to the surface of the iron plate (ζ = 〇) The direction of the ζ axis changes (see Haus, HermanA.,

Electromagnetic Fields and Energy， 5th Ed·， pp 104-105，Prentice Hall, NJ，1989，以 SI 國際單位呈現），其為： ……：.....Electromagnetic Fields and Energy, 5th Ed·, pp 104-105, Prentice Hall, NJ, 1989, presented in SI International), which is: ...:.....

當中ε。= 8·85 X 1〇-12 Farad/meter是真空的介電係數 (permittivity)。理論上，電位參考值〇是在離鐵盤無限遠處（即ζ ~> 〇〇)。但是，為了實用上的目的，只要在，例如，距離z > 2R時，我們便能將該點之φ定為φ〜〇參考電位，而將公式（5)中之電位φ視為在ζ處之近似電位值。假如一開始施加在鐵盤上的鎳一63總數為ΝΑ〇，則總 200806814 ，何便為Q =隐〇 (-e)(即一般在此起始階段，電子漏失於環境的速率遠小於電子載入的速率時），e =丨.6 X i〇_19 c 是單電子電荷，而N〜NA〇x(l-elt)，其中又=2 2 χ 1〇一1〇 S是鎳〜63的衰變常數，而t則代表自施加本發明的塗佈後所經過的時間。所以，由公式⑸，當R》z(即：近鐵盤表面）時，可見：Where ε. = 8·85 X 1〇-12 Farad/meter is the permittivity of vacuum. In theory, the potential reference value 〇 is at infinity from the iron plate (ie ζ ~> 〇〇). However, for practical purposes, as long as, for example, the distance z > 2R, we can set the φ of the point to the φ~〇 reference potential, and the potential φ in the formula (5) as the ζ Approximate potential value. If the total number of nickel-63 applied to the iron plate is ΝΑ〇, then the total 200806814, why is Q = concealment (-e) (that is, generally at this initial stage, the electrons are lost to the environment at a much slower rate than the electrons. When loading rate), e = 丨.6 X i〇_19 c is a single electron charge, and N~NA〇x(l-elt), where again = 2 2 χ 1〇1〇S is nickel~ The decay constant of 63, and t represents the time elapsed since the application of the coating of the present invention. Therefore, from equation (5), when R"z (ie: near the surface of the iron plate), it can be seen:

〜一 (6) • tR〜lm，而鎳一63亦僅有極小的量，例如NAq〜6 〇2 χ 1(p (亦即·一百億分之一莫耳（mole)，或者，重量約0 〇〇6 #g)時，只要費大約36小時便能讓鐵盤上的電位達到一5 伏。接下去，一個在電子供應與漏失之競爭下的平衡點將 ^建立，然而它的實際電位數值將依實際情況而決定。像逆樣達成的陰極保護可以持續超過1〇〇年。至於相關的最大放射/舌性為又編，亦即1· 3 X 1〇4 Bq (遠小於1〇5 Bq)，可以报容易的符合各個核輻射管制規範。儘管如此，在那些 _ ^有鬲度腐蝕性的特殊情況中（亦即，電子漏失相當可觀時），使用較高濃度的貝它射源可能是需要的，然而對這樣的操作，更嚴格的控管將是必要的。另外，不像習知的陰極保護作法，其皆因各外在因素所引致的濃度電池形成（見第2圖）而仍然受到腐儀的威脅’本發明的方法則以提供豐足的貝他電子逆轉Fe —以+ + 2e反應，進而壓制濃度電池的形成，或者更精確地，氧飢鑛極（oxygen-starved an〇de)的產生（見第4圖）。此外’非但不像傳統外加電壓法（其完全依賴所使用的陽 20 200806814 二2成封閉電迴路）會對鄰近設備帶來迷散電流引致私f相反的’本發明之貞他射騎射㈣帶負電的迷、子則g對這些鄰近設備提供它們本來沒有的額外陰極保護。換姑說，由於實現本發·不需要—個封閉的電 2坦路’ ^鋪近設純地被迷散絲的貝他電子牙戴上負，使它們不會魏陽極，因聽不會腐钱。、、有好幾個綠可崎貝他綱導人油漆以及其他塗佈材料、(含·烟漆（laequers))之巾，貝他射源在被加 =該塗佈物貝中之前—般係為微細粉末的形式，而每一個 ;刀末顆粒’、有小於1QQ游的直徑。例如，使用從研究用原子爐導引出來的熱中子轟擊鎳_62的微細粉末便可以直接產出富含鎳-63的微細粉末。或者，可以將相同的方法用在鎳-62金屬薄片上以得到富含鎳一⑽的樣本，接著再將 ^溶於猶（nitHeaeid) _為赠錄於魏或鋼製 =表面的溶液，而硝酸本身則在最後蒸發掉。後者的方式還有額外的好處，亦即，當鐵遇到硝酸時，鐵表面迅速而均勻的被腐蝕而形成一層薄而具保護作用的氫氧化物 (hydroxide)塗佈’因而額外的達成所謂的”陽極保護"（見 Donald R. Askeland, The Science and Engineering of~ one (6) • tR~lm, and nickel-63 is also only a very small amount, such as NAq~6 〇2 χ 1 (p (that is, one billionth of a mole), or, weight At about 0 〇〇6 #g), it takes about 36 hours to get the potential on the iron plate to reach 5 volts. Next, a balance point in the competition between electron supply and loss will be established, but its actual The potential value will be determined according to the actual situation. The cathodic protection achieved by the reverse sample can last for more than 1 year. As for the related maximum radiation/tongue, it is also programmed, that is, 1·3 X 1〇4 Bq (far less than 1) 〇5 Bq), can be easily reported to comply with various nuclear radiation control regulations. However, in those special cases where _ ^ is highly corrosive (that is, when electron leakage is considerable), use a higher concentration of beta. A source may be needed, but for such operations, tighter control will be necessary. In addition, unlike conventional cathodic protection practices, the concentration of cells due to external factors is formed (see section 2)) and still threatened by the rotator' method of the present invention to provide sufficient Beta-Electronics reverses Fe—reacts with + + 2e, which in turn suppresses the formation of a concentration cell, or more precisely, the generation of oxygen-starved an〇de (see Figure 4). The traditional applied voltage method (which relies entirely on the use of the yang 20 200806814 22-inch closed circuit) will bring the faint current to the neighboring device, which will lead to the opposite of the private invention. Then g provides these neighboring devices with additional cathodic protection that they did not have. In other words, because of the implementation of this hair, there is no need for a closed electrical 2 Tan Road ' ^ paved near the purely fascinated beta electronic teeth Put on the negative, so that they will not be Wei anodes, because they will not rot money. There are several green sakisaki shells paint and other coating materials, (including laquerers) towels, The beta injection source is in the form of a fine powder before being added to the coating, and each; the end of the particle 'has a diameter less than 1QQ. For example, using the atomic furnace from the research The hot neutrons that come out bombarding the fine powder of nickel _62 can be straight A fine powder rich in nickel-63 is produced. Alternatively, the same method can be used on a nickel-62 metal foil to obtain a sample rich in nickel one (10), and then dissolved in y (nitHeaeid) _ as a gift In Wei or steel = surface solution, and nitric acid itself is evaporated at the end. The latter way has the added benefit that when the iron encounters nitric acid, the iron surface is quickly and uniformly corroded to form a thin layer. And the protective hydroxide coating' thus additionally achieves the so-called "anode protection" (see Donald R. Askeland, The Science and Engineering of

Materials, pp. 797, PWS^KENT Publishing, Boston, MA, 1989) 〇明注忍，在本實施例的精神下，本發明的方法涵蓋所有已經例行地被使用於各種情況中的一般油漆與塗佈的作法。它們包括，例如，粉刷油漆、粉體塗裝（p〇wder㈣ 200806814 ting)、熱喷霧塗裝（thermal spray coating)、擴散塗裝（diffusion coating)、化成皮膜（conversi〇n co ating)、電沈積（electro-deposition)、非電鍍沈積 (electroless deposition)、電鍛（electroplating) 、陽極處理（anodizing)等等，而且可被用於車輛、橋樑、電塔、工具等等。在一些情形裡，當所採取的塗裝方式為電沈積或非電It沈積時，所用的鎳一63則身兼負電載子提供者與放射性同位素的兩個雙重角色。與此相較的，Materials, pp. 797, PWS^KENT Publishing, Boston, MA, 1989) In the spirit of the present embodiment, the method of the present invention covers all general paints that have been routinely used in various situations. Coating method. These include, for example, stucco paint, powder coating (p〇wder (4) 200806814 ting), thermal spray coating, diffusion coating, conversi〇n co ating, electricity Electro-deposition, electroless deposition, electroplating, anodizing, etc., and can be used for vehicles, bridges, electric towers, tools, and the like. In some cases, when the coating method employed is electrodeposition or non-electric It deposition, the nickel-63 used has both the dual roles of negatively charged carrier and radioisotope. Compared with this,

Hampikian 和Scott (Patent PCT/US99/19998， May 25， 2000)所揭示的溶液都包含至少一種溶解的載子金屬離子，以及一種懸浮於溶液中但不溶解的放射性同位素或其化合物。 2·製造内含貝他射源的新穎鋼、合金、陶瓷、複合材料、以及聚合物，作為新的抗腐蝕材料在此實施例中，貝他射源，如鎳_63，是在製造產品的時候被放入而成為新產品的一部份。產品製造過程，如金屬熔融，的高溫並不會對這些貝他射源造成損害，因為像這些平常的熱（即·只要不是能造成核反應的能量）都不足以摧毀自然核種衰變引致的放射活性。所以，包含錄—63 的金屬、合金、或化合物，如鋼、複合材料、陶瓷、以及聚合物（polymers)等都可以很直接的被製造出來。像這樣，許多新穎、耐久（如··長過年）的抗雜材料，以及它們的新朗，都會接續的出現。舉例來說，對金屬而 22 200806814 石’防鏽電銲用共熔相（eutectic)銲料、混凝土橋中的抗氯鋼樑、工業化學生產用抗鹵素鐵容器；以及對非金屬而言，抗氧化橡膠、用以裝載高溫腐蝕溶液的容器，如抗腐姓陶竟腔（chamber)等等。 3·產製用於人體的抗腐餘新穎生醫材料將各種裝置植入人體在今日已是一個例行的醫療行為，例如包括人工骨骼、復健（rehabilitation)及美容 (cosmetology)材料、假牙（denture)、心臟脈搏調整裝置(cardiac pacemaker)、心臟瓣膜（car(jiac orifice) 等的外科植入。這些植入人體的生醫材料本身在富含氯的體液壞境中需要具有非常低的腐#率，而且由腐钕引致的產物也不忐夠造成毒性和對人體組織的傷害，例如疼痛、血凝（blood coagulation)、感染、對組織成長或體内反應的干涉等。除了上述以外，還有牽涉甚廣的許多醫療上 ⑩ 的考置。例如，在-些情形裡，為了利於導致較佳的骨胳與肌肉成長，醫師們常屬意採用多孔的燒結（sintered) 金屬。再者，-般觀她能防細獨鋼也許並不適合許多醫療用途，例如因為其含有鎳會對一些病患造成過敏的反應，尤其是當不鏽鋼開始腐姓的時候。由於這樣的醫療複雜性與高標準考量，要在_不__下選出符合各個不同目的又經濟的生醫材料往往如相難的。本發明提供了-個替代選擇，亦即其能使適合各不同情形之廉 4貝又付順人體的生醫材料擁有其以前所不具的抗腐蝕的能 23 200806814 耐。例如，在含氯濃度甚高的人體環境中，姑_鉻（(；：〇_&) 或鈦（Ti (titanium))合金一般要比不鏽鋼更耐腐蝕，但是，儘管如此，它們也會腐蝕，尤其是當它們必須與其他金屬接觸時即會造成原電池（galvanic)、凹坑（pH)、和裂隙（crevice)腐蝕。此外，它們價格昂貴，而且從機械特性的觀點來看，可能並不是报適當的材料選擇。一個本發明的替代方案可能是，例如，一個由銘一鉻合金或鈦合金包封的含鎳一63的鋼結構。由鎳一63釋出的電子可以令鋼及銘一鉻合金兩者免於被氧化及進而腐姓。同時，人體組織也因為銘一鉻合金的包封而不會接觸到鋼中所含的鎳，故也不會引起過敏反應（見第6圖，本發明的一個在生醫上的應用：一含鎳一63的人工鋼製小腿骨14〇，上面披覆有録—鉻合金塗裝160)。類似的作法也可以應用在其他的合金、4复合材料、聚合物、以及陶瓷，端視何者適合所面對的情況。因此，正如本實施例所揭露的，本發明的方法可以提供抗氧化解決方案，用於產製可植入人體内的裝置，包括人工膝蓋、腿骨、及心律調整器。 4.施加抗代謝物於附著在船身、橋樑、鑽油台、冷凝器及地下設施微生物腐姓（microbial corrosion)，以及由此引致的進一步變質（deterioration)，對土壤中的設施、管路 24 200806814 内壁、熱交換器、冷凝器、飛行器油箱、鑽油平台、以及船身等而言，一直是個嚴重的威脅。人們如今知道這是由於細菌、海藻（algae)、真菌（fungi)、霉菌（m〇id)、黴菌（mildew)等因攝食周圍的水與有機物所造成的現象。幾乎所有的微生物都會運用它們的微有機膜 (micro-organic membranes)或分泌的黏液（secreted adhesives)作為沈積以在上述結構上建立氧濃度電池 (oxygen concentration cells)。一些較為人所知的微生物是（見，例如，Bradford，Samuel A.，Corrosion Control，Chapman & Hall，1992)，首先，硫酸根還原菌 (sulfate-reducing bacteria (SRB))，其專門將土壤中的硫酸根離子（SO/-)還原為硫離子（s2_)，後者再與從氧饥餓區之鐵（當作陽極）逸出的亞鐵離子（ferT〇us i〇ns (Fe ))在氧豐足區結合為硫化鐵（ir〇nsuim(Fes))。這些硫化鐵的沈積接著變成比鐵更有效率的陰極，因而加速氧豐足區之鐵的腐钱。另外，生酸細菌 (acid-producining bacteria (APB))則會氧化硫或硫化物使之變成硫酸（sulfuric acid (ΗΑΟ4))，後者對許多物質而言是強氧化劑。再則，鐵氧化性細菌 (iron了ddizingbacteria (I〇B))以亞鐵離子（ferr〇us ion (Fe ))為食而產出鐵離子（仏订化丨〇耶（Fe3+))，後者再進步形成像門把狀的Fe2〇3鐘腫瘤。另外，微生物附著於船身底部雜會剌其仙它們為捕食對象的海洋生物來械更大的積聚。這翻結果常常導餘運燃料成 25 200806814 本的大幅增加。在所有的微生物腐靖程當t，微生物體⑽生物化學反應是基本而不可或缺的。例如，由祕硫酸㈣原菌 (SRB)所進行的腐蝕是靠著它們體内的氫化 (hydrogenation)酵素的催化作用方得以完成。因此，除了針對雜過程本身（此例為微生物所造成），正如前面的諸實施例㈣作法，本發_方法也可峨演抗代謝物 (anti-metabonte)的角色逕自驅除微生物它們本身。換句話說，儘管對人類不具麟性，本發_抗氧化法卻可以重創微生_轉生的_生化氧倾原反應程序，因而最後將它娜離。例如’干涉它們生命攸騎氧化性猶化作用（oxidative phosphorylation，見，例如，Dr· Michael W. King's biochemistry website http··//web· indstate· edu/thcme/mwking/^^ 程中的重要氧化反應，明顯地將會觸發在微生物體内一系列的有害反應。故其可阻礙微生物體内的維生氧化反應的方式作為產品及環境防霉與抗菌之表面保護物質，該產品及環境包括傢具、冰箱、瓷磚以及貨艙。因此’正如本實施例所揭藤的’本^發"明的方法可以同時提供抗氧化與抗微生物兩個解決方案。特別地，船身和船塢’不論是經過含鎳一63的塗裝處理或者它們本身即是由含鎳一63的合金材料構成，都將變得能長久（長於1〇〇年）防鏽與抗微生物。雖然本發明已以較佳實施例揭露如上，然其並非用來 26 200806814 限定本發明之顧翻，任何熟知此領域技藝者，在不脫離本發明之精神和範_，t可在财與細紅作更動與潤飾。例如，為了其他較短期的目的，所使用的貝他射源 (如鎳―63)也可以被僅具有小於十年半軸的別的核種取代^絲源也可峨製備成有機化合物的形式，而不一定是要純元素或元素溶液的形態。【圖式簡單說明】第1圖，描述一般腐蝕理論所根據的習知電化學電池制' 第2圖，描述由於在金屬表面上的沈積所觸發的習知濃度電，形成過程，其係—侧於—般電化學電池的特例。第3圖，顯示一習知’，被動”防鏽法的一個應用，其係利甩一地面上之絲極（_咖ode)來轉對地底下一鐵製結構之陰極保護所需的外加電壓。第姻，揭示本發明的方法中，以提供從貝他射源（如鎳 -63)射出的電子來阻止並逆轉鐵表面上濃度電池之腐蝕陽極反應的原理。第5圖，揭示一個以本發日月的方法作鐵表祕綱例子，其係將内含具非常長半軸之舰射_油漆或塗料塗佈於鐵表面。第6圖，描述本發明的方法在生醫材料上的一個應用，即：產製貝他射源服、具抗腐鱗性的人工骨路。【主要元件符號說明】 1 :陽極 27 200806814 • 2 :陰極 3、10 :沈積 4 ·低氧區 5:氧豐足區 6 :光陽極 7:電洞消除器 8 ·電源 9:地下鋼鐵結構 • 16 ·· ΙΤ0玻璃（銦錫氧化物） 17 :鐵 18 :鐵鐘 19:金屬連接 20 :含錄-63的鐵 40 :氧叙餓區域 . 60:氧豐足區域 80 :油漆 • 100 :鐵結構 120 :額外塗佈 130 :貝他電子 140 :小腿骨 160 :鈷一鉻合金塗裝 28The solutions disclosed by Hampikian and Scott (Patent PCT/US99/19998, May 25, 2000) all contain at least one dissolved carrier metal ion, and a radioisotope or a compound thereof suspended in solution but not dissolved. 2. Manufacturing novel steels, alloys, ceramics, composites, and polymers containing beta mobile sources as new corrosion resistant materials. In this embodiment, a beta source, such as nickel _63, is in the manufacture of the product. It was put into a part of the new product. The high temperature of the product manufacturing process, such as metal melting, does not cause damage to these beta injection sources, because such ordinary heat (ie, as long as it does not cause nuclear reactions) is not enough to destroy the radioactivity caused by the decay of natural nuclear species. . Therefore, metals, alloys, or compounds containing -6, such as steel, composites, ceramics, and polymers, can be directly fabricated. In this way, many novel, durable (such as the Chinese New Year) anti-heteroplastic materials, as well as their new, will continue to emerge. For example, for metal and 22 200806814 stone 'eutectic solder for anti-rust welding, anti-chlorine steel beam for concrete bridge, anti-halogen iron container for industrial chemical production; and anti-oxidation for non-metal Rubber, a container for loading a high temperature corrosive solution, such as a corrosion resistant family of chambers and the like. 3. Production of anti-corrosion for the human body. New biomedical materials. Implanting various devices into the human body is a routine medical practice today, including artificial bones, rehabilitation and cosmetic materials, and dentures. (denture), cardiac pacemaker, cardiac implant (carc orifice), etc. These biomedical materials implanted in the human body need to have very low in the chlorine-rich body fluid environment. Corrosion # rate, and the products caused by rot are not enough to cause toxicity and damage to human tissues, such as pain, blood coagulation, infection, interference with tissue growth or in vivo reactions, etc. There are also many medical treatments that involve a wide range of subjects. For example, in some cases, in order to facilitate better bone and muscle growth, physicians often prefer to use porous sintered metal. She can prevent fine steel from being used for many medical purposes, for example because it contains nickel, which can cause allergic reactions in some patients, especially when stainless steel is opened. When it comes to humiliation, due to such medical complexity and high standards, it is often difficult to select biomedical materials that meet different purposes and economics under ___. The present invention provides an alternative. That is, it can make the biomedical materials suitable for different situations and have the anti-corrosion energy that was not previously available. For example, in a human environment with a very high concentration of chlorine, agglomerate ((;:〇_&) or Titanium (Titanium) alloys are generally more resistant to corrosion than stainless steel, but, nevertheless, they corrode, especially when they must be in contact with other metals. Galvanic, pit (pH), and crevice corrosion. In addition, they are expensive and may not be an appropriate material choice from a mechanical point of view. An alternative to the present invention may be For example, a steel structure containing nickel-63 encapsulated by a chrome alloy or a titanium alloy. The electrons released by the nickel-63 can protect both the steel and the chrome alloy from oxidation and rot. Simultaneously The human tissue is also not exposed to the nickel contained in the steel because of the encapsulation of the chrome alloy, so it does not cause an allergic reaction (see Figure 6, a biomedical application of the invention: a nickel-containing A 63-section artificial steel calf bone 14 〇, covered with a record - chrome alloy coating 160). Similar practices can also be applied to other alloys, 4 composite materials, polymers, and ceramics, depending on which is suitable Facing the situation. Thus, as disclosed in this embodiment, the method of the present invention can provide an antioxidant solution for the production of devices that can be implanted into a human body, including artificial knees, leg bones, and heart rhythm adjusters. 4. Application of antimetabolites to microbial corrosion attached to the hull, bridges, oil rigs, condensers and underground facilities, and the resulting deterioration, to facilities and pipelines in the soil. 24 200806814 Intrinsic walls, heat exchangers, condensers, aircraft fuel tanks, oil rigs, and hulls have always been a serious threat. People now know that this is caused by bacteria, algae, fungi, mold, mildew, etc. caused by feeding water and organic matter around them. Almost all microorganisms use their micro-organic membranes or secreted adhesives as deposits to build oxygen concentration cells on the above structures. Some of the more well-known microorganisms are (see, for example, Bradford, Samuel A., Corrosion Control, Chapman & Hall, 1992), first, sulfate-reducing bacteria (SRB), which specifically The sulfate ion (SO/-) in the reduction is reduced to sulfur ion (s2_), which in turn is ferrous ion (ferT〇us i〇ns (Fe)) which escapes from the iron in the oxygen starvation zone (as the anode) In the oxygen-rich foot zone, it is combined into iron sulfide (ir〇nsuim (Fes)). The deposition of these iron sulphide then becomes a more efficient cathode than iron, thus accelerating the rot of iron in the oxygen-rich area. In addition, acid-producining bacteria (APB) oxidize sulfur or sulfides to become sulfuric acid (ΗΑΟ4), which is a strong oxidant for many substances. Furthermore, iron-oxidizing bacteria (iron ddizing bacteria (I〇B)) produce iron ions (Fe3+) by feeding on ferrium (Fe) ions. Further progress is made to form a Fe2〇3 bell tumor like a doorknob. In addition, the microbes attached to the bottom of the hull will be more concentrated in the marine life of the predators. This result often leads to a significant increase in the amount of fuel that has been transferred to 25 200806814. In all microbial rot, the microbial (10) biochemical reaction is essential and indispensable. For example, corrosion by the secret sulfuric acid (S) protobacteria (SRB) is accomplished by the catalytic action of hydrogenation enzymes in their bodies. Thus, in addition to the heterogeneous process itself (in this case by microorganisms), as in the previous examples (iv), the present method can also act as an anti-metabonte to self-eviate the microorganisms themselves. In other words, although it is not lining for humans, the _ antioxidant method can reinvent the _ biochemical oxygenation process, which is the result of the _ biochemical oxygenation process. For example, 'interfering with their oxidative phosphorylation, see, for example, Dr. Michael W. King's biochemistry website http··//web· indstate· edu/thcme/mwking/^^ The reaction will obviously trigger a series of harmful reactions in the microorganisms, so it can hinder the way of vitamins in the microorganisms. As a product and environmental anti-mildew and anti-bacterial surface protection substances, the products and environment include furniture. , refrigerators, tiles, and cargo holds. Therefore, 'the method of 'this hair' according to the embodiment of the present invention can provide both anti-oxidation and anti-microbial solutions. In particular, the hull and the dock' The coating treatment of nickel-containing 63 or they themselves consists of an alloy material containing nickel-63, which will become rust-proof and antimicrobial for a long time (longer than one year). Although the invention has been preferably implemented The disclosure of the above is not intended to limit the invention, and any person skilled in the art, without departing from the spirit and scope of the present invention, may Fortunately, for the sake of other short-term purposes, the beta source (such as nickel-63) used can also be replaced by other nuclear species with less than a decade and a half axis. It can be prepared in the form of an organic compound, not necessarily in the form of a pure element or element solution. [Simplified Schematic] Figure 1 depicts a conventional electrochemical cell system based on the general corrosion theory. Describe the conventional concentration of electricity triggered by deposition on a metal surface, the formation process, which is a special case of the side-like electrochemical cell. Figure 3 shows an application of a conventional 'passive' rust-proof method. , which is a filament on the ground (_ café) to turn the applied voltage required for the cathodic protection of the next iron structure on the ground. The marriage reveals the method of the present invention to provide a shot from beta. The electrons emitted by the source (such as nickel-63) prevent and reverse the principle of the corrosive anode reaction of the concentration cell on the iron surface. Figure 5 shows an example of the iron table secret by the method of the present day and month. Containing a ship with a very long semi-axis Or the coating is applied to the surface of the iron. Fig. 6 is a view showing an application of the method of the present invention to a biomedical material, that is, an artificial bone path for producing a beta-ray source garment and having anti-corrosion scale. Description] 1: Anode 27 200806814 • 2: Cathode 3, 10: Deposition 4 • Low oxygen zone 5: Oxygen foot zone 6: Photoanode 7: Hole eliminator 8 • Power supply 9: Underground steel structure • 16 ·· ΙΤ0 glass (Indium Tin Oxide) 17: Iron 18: Iron Bell 19: Metal Connection 20: Iron 40 with Record-63: Oxygen Hungry Area. 60: Oxygen Foot Area 80: Paint • 100: Iron Structure 120: Additional Coating 130: Beta Electronics 140: Calf 160: Cobalt-chromium coating 28

Claims

200806814 X. Patent application scope: The anti-oxidation method of Bu-type decay electrons, which is adjacent to novel and passive substances resistant to the generalized oxidation reaction, including the provision of raw materials required for the manufacture of known substances in the above process. Guided by a quantitative endurance beta cell source; 'Therefore - with a long-lasting anti-oxidation product, it will be used to provide the required electrons in a spontaneous way to establish cathodic protection measures.

2. The method of claim i, wherein the resistance to the generalized oxidation reaction of Lin Ying, the passive material covers metals, including pure metals, alloys; and non-metals, including pottery, polymers, and composite materials. 3. The method of claim 1, wherein the beta injection source is selected from the group consisting of long half-lives, including nickel ~ (10), edit one 113, and chromium one 99. 4. The method of claim i, wherein the ability to resist the generalized oxidation reaction of Lin Ying and the passive material is to make the scales, including the hull, the body, the underground steel structure, and the bridge. 5. The method of claim i, wherein the new, passive material capable of resisting the generalized oxidation reaction is a eutectics solder used in the electrical seam and filler industries. 6. The method of claim 1, wherein the novel, passive material capable of resisting the generalized oxidation reaction is a ceramic, which is fabricated into a container for loading a high temperature etching solution. 29 200806814 7. If you apply for a patent scope! In the method described, the passive substance is a biomedical material, which is used: a device that is implanted in a human body, including an artificial knee, a leg bone, and a heart rhythm. 8 as described in claim 7 The method, the device that diffuses out of the device in the complex, especially the recording _ ̄ ίί, can be applied to the surface of the body by applying a layer - such as cobalt-chromium alloy money alloy (four) cloth to very low . 9, - kind of profit (4) only the financial law side rust-proof coating materials, such as paint, transparent paint, including: with a new supply of coating materials in Jixian; add __ predetermined amount in the coating material The beta source; it is produced by a new coating material with anti-rust effect, which is: Γ provides electrons to the material coated by it to achieve cathodic protection. The source may apply for the method described in item 9 of the patent, wherein the beta injection and the supply of a group of long-term half-years, including nickel ~ 63, record one 113, and wrong one 99 〇 11, such as the scope of patent application The method of item 9, wherein the beta injection = in the form of a fine powder prior to breaking the coating f, and each powder particle has a diameter of less than 100 Å. The method of claim 3, wherein the coating of the method of claim 9, wherein the new coating 200806814 substance is applied to a known surface. Treatment behavior, including paint, powder coating, thermal spray coating, diffusion coating, conversion coating, electrodeposition (electro-deposition) ), electroless deposition, electroplating, and anodizing. 14. The method of claim 9, wherein the new coating material is used as a protective structure, such as a hull, to protect against microbial adhesion and anaerobic anti-metabolites, which interfere with the microorganisms. The metabolic reaction within it drives the microorganism away. 15. The method according to claim 9, wherein the new coating material is a surface protection material for preventing mildew and oxidation in microorganisms, and the product and environment are anti-mildew and antibacterial surface protection substances. Includes furniture, fridge, tiles and cargo hold.

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