1292439 九、發明說明： 【發明所屬之技術領域】 本發明是有關於一種氫化锆析出方位重排方法與裝置。尤其 _ 是指一種利用内外管壁壓力差配合熱處理過程使該锆合金護套氫 化錯方位重排之一種錯合金護套氫化錄析出方位重排方法與裝 置。 一 • 【先前技術】 鍅合金材料具有中子吸收截面小和優異的抗腐蝕性及機械性 質，因此廣泛地用於核能工業中。然而由於運轉環境下的中子照 、 射脆化以及吸氫效應，核燃料锆合金護套延展性與破壞特性隨著 • 核燃料之燃耗度增加逐漸劣化。因此，為確保核燃料運轉操作安 全與可靠性，核燃料完整性為核安管制機構與核能工業界共同關 切之研究議題。 造成錯合金虱脆化效應主要係因氫化錯析出所致。正常運轉 狀態下，鍅合金護套氫化鍅大致均沿箍環方向（H00p directiQn) 析出，此即環向氫化錄，如圖一所示。锆合金護套内部所形成之 環向氫化锆比例隨電廠運轉燃耗度增加而增加，因此，錯合金護 套之延展性相對降低，不過即使锆合金護套含氫量達1000ppm，其 仍保有法規所要求1%之延性。然而在1963年，美國薩瓦納河 - (Savannah River，USA)電廠破損燃料檢驗發現，如果鍅合金護套 中氫含量僅需約50-1 OOppm，但是氫化锆析出平面若垂直於作用力 方向（即徑向氫化锆），如圖二所示，則該鍅合金護套即呈完全脆 6 1292439 性之破壞特性。由此可見，徑向氫化錯對護套機械性質劣化效應 遠大於環向氫化锆的影響。 現今核能工業正朝向提高核燃料燃耗度目標努力，以減少用 過燃料棒數量，並提昇核燃料經濟效益。然而延長燃料棒運轉燃 ' 耗度時’隨之增加的照射分裂氣體壓力與燃料丸一護套交互作用 -效應（Pellet-Cladding Mechanical Interacti〇n; pcMI)使護套 壁或，部位置承錄大的環向應力，高祕核麟齡金護套因 徑向氫化糾破損騎在危機A幅提高。此外，用過核燃料自燃 ♦料水池取出傳送裝載於乾式貯存桶過程中，因燃料罐乾燥作業之 故’護套最高溫度可能達働。(:以上，護套中部分氫化翻而溶 解。隨著貯存時間增長，錯合金護套蜆變熱(Decay Heat)與溫度 逐漸降低’氫化錯重新析出。因分裂氣體内壓或燃料丸_護套交 互作用效應施加環向應力於護套上，有利徑向氫化錯析出。 綜合上述，亟需一種锆合金護套氫化锆析出方位重排方法與 裝置來提供氫化錯樣品需求以瞭解徑向氫化錯形成機制及其所引 起相關材料劣化問題。 ^ m 【發明内容】 - 本發明的主要目的是提供一種鍅合金護套氫化鍅析出方位重 • 排方法與裝置，其係糊内外管壁壓力差配合熱處理過程，達到 使結合金護套氫化錯析出物之方位由環向轉換成徑項之目的。 • 為了達到上述之目的，本發明提供一種鍅合金護套氫化鍅析 、，方位重排方法，其係包括有下列步驟··（a)將一鍅合金護套管進 行-氫化處理’使經由該氫化處理而產生之氫化鉛沿該錯合金護 套之管壁環向進行分佈；⑹然後，使該錯合金護套管内壁以及外 7 1292439 壁產生一壓力差；以及(C)最後，對該告合金護套管反覆進行加熱 冷卻之熱處理程序。 較佳的是，該步驟(b)更包括有下列步驟··（bl)封閉該鍅合 金護套管之一端；以及(b2)於該鍅合金護套管之另一端填充一物 質使該鍅合金護套管内壁產生高壓以大於該鍅合金外壁所承受之 • 壓力。 為了達到上述之目的，本發明提供一種锆合金護套氫化鍅析 出方位重排裝置，其係包括··一爸體；一蓋體，其係覆蓋於該爸 曝體上，使該頻_成可容置—齡金護套f之―密_間，該 錯合金護套管之-端係設置於該蓋體上，而另一端係以一罩體^ 閉，熱源產生裝置，其係設置於該釜體之外圍，以提供熱源給 該齡金護套管；以及—高壓產生裝置，其係與該蓋體相連接、， 該高壓產生裝置可充填一高壓物質至該锆合金護套管内壁。 【實施方式】 瞻為使貴審查委員能對本發明之特徵、目的及功能有更進一 步的認知與瞭解，下文特將本發明之裝置_關細部結構以及設 柏理念原由進行朗，以使得審查委貞可以了解本發明之特 點，詳細說明陳述如下·· 首先簡述本發明之原理，氫化锆方位重排或徑向氫化鍅析出 物形成機觀雜，受氫含量、護套溫度及環向應力 ，冷卻速率， 週期數與溫度差及材料冶金特性等因素左右。根據相關研 九、、、。果，氫化錯析出方位排列主要受鍅合金基地材料應力狀態所 ^配’此應力狀態包括護套本身殘留應力、運轉時所受外力以及 斤出時產生之應變。由於氫化錯密度略低於錯合金基地材料，護 8 1292439 套材料由冷卻時，統麵向沿平行外加縣力或垂直 張應力方向侧析出，藉崎傭㈣封目體麵化所產生之 應隻月b因此若遵套局部區域出現較大的環向應力時，形成徑 向氫化錯機率對應提高，此即為本發明之基本原理。 請參閱圖三A所示，該圖係為本發明锆合金護套氫化锆析出 方位重排方法難實職㈣㈣。域化_^綠重排方 其係包括有下列步驟：首先，進行步驟31提供-齡金護套 管；織断步驟32，對驗合金護套管進行—氫化處理，使得 錯與氫產生氫化錯之析肢應。此時域化錯之·物會沿著該 錯合金護套管之環行方向進行分布，請參閱圖一所示。 接下來，進行步驟33，使該鍅合金護套管内壁以及外壁產生 一壓力差。最後進行步驟34，對該告合金護套管反覆進行加熱以 及冷卻之熱處理程序。由於加熱以及冷卻之熱處理程序之目的是 為了控制鍅合金護套管之鍅合金對於氫化锆之溶解度，藉由溫度 之升高提高鍅合金對於氫化锆之溶解度。再藉由溫度之下降，使 該氫化锆析出，此時由於該锆合金護套管之管壁承受壓力差，因 此當溫度下降而析出氫化錯時，藉由該壓力差使得氫化錯析出物 沿著該結合金護套管徑向進行排列，如圖二所示。 請參閱圖三B所示，該圖係為本發明锆合金護套氫化鍅析出 方位重排方法中之提供壓力差之較佳實施流程示意圖。要產生如 步驟33之壓力差，首先先進行步驟331，封閉該锆合金護套管之 一端。然後進行步驟332，於該錘合金護套管之外部環境中，充填 低壓之氣體。最後再進行步驟333，充填一物質使該鍅合金護套管 内壁產生之壓力大於該鍅合金外壁所承受之壓力。在本實施例 中’該氣體係為氨氣，該物質係為純水。 9 1292439 為了更清楚的了解本發明方法之精 示’該圖係為本發明錯合金護套氯化_ ‘重=== ^]τγ 同壓釜11 -熱源產生裝置13以及—高 蒼η包括有一蓋體⑴以及，2。該蓋體二 於該紐112上，麟紐瓜_射容置-齡金護it 之:_ m。該_'產生裝置13，其係設置於該爸體;1292439 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a method and apparatus for zirconia precipitation orientation rearrangement. In particular, _ refers to a method and apparatus for hydrostatic recording of azimuth rearrangement by using a pressure difference between inner and outer walls and a heat treatment process to hydrogenate the zirconium alloy sheath in a misaligned orientation. 1. [Prior Art] Niobium alloy materials are widely used in the nuclear energy industry because of their small neutron absorption cross section and excellent corrosion resistance and mechanical properties. However, due to the neutron irradiation, embrittlement and hydrogen absorption effects in the operating environment, the ductility and failure characteristics of the nuclear fuel zirconium alloy sheath gradually deteriorate with the increase of the fuel economy of the nuclear fuel. Therefore, in order to ensure the safety and reliability of nuclear fuel operation, nuclear fuel integrity is a research issue that is closely related to nuclear safety regulatory agencies and the nuclear industry. The effect of causing the wrong alloy embrittlement is mainly due to the mis-precipitation of hydrogenation. Under normal operating conditions, the niobium alloy sheathed hydrogenated niobium is generally precipitated along the hoop direction (H00p directiQn), which is the hoop hydrogenation record, as shown in Figure 1. The proportion of hoop zirconium formed inside the zirconium alloy sheath increases with the increase of the fuel consumption of the power plant. Therefore, the ductility of the mis-alloy sheath is relatively reduced, but even if the zirconium alloy sheath has a hydrogen content of 1000 ppm, it still retains The 1% ductility required by the regulations. However, in 1963, the Savannah River (USA) power plant damaged fuel test found that if the hydrogen content of the niobium alloy sheath only needs about 50-1 OOppm, but the zirconium hydride precipitation plane is perpendicular to the direction of the force. (ie radial zirconium hydride), as shown in Figure 2, the bismuth alloy sheath is completely fragile 6 1292439. It can be seen that the effect of radial hydrogenation on the mechanical properties of the sheath is much greater than that of the circumferential zirconium hydride. The nuclear industry is now working towards the goal of increasing the fuel economy of nuclear fuels to reduce the number of used fuel rods and increase the economic efficiency of nuclear fuels. However, when the fuel rod is operated, the consumption of the splitting gas pressure increases with the fuel pellet-sheath-effect (Pellet-Cladding Mechanical Interacti〇n; pcMI) to record the wall or the position of the sheath. The large hoop stress, the high-density nucleus gold sheath is increased due to the radial hydrogenation correction damage in the crisis A. In addition, the self-ignition of nuclear fuel is used to remove and transport the tank in the dry storage tank. Due to the drying operation of the fuel tank, the maximum temperature of the sheath may reach 働. (: Above, the partial hydrogenation in the sheath turns to dissolve. As the storage time increases, the wrong alloy sheath becomes hot (Decay Heat) and the temperature gradually decreases, and the hydrogenation error is re-precipitated. Due to the internal pressure of the split gas or the fuel pellet The set of interaction effects exerts hoop stress on the sheath, which facilitates radial hydrogenation mis-precipitation. In summary, there is a need for a zirconium alloy sheathed zirconium hydride precipitation orientation rearrangement method and apparatus to provide hydrogenation error sample requirements for radial hydrogenation. The fault formation mechanism and the related material degradation problems caused by it. ^ m [Summary of the Invention] - The main object of the present invention is to provide a method and a device for argon alloy sheath hydrogenation enthalpy azimuth weight discharge, which is the pressure difference between the inner and outer walls of the paste In combination with the heat treatment process, the orientation of the hydrogenated mis-precipitate of the bonded gold sheath is converted from the circumferential direction to the diameter term. • In order to achieve the above object, the present invention provides a hydrogenation deuteration and orientation rearrangement method for a niobium alloy sheath. The method includes the following steps: (a) performing a hydrogenation treatment on a tantalum alloy sheathed tube to cause the hydrogenation lead produced by the hydrogenation treatment to follow the same The wall of the gold sheath is circumferentially distributed; (6) then, a pressure difference is generated between the inner wall of the wrong alloy sheathed tube and the outer wall of 1 1292439; and (C) finally, the alloy sheathed tube is repeatedly heated and cooled. Heat treatment procedure. Preferably, the step (b) further comprises the following steps: (b) sealing one end of the niobium alloy sheath tube; and (b2) filling a substance at the other end of the niobium alloy sheath tube The inner wall of the beryllium alloy sheathed tube is subjected to a high pressure to be greater than the pressure which the outer wall of the niobium alloy is subjected to. In order to achieve the above object, the present invention provides a zirconium alloy sheathed hydrogenated deuterium precipitation azimuth rearrangement apparatus, which comprises a dad body; a cover body, which is covered on the dad's body, so that the frequency can be accommodated - the age of the gold sheath f - the dense, the wrong alloy sheathed tube - the end system is set in the a cover body, and the other end is closed by a cover body, and a heat source generating device is disposed on the periphery of the kettle body to provide a heat source to the gold sheathed pipe of the age; and a high pressure generating device is coupled thereto The cover body is connected, and the high pressure generating device can be filled with a high pressure object To the inner wall of the zirconium alloy sheathed tube. [Embodiment] To enable the reviewing committee to have a further understanding and understanding of the features, objects and functions of the present invention, the following is a device for the present invention. The concept is based on the original reason, so that the review committee can understand the characteristics of the present invention. The detailed description is as follows: First, the principle of the present invention is briefly described, the zirconium hydride orientation rearrangement or the radial hydrogenation decant formation machine is observed, and hydrogen is accepted. The content, sheath temperature and hoop stress, cooling rate, number of cycles and temperature difference, and metallurgical properties of the material are related. According to the relevant research, the results of hydrogenation and misalignment are mainly affected by the stress state of the alloy base material. ^This 'stress state includes the residual stress of the sheath itself, the external force during operation and the strain generated when the hammer is out. Since the hydrogenation fault density is slightly lower than the wrong alloy base material, the protector 8 1292439 sets of materials are cooled when facing Separated along the direction of the parallel plus the county force or the vertical tensile stress, and the formation of the surface by the Kawasaki maid (4) should be only the month b. When a large hoop stress occurs in the domain, the formation of the radial hydrogenation error rate is correspondingly increased, which is the basic principle of the present invention. Please refer to FIG. 3A, which is a schematic diagram of the zirconium alloy sheath zirconium hydride zirconium precipitation azimuth rearrangement method (4) (4). The domain _^green rearrangement system comprises the following steps: first, step 31 is provided to provide an age-old gold sheath tube; and in step 32, the alloy sheath tube is subjected to hydrogenation treatment to cause hydrogenation of hydrogen and hydrogen. The wrong limb should be. At this time, the object of the domain is distributed along the direction of the ring of the wrong alloy sheath tube, as shown in Figure 1. Next, step 33 is performed to cause a pressure difference between the inner wall and the outer wall of the niobium alloy sheath tube. Finally, in step 34, the alloy sheathed tube is repeatedly heated and subjected to a heat treatment procedure for cooling. Since the purpose of the heat treatment procedure of heating and cooling is to control the solubility of the niobium alloy of the niobium alloy sheathed tube with respect to zirconium hydride, the solubility of the niobium alloy for zirconium hydride is improved by the increase in temperature. Further, the zirconium hydride is precipitated by a decrease in temperature. At this time, since the wall of the zirconium alloy sheathed tube is subjected to a pressure difference, when the temperature is lowered to precipitate a hydrogenation error, the hydrogenation error is caused along the pressure difference. The combined gold sheath tube is arranged radially, as shown in FIG. Please refer to FIG. 3B, which is a schematic diagram of a preferred embodiment of the pressure difference provided in the method for hydrogenation enthalpy precipitation orientation of the zirconium alloy sheath of the present invention. To produce a pressure differential as in step 33, first step 331 is performed to close one end of the zirconium alloy sheath tube. Then, in step 332, a low pressure gas is filled in the external environment of the hammer alloy sheathed tube. Finally, step 333 is performed to fill a material such that the pressure generated on the inner wall of the niobium alloy sheathed tube is greater than the pressure applied to the outer wall of the niobium alloy. In the present embodiment, the gas system is ammonia gas, and the material is pure water. 9 1292439 For a clearer understanding of the method of the present invention, the figure is the chlorination of the wrong alloy sheath of the present invention _ 'heavy === ^] τ γ with the autoclave 11 - heat source generating device 13 and - high There is a cover (1) and, 2. The cover body is located on the New Zealand 112, and the lining of the guillotine is _m. The _' generating device 13 is disposed on the dad body;
之外圍’峨供舰職齡金護奸2，雜難絲置13可 以為電熱官，但不在此限。該高壓產生健12，其係與該蓋 相連接，該高壓產生裝置12可提供壓力給充填於該錯合金護套管 内之-物質，使該物質產生高壓伽於雜合金護套管2之内壁。 ^接下來配合_測本裝置之操作流程H齡金護套 管2做均勻氫化處理，使錄合金内氫化錯達設定濃度，並沿著锆 合金護套管2之1Β周方向形成環向分佈，以模擬真實燃料棒 轉環境下之吸氫行為。 ' 然後，將均勻氫化之錐合金護套管2 一端以一罩體22封住， 以防止壓力外洩，在本實施例中，該罩體22係為一高壓螺絲，但 不在此限。而該锆合金護套管2之另一端則裝置於該高壓釜丨丨之 蓋體111上。此蓋體111與高壓水環管路1〇相通，該管路1〇之 另一端連接該高壓產生裝置12,藉由該高壓產生裝置12以提供锆 合金護套管2足夠内壓力，以模擬實際高然耗核燃棒料内部所承 受之壓力。 緊接著，將鎖有結合金護套管2之蓋體111與高壓釜11之爸 體112結合並鎖緊’使該該錐合金護套管2内壁充滿純水92，利 用該高壓產生裝置2對該純水增壓以形成高壓純水90，進而使錄 1292439 合金護套管壁承受-壓力（高壓）；為求良好熱傳導效果，該密閉 空間113内則填適量滿氦氣91 (低壓），但不在此限。並藉由差壓 及控制器使錯合金護套管2於升降降溫等熱處理過程中維持設定 之内外壓力差。 ' " 最後，利用高壓爸11外壁之熱源產生裝置13，對該鍅合金護 套管2實施循環固溶處理(Soluti〇n Treatment)。當該金護 套管2加熱至設定固溶溫度時，鍅合金護套管2内部^氫化 錯將固溶進入锆合金基地(Matrix)中。緩慢冷卻時，固溶之氫原 子開始析出，由於基地材料受到徑向應力93之故，如圖五所示， 重新析出之氫化料部分會沿雜向制。藉由反覆加熱冷卻之 熱處理程序’環向氫化錯將逐漸轉向成為徑向氫化錯至'二定比 例，而達到方位重排之目的。 〇 唯以上所述者’僅為本發明之齡實_，當不能以之限制 本發明範圍。.本發鴨保之方法中所提到之步驟順序僅實 施例之綱，即大凡依本發明申請專娜騎做之解變化及修 飾’仍將*失本發明之要義所在，故㈣視為本發日㈣進一步 施狀況。 综合战’經由本㈣提供之裝砂狀村 向虱化錯形成機制及其所引起相關材料劣化問題所需要之 提供核電廠進行研究，因此可以滿聽界 :^樣如以 定申業之發展’誠已符合㈣專利法所規 =申=發明所需具備之要件，故爰依法呈提發明專利 5月貝審查委員允撥時間惠予審視，並賜準專利為禱。月〇 1292439 【圖式簡單說明】 圖-係為錯合金護套管截面中環向氳化鍅分布示意圖。 圖二係為錯合金護套管截面中徑向氳化#分布示意圖。 圖三A係為本發明錯合金護套氫化鍅析出方位重排方法較 施流程示意圖。 耳 圖三B係為本發明鍅合金護套氫化鍅析出方位重排方法中之 供壓力差之較佳實施流程示意圖。 圖四係為本發明锆合金護套氫化锆析出方位重排裝置之 施例示意圖。 、 父 圖五係為本發明之锆合金護套管内壁受壓力作用示咅圖。 【主要元件符號說明】 氮化結析出方位重排裝置 10- 管路 11- 向壓爸 11卜蓋體 112- 爸體 113- 密閉空間 12 -高壓產生裝置 13-熱源產生裝置 2-锆合金護套管 20- 外壁 21- 内壁 12 1292439 22-罩體 90- 高壓純水 91- 氦氣 92*純水 93-徑向應力 3-氫化錄析出方位重排方法The periphery of the 峨 峨 峨 职 职 职 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 The high pressure generating spring 12 is connected to the cover, and the high pressure generating device 12 can supply pressure to the material filled in the wrong alloy sheath tube, so that the material generates high pressure and is galvanized on the inner wall of the miscellaneous alloy sheath tube 2. . ^ Next, the H-age gold sheath tube 2 is uniformly hydrogenated in accordance with the operation procedure of the measuring device, so that the hydrogenation in the alloy is incorrectly set to a concentration, and a circumferential distribution is formed along the circumferential direction of the zirconium alloy sheath tube 2. To simulate the hydrogen absorption behavior of a real fuel rod to the environment. Then, one end of the evenly hydrogenated tapered alloy sheath tube 2 is sealed with a cover 22 to prevent pressure leakage. In the present embodiment, the cover 22 is a high pressure screw, but not limited thereto. The other end of the zirconium alloy sheathed tube 2 is mounted on the lid 111 of the autoclave. The cover body 111 is in communication with the high-pressure water ring line 1 , and the other end of the line 1 is connected to the high-pressure generating device 12, and the high-pressure generating device 12 is provided to provide sufficient internal pressure of the zirconium alloy sheath tube 2 to simulate Actually, it consumes the pressure inside the nuclear fuel bar. Next, the lid body 111 locked with the gold sheath tube 2 is combined with the dad body 112 of the autoclave 11 and locked. The inner wall of the cone alloy sheath tube 2 is filled with pure water 92, and the high pressure generating device 2 is utilized. The pure water is pressurized to form high-pressure pure water 90, and then the wall of the 1292439 alloy sheath tube is subjected to -pressure (high pressure); in order to obtain a good heat conduction effect, the sealed space 113 is filled with a full amount of helium gas 91 (low pressure). , but not limited to this. And the differential alloy and the controller maintain the set internal and external pressure difference during the heat treatment such as lifting and lowering by the differential pressure and the controller. ' " Finally, the heat treatment device 13 of the outer wall of the high pressure dad 11 is used to perform a solution solid solution treatment (Soluti〇n Treatment). When the gold sheath 2 is heated to the set solution temperature, the internal hydrogenation of the niobium alloy sheath tube 2 will solidify into the zirconium alloy base. When slowly cooled, the dissolved hydrogen atoms begin to precipitate. Since the base material is subjected to radial stress 93, as shown in Fig. 5, the re-precipitated hydrogenate portion will be produced in a heterogeneous manner. The heat treatment procedure by repeated heating and cooling, the hoop hydrogenation error, will gradually turn into a radial hydrogenation error to a ratio of two to achieve the purpose of orientation rearrangement.唯 Only the above is only the age of the present invention, and the scope of the present invention cannot be limited thereto. The sequence of steps mentioned in the method of the present invention is only the outline of the embodiment, that is, the solution to the change and modification of the application of the application of the invention by the invention is still the main meaning of the invention, so (4) This issue (4) is further applied. The comprehensive warfare will provide research on nuclear power plants required by the sand-filled villages provided by this (4) to the formation mechanism of the faults and the deterioration of related materials, so that it can be heard in the world: 'Cheng has met the requirements of the (4) Patent Law = Shen = the necessary elements of the invention, so the invention patent was filed according to law. May Bay Review Committee allowed the time to review and granted the patent as a prayer.月〇 1292439 [Simple description of the diagram] Figure- is a schematic diagram of the distribution of circumferential bismuth telluride in the section of the wrong alloy sheathed tube. Figure 2 is a schematic diagram of the radial deuteration # distribution in the cross section of the wrong alloy sheathed tube. Fig. 3A is a schematic diagram showing the process of the orientation and rearrangement of the hydrogen alloy in the wrong alloy sheath of the present invention. The ear 3B is a schematic diagram of a preferred implementation flow of the pressure difference in the method for hydrogenation enthalpy precipitation of the bismuth alloy sheath of the present invention. Fig. 4 is a schematic view showing an example of a zirconium alloy sheathed zirconium hydride zirconium precipitation azimuth rearrangement device. The parent figure is the pressure diagram of the inner wall of the zirconium alloy sheathed tube of the present invention. [Main component symbol description] Nitrided junction precipitation rearrangement device 10 - Pipeline 11 - Pressure dad 11 cover body 112 - Dad body 113 - Confined space 12 - High pressure generating device 13 - Heat source generating device 2-Zirconium alloy protection Casing 20 - Outer wall 21 - Inner wall 12 1292439 22 - Cover 90 - High pressure pure water 91 - Helium 92 * Pure water 93 - Radial stress 3-Hydrogen recording and orientation rearrangement method
31〜34-步驟 331〜332-步驟31~34-step 331~332-step
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