200844431 九、發明說明 【發明所屬之技術領域】 本發明係關於作爲絕緣·冷卻媒體而使用矽膠液的電 性機器用矽膠液之劣化診斷裝置及電性機器用矽膠液之劣 化診斷方法。 【先前技術】 [周知例] 先前，在使用絕緣·冷卻媒體的電性機器之變壓器的 絶緣·冷卻媒體係使用鑛油等的絕緣油。 代替此鑛油作爲變壓器的絕緣·冷卻媒體而藉由使用 難燃性的矽膠液，可使變壓器的防火性提高，而且藉由變 高運轉溫度而可謀求電性機器的緊緻化。 然而，在作爲絶緣·冷卻媒體而使用矽膠液的情況， 係若比先前更變高電性機器的運轉溫度，則產生因矽膠液 的熱劣化所致之低分子量、低沸點的分解物。 若於矽膠液，此分解物大量地產生，則因爲矽膠液的 引火溫度（以下，稱爲引火點）下降，所以有矽膠液變得容 易引火的問題。此分解物的生成量係電性機器的運轉溫度 越高則變得越多。 在日本特開平1 0-3 3 2682號公報，係開示：藉由將被 使用於油浸電性機器的電性絕緣油進行昇溫加熱而測定化 學發光數，評估電性絕緣油的劣化程度之技術。 在日本特開平3 - 1 872 06號公報，係開示：在油浸變壓 200844431 器、油浸電抗器等的油浸電性機器之槽上部配置複數個氣 體檢測器的同時，作爲如已產生的可燃性氣體爲有效率地 被導入至各氣體檢測器般的槽構造，確實地檢測電性機器 的絕緣破壞或局部加熱等的異常之技術。 在日本特開昭5 9- 1 7 668 3號公報，係開示··測定電性 絕緣用矽膠液的熱重量特性，由該特性曲線求出耐熱指標 TGI(°C ) ’在此成爲某個値（325 °C )以下時，判定矽膠液已 劣化之技術。 在曰本特開昭54- 1 1 4290號公報，係開示：在注入絕 緣油的電性機器’藉由從將絕緣油中的氣體成分在常溫起 泡（bubbling)而抽出至氣相，進行分析的技術。 專利文獻1:日本特開平10-332682號公報 專利文獻2:日本特開平3_：187206號公報 專利文獻3 :日本特開昭5 9 - 1 7 6 6 8 3號公報 專利文獻4:日本特開昭54- 1 1 4290號公報 【發明內容】 若矽膠液爲熱劣化則環聚物產生，其主成分爲3聚物 、4聚物、5聚物。 了解：劣化越進行，則環聚物的產生量變得越多。3 聚物、4聚物、5聚物係沸點低、容易蒸發。在未劣化之初 期狀態，係幾乎不包含環量體。 因劣化’亦產生低分子量的直鏈化合物。但是在未劣 化的初期狀態，亦含有低分子量的直鏈化合物。因而，即 -5- 200844431 使在初期狀態，某程度的低分子量的直鏈化合物亦蒸發。 前述專利文獻3，係將矽膠液以一定量抽出，將此以 一定溫度梯度加熱，使低分子量的化合物蒸發，由重量減 少了 1 0 %以及2 0 %時的加熱溫度而求出劣化的指數，但因 爲於矽膠液係即使在初期狀態亦含有低分子量的直鏈化合 物，所以有藉由重量的減少量（也就是蒸發量）係對劣化的 判定欠缺正確度的問題。 另外，重量減少20%的溫度亦從3 5 0度C變爲3 70度C ，在如此高的溫度，係可預知：因爲正常的矽膠液熱分解 而變化爲低分子化合物，所以對熱劣化的判定帶來不良影 響。 本發明者等，在實驗上確認：在矽膠液中產生的低分 子量的環聚物係作爲熱劣化的指標而可使用之情事’而達 到產生本發明。 也就是，以將矽膠液中的環聚物進行定量分析’而可 正確地把握熱劣化的狀態。 藉由矽膠液的熱劣化而產生的低分子量、低沸點的分 解物之主成分，係具有與矽膠液相同的基本化學構造之環 狀的化合物。因此，在矽膠液中將爲矽膠液的分解物之環 狀化合物選擇性地分析、定量爲困難。 本發明的目的，係在提供··可將作爲矽膠液浸電性機 器之絕緣·冷卻媒體而使用的矽膠液之熱劣化’正確而且 簡便地診斷之電性機器用矽膠液的劣化診斷裝置及電性機 器用矽膠液的劣化診斷方法。 -6 - 200844431 [用以解決課題的手段] 本發明之電性機器用的矽膠液的劣化診斷裝置，係具 備：電性機器、和將此電性裝置收容於內部的槽、和貯藏 於前述槽內而絕緣·冷卻前述電性裝置之矽膠液、和將前 述槽內的矽膠液的一部分採取至該槽的外部之採取配管、 和加熱以前述採取配管而採取的矽膠液而使含有於矽膠液 中的環狀化合物蒸發氣化之氣體成分採取容器、和將在前 述氣體成分採取容器已蒸發氣化之環狀化合物進行定量分 析之氣體分析裝置、和根據在前述氣體分析裝置進行分析 的環狀化合物的分析値而判斷矽膠液的劣化狀況之判定裝 置、和顯示在前述氣體分析裝置已進行分析的環狀化合物 的分析値、以及/又或是在前述判定裝置已判斷的矽膠液 的劣化狀況之顯示裝置，而作爲其特徵。 另外，本發明的電性機器用的矽膠液之劣化診斷方法 ，係被收容於槽的內部，藉由貯藏於該槽內的矽膠液而被 絕緣而冷卻之電性機器用的矽膠液之劣化診斷方法，以： 將前述槽內的矽膠液之一部分通過採取配管而採取至該槽 的外部，將此已採取之矽膠液供給於氣體成分採取容器， 加熱該氣體成分採取容器而使被含有於矽膠液中的環狀化 合物蒸發氣化，將此已蒸發氣化的環狀化合物供給於氣體 分析裝置而以該氣體分析裝置進行定量分析，根據以該氣 體分析裝置已分析的環狀化合物之分析値而以判定裝置判 斷矽膠液的劣化狀況，將以此氣體分析裝置已分析的環狀 200844431 化合物之分析値以及/又或是以判定裝置已判斷之矽膠液 的劣化狀況，顯示於顯示裝置，作爲其特徵。 [發明的效果] 如藉由本發明，則因爲將由作爲矽膠液浸電性機器的 絕緣·冷卻媒體而使用的矽膠液之熱劣化而產生的低分子 量、低沸點的環狀化合物，在現場（on-site)可效率佳而且 簡便地測定，所以可實現：可正確而且簡便地診斷作爲矽 膠液浸電性機器的絕緣·冷卻媒體而使用的矽膠液的熱劣 化之，電性機器用矽膠液之劣化診斷裝置以及電性機器用 矽膠液之劣化診斷方法。 【實施方式】 接著關於本發明的實施例的矽膠液浸電性機器之矽膠 液的劣化診斷裝置及矽膠液的劣化診斷方法，使用圖面而 說明。 [實施例1] 作爲本發明的實施例的矽膠液浸電性機器之一例，說 明矽膠液浸變壓器之構成。 第1圖係表示爲本發明的一實施例的矽膠液浸變壓器 之劣化診斷裝置的構成之物，在此矽膠液浸變壓器，係各 具備槽1、與配置於槽1的內部的鐵心2、與被安裝於鐵心2 的內側捲線3與外側捲線4、與絕緣筒5。 -8 - 200844431 於槽1的內部，係收容：用以絕緣·冷卻這些鐵心2與 內側捲線3及外側捲線4之絕緣·冷卻媒體的矽膠液6、和 存在於此矽膠液6的上方之氮氣氣體7。 於槽1的外部，係設置用以冷卻被收容於槽1的內部的 絶緣·冷卻媒體之矽膠液6的冷卻器8，此槽1與氮氣氣體7 係通過個別配設於該上部與下部的冷卻配管9a、9b而連 接。 被收容於槽1的內部的絕緣·冷卻媒體之矽膠液6，爲 有機矽化合物的聚合物’爲具有下述的（1)式、或（2)式所 示之化學構造式的直鏈狀的化合物。亦有被稱爲矽油的情 況，但基本上兩者爲相同之物。這些係單獨使用、混合使 用亦佳，但使用表示於（1)式之二甲基矽膠液爲理想。 ch3 ch3 ch3。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 [Prior Art] Conventionally, an insulating oil such as mineral oil is used for the insulation/cooling medium of a transformer using an electric device of an insulating/cooling medium. By using this mineral oil as an insulating/cooling medium for the transformer, by using a flame retardant silicone liquid, the fire resistance of the transformer can be improved, and the electric machine can be tightened by increasing the operating temperature. However, when the silicone liquid is used as the insulating/cooling medium, if the operating temperature of the high-electricity machine is higher than before, a low-molecular-weight, low-boiling decomposition product due to thermal deterioration of the silicone liquid is generated. If the decomposition product is produced in a large amount in the silicone liquid, the temperature at which the silicone liquid is ignited (hereinafter referred to as the ignition point) is lowered, so that the silicone liquid becomes liable to cause ignition. The amount of decomposition of this decomposition product increases as the operating temperature of the electrical machine increases. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. 1 0-3 3 2682 discloses that the number of chemiluminescence is measured by heating and heating an electrical insulating oil used in an oil-immersed electric device, and the degree of deterioration of the electrical insulating oil is evaluated. technology. Japanese Laid-Open Patent Publication No. Hei 3 - 1 872 06 discloses that a plurality of gas detectors are disposed on the upper portion of a tank of an oil-immersed machine such as an oil-immersed transformer 200844431 or an oil-immersed reactor. The flammable gas is a technique that is introduced into the groove structure of each gas detector efficiently, and reliably detects an abnormality such as insulation breakdown or local heating of the electric device. In Japanese Laid-Open Patent Publication No. Sho 59-9767, the thermal weight characteristics of the silicone liquid for electrical insulation are measured, and the heat resistance index TGI (°C) is obtained from the characteristic curve. When 値 (325 °C) or less, the technique of determining that the silicone liquid has deteriorated is determined. In Japanese Patent Laid-Open Publication No. SHO 54-119, the disclosure of the present invention is to disclose that an electric device in which insulating oil is injected is extracted from the gas phase by bubbling a gas component in the insulating oil at room temperature. Analytical technology. Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Publication No. Sho 54-1 1 4290. SUMMARY OF THE INVENTION When a silicone liquid is thermally deteriorated, a cyclic polymer is produced, and its main component is a 3-mer, a 4-mer, and a 5-mer. It is understood that the more the deterioration progresses, the more the amount of cyclization produced becomes. The 3-mer, 4-mer, and 5-mer have a low boiling point and are easily evaporated. In the initial state without deterioration, the ring body is hardly contained. A low molecular weight linear compound is also produced due to deterioration. However, in the initial state which is not deteriorated, a low molecular weight linear compound is also contained. Thus, i.e., -5-200844431 causes a certain degree of low molecular weight linear compound to evaporate in an initial state. In the aforementioned Patent Document 3, the silicone liquid is extracted in a certain amount, and this is heated at a constant temperature gradient to evaporate the low molecular weight compound, and the deterioration index is obtained by reducing the heating temperature by 10% and 20% by weight. However, since the silicone liquid system contains a linear compound having a low molecular weight even in an initial state, there is a problem that the amount of reduction in weight (that is, the amount of evaporation) is insufficient for the determination of deterioration. In addition, the temperature at which the weight is reduced by 20% is also changed from 350 degrees C to 3 70 degrees C. At such a high temperature, it is predicted that since the normal silicone liquid is thermally decomposed and changed into a low molecular compound, it is thermally degraded. The judgment has an adverse effect. The inventors of the present invention have experimentally confirmed that the low molecular weight cyclopolymer produced in the silicone liquid can be used as an indicator of thermal deterioration, and the present invention has been made. That is, the state of thermal deterioration can be accurately grasped by quantitatively analyzing the cyclic polymer in the silicone liquid. The main component of the low molecular weight and low boiling point decomposed product which is produced by thermal deterioration of the silicone liquid is a cyclic compound having the same basic chemical structure as the silicone liquid. Therefore, it is difficult to selectively analyze and quantify the cyclic compound which is a decomposition product of the silicone liquid in the silicone liquid. An object of the present invention is to provide a deterioration diagnostic apparatus for a silicone liquid for electrical equipment that can accurately and easily diagnose the thermal deterioration of a silicone liquid used as an insulating and cooling medium for a silicone fluid-immersed device. A method for diagnosing degradation of silicone fluid for electrical equipment. -6 - 200844431 [Means for Solving the Problem] The deterioration diagnosis device for the silicone resin for an electric device according to the present invention includes an electric device, a groove for housing the electric device therein, and a storage device In the tank, insulating and cooling the silicone liquid of the electric device, taking a part of the silicone liquid in the tank to the outside of the tank, and heating the silicone liquid taken by the piping as described above to be contained in the silicone a gas component for vaporizing and vaporizing a cyclic compound in a liquid, a gas analyzer for quantitatively analyzing a cyclic compound in which the gas component is vaporized and vaporized, and a ring for analysis according to the gas analyzer The analysis device for determining the deterioration state of the silicone liquid, the analysis of the cyclic compound which has been analyzed by the gas analysis device, and/or the deterioration of the silicone liquid which has been judged by the above determination device A display device of the condition is characterized as being. Further, the method for diagnosing the deterioration of the silicone liquid for an electric device according to the present invention is a deterioration of the silicone liquid for electrical equipment which is housed in the inside of the tank and is insulated and cooled by the silicone liquid stored in the tank. The diagnosis method is: taking a part of the silicone liquid in the tank to the outside of the tank by taking a pipe, supplying the used silicone liquid to the gas component take-up container, and heating the gas component to take the container to be contained in The cyclic compound in the silicone liquid is vaporized and vaporized, and the vaporized gasified cyclic compound is supplied to the gas analysis device for quantitative analysis by the gas analysis device, and the cyclic compound analyzed by the gas analysis device is analyzed. The determination device determines the deterioration state of the silicone liquid, and displays the analysis of the cyclic 200844431 compound analyzed by the gas analysis device and/or the deterioration state of the silicone liquid judged by the determination device, and displays it on the display device. As its characteristics. [Effects of the Invention] According to the present invention, a low-molecular-weight, low-boiling cyclic compound produced by thermal deterioration of a silicone liquid used as an insulating/cooling medium for a silicone liquid-immersive device is on site (on -site) is highly efficient and easy to measure, so it can be used to accurately and easily diagnose the thermal deterioration of the silicone liquid used as the insulation and cooling medium for the silicone liquid immersion machine. The deterioration diagnosis device and the deterioration diagnosis method for the silicone liquid for electric equipment. [Embodiment] Next, the deterioration diagnosis device for the silicone liquid of the silicone liquid immersion machine according to the embodiment of the present invention and the deterioration diagnosis method of the silicone liquid will be described with reference to the drawings. [Embodiment 1] As an example of a silicone liquid immersion machine of an embodiment of the present invention, a configuration of a silicone liquid immersion transformer will be described. Fig. 1 is a view showing a configuration of a deterioration diagnosing device for a silicone immersion transformer according to an embodiment of the present invention, wherein the silicone immersion transformer includes a groove 1 and a core 2 disposed inside the groove 1. The inner winding wire 3 and the outer winding wire 4, which are attached to the core 2, and the insulating cylinder 5. -8 - 200844431 The inside of the tank 1 accommodates: a silicone liquid 6 for insulating and cooling the insulation and cooling medium of the core 2 and the inner winding 3 and the outer winding 4, and nitrogen gas present above the silicone 6 Gas 7. A cooler 8 for cooling the silicone liquid 6 of the insulating/cooling medium accommodated in the inside of the tank 1 is provided outside the tank 1, and the tank 1 and the nitrogen gas 7 are individually disposed in the upper portion and the lower portion. The pipes 9a and 9b are cooled and connected. The silicone resin 6 of the insulating and cooling medium accommodated in the inside of the tank 1 is a linear polymer having the chemical structure formula represented by the following formula (1) or (2). compound of. There is also a situation known as oyster sauce, but basically the two are the same. These are preferably used singly or in combination, but it is preferred to use a dimethyl hydrazine solution represented by the formula (1). Ch3 ch3 ch3
I I I CH3 — Si — O —（ Si — 0 )n— Si — CH3 ···("!)I I I CH3 — Si — O —( Si — 0 )n— Si — CH3 ···("!)
I I I ch3 ch3 ch3 CHq CgHg CH3 CH3I I I ch3 ch3 ch3 CHq CgHg CH3 CH3
II I I CH3 — Si — 0 -（Si 一 〇)p_ (Si — 0)q-Si — CH3 ··· (2)II I I CH3 — Si — 0 —(Si 〇)p_ (Si — 0)q-Si — CH3 ··· (2)
II II ch3 c6h5 ch3 ch3 被收容於槽1的內部的絶緣·冷卻媒體之矽膠液6係通 過上部的冷卻配管9a而從槽1的內部朝向冷卻器8的內部 以箭頭所示的方式流動’在冷卻器8被冷卻之後’通過下 -9- 200844431 部的冷卻配管9b而從冷卻器8再度送入槽1的內部，將具 備於槽1的內部之鐵心2、內側捲線3、外側捲線4冷卻，以 奪走從鐵心2、內側捲線3、外側捲線4產生的焦耳熱的方 式發揮機能。 鐵心2係於藉由個別被安裝於上部和下部的固定零件 10a、10b而夾緊保持。 於內側捲線3和外側捲線4的上部係個別設置絕緣物1 i 、1 2，於內側捲線3和外側捲線4的下部亦個別設置絕緣物 1 3、14。另外，於鐵心2的中心側係形成冷卻鐵心2的冷卻 用之液導入部1 5。 本實施例的矽膠液浸變壓器，係爲了將藉由絕緣·冷 卻媒體的矽膠液6之熱劣化而產生的低分子量、低沸點的 環狀化合物，藉由加熱矽膠液6而使矽膠液6的液面上之氣 相部分蒸發、氣化而作爲氣體成分而進行分析，所以設置 由以下的構成所形成之分解物分析裝置。 也就是，具備：配設於槽1的下部而採取槽1的內部之 矽膠液6的配管1 6、和連接此配管1 6而設置，使已採取的 矽膠液6加熱蒸發而用以採取氣體成分之氣體成分採取容 器1 7、和連接於氣體成分採取容器1 7而設置，將使矽膠液 6力口熱蒸發而已採取之氣體成分從氣體成分採取容器η導 出之氣體配管1 8、和連接此氣體配管1 8而設置，分析從被 導出的矽膠液6採取的氣體成分之氣體分析裝置1 9、和根 據以此氣體分析裝置1 9分析之氣體成分與劣化的基準値的 比較，而判斷矽膠液的劣化狀況之判定裝置3 0、和顯示： -10- 200844431 以氣體分析裝置1 9分析之氣體成分、或是以判定裝置30判 定之矽膠液的劣化狀況之顯示裝置3 2，而構成電性機器用 石夕膠液之劣化診斷裝置。 另外，爲了使已採取的矽膠液6中的環狀化合物蒸發 、氣化，所以於氣體成分採取容器1 7的外側係設置加熱矽 膠液6的加熱器20。在此氣體成分採取容器1 7，係藉由加 熱器20而加熱內部的矽膠液6，使藉由熱劣化而產生的低 分子量、低沸點的環狀化合物蒸發、氣化之加熱溫度’係 設定爲約l〇〇°C〜220°C、理想爲約150°C〜200°C。 於第2圖表示矽膠液的加熱溫度與環聚物的離子強度 的關係之特性圖。第2圖係爲了作爲劣化的指標而分析環 聚物，而硏究：在已提高矽膠液的溫度的情況之3聚物、4 聚物、5聚物的各成分之蒸發·氣化舉動的結果。 觀察係藉由產生氣體分析法（EGA-MS : Evolved Gas Analysis - Mass Spectrometry)而進行。 爲了提高測定感度，試料係不使用矽膠液的熱劣化品 ，而使用於矽膠液添加了二甲基矽的3聚物（D 3 )、4聚物 (D4)、5聚物（D 5)之物。將試料放入槽之後在以He氛圍使 其安定，以昇溫速度l〇°C /min從50 °C開始昇溫加熱試料 ，至300 °C將連續產生的氣體導入質量分析裝置（mass spectrometer) ° 作爲對應於環聚物D3、D4、D5之特徵離子，選擇 M/Z値，也就是離子的質量（M)與電荷數（Z)的比爲207、 28 1、3 5 5之物，測定各離子強度、和該全離子流（Total -11 - 200844431II II ch3 c6h5 ch3 ch3 The silicone liquid 6 of the insulating/cooling medium accommodated in the inside of the tank 1 flows through the upper cooling pipe 9a from the inside of the tank 1 toward the inside of the cooler 8 as indicated by an arrow. After the cooler 8 is cooled, it is again sent into the inside of the tank 1 from the cooler 8 through the cooling pipe 9b of the lower -9-200844431, and the core 2, the inner winding 3, and the outer winding 4 provided inside the tank 1 are cooled. The function of the Joule heat generated from the core 2, the inner winding line 3, and the outer winding line 4 is taken away. The core 2 is clamped and held by the fixing members 10a and 10b which are individually attached to the upper and lower portions. The insulators 1 i and 1 2 are separately provided on the upper portions of the inner winding wire 3 and the outer winding wire 4, and the insulators 1 3 and 14 are separately provided on the lower portions of the inner winding wire 3 and the outer winding wire 4. Further, a liquid introduction portion 15 for cooling the cooling core 2 is formed on the center side of the core 2. The silicone liquid immersion transformer of the present embodiment is a low molecular weight, low boiling point cyclic compound produced by thermal deterioration of the silicone liquid 6 by the insulating/cooling medium, and the silicone liquid 6 is heated by heating the silicone liquid 6 Since the gas phase on the liquid surface is partially vaporized and vaporized and analyzed as a gas component, a decomposition product analysis device formed by the following configuration is provided. In other words, the pipe 16 is disposed in the lower portion of the tank 1 and takes the silicone liquid 6 inside the tank 1, and is connected to the pipe 16 to heat the vaporized liquid 6 to take gas. The gas component of the component is provided in a container 17 and a gas component is connected to the gas container 1 to be used, and the gas component taken from the gas component is taken from the gas component to the gas pipe 18 and connected. The gas pipe 18 is provided, and the gas analyzer 1 9 for analyzing the gas component taken from the derived silicone liquid 6 is compared with the gas component analyzed by the gas analyzer 19 and the reference 劣化 of the deterioration. The determining device 30 of the deterioration state of the silicone liquid and the display: -10- 200844431 The gas component analyzed by the gas analyzer 19 or the display device 3 2 which is the deterioration state of the silicone liquid determined by the determining device 30 is configured. Deterioration diagnostic device for Shixia glue for electric machines. Further, in order to evaporate and vaporize the cyclic compound in the silicone liquid 6 to be taken, the heater 20 for heating the silicone 6 is provided outside the container 17 of the gas component. In this gas component, the container 17 is used to heat the internal silicone liquid 6 by the heater 20, and the heating temperature of the low molecular weight and low boiling point cyclic compound generated by thermal deterioration is vaporized and vaporized. It is about 1 ° C to 220 ° C, preferably about 150 ° C to 200 ° C. Fig. 2 is a characteristic diagram showing the relationship between the heating temperature of the silicone liquid and the ionic strength of the cyclopolymer. In the second graph, the cyclopolymer is analyzed as an indicator of deterioration, and the evaporation/gasification of each component of the 3-mer, the 4-mer, and the 5-mer in the case where the temperature of the silicone liquid is increased is increased. result. The observation was carried out by gas generation analysis (EGA-MS: Evolved Gas Analysis - Mass Spectrometry). In order to improve the sensitivity of the measurement, the sample is a non-thermally deteriorated product of a silicone liquid, and a 3-mer (D 3 ), a 4-polymer (D4), and a 5-polymer (D 5) to which a dimethyl hydrazine is added to a silicone liquid. Things. After the sample was placed in the tank, it was stabilized in a He atmosphere, and the sample was heated from 50 ° C at a temperature increase rate of 10 ° C /min, and the continuously generated gas was introduced into a mass spectrometer (mass spectrometer) at 300 ° C. As the characteristic ions corresponding to the nucleus polymers D3, D4, and D5, M/Z 値 is selected, that is, the ratio of the mass (M) of the ions to the number of charges (Z) is 207, 28 1 , 3 5 5 , and the measurement is performed. Ionic strength, and the total ion current (Total -11 - 200844431
Ion Current)。 至5 0〜3 0 0 t：於He氛圍下加熱矽膠液，於 圖2中，顯示將M/Z値207以一點虛線表示，將M/Z値281 以實線表示，將M/Z値3 5 5以虛線表示之結果。 關於任一之環聚物，都在80〜90 °C左右開始蒸發·氣 化，在22(TC左右放出全部的環量體。因而，加熱溫度係 可作爲100°C〜220°C左右。 另外，藉由加熱至150 °C〜220 °C而可短縮觀察時間， 可效率佳地進行測定。而且，若是設爲比230〜250 °C更高 溫，則再次檢測環聚物。此係可預知：藉由作爲高溫，而 開始矽膠液的分解、和分解生成物的蒸發·氣化。 在表示於第1圖之矽膠液浸變壓器之氣體成分採取容 器1 7，係藉由以加熱器20而加熱已收容於氣體成分採取容 器17的內部之特定量的矽膠液6，使因矽膠液6的熱劣化而 產生的低分子量、低沸點的環狀化合物，蒸發、氣化爲氣 體成分採取容器1 7的內部之矽膠液面上的氣相部分而使氣 體成分形成。 作爲採取特定量的矽膠液的手段，係例如可舉出：將 閥（2 1 a)打開一定時間而採取大略一定量的矽膠液，預先 設置測定已採取的矽膠液的重量之手段。 藉由加熱而蒸發、氣化爲氣體成分採取容器17的內邰 的氣相部分之因矽膠液6的熱劣化而產生的低分子量化合 物的氣體成分，係通過氣體配管18而被送至氣體分析裝置 19，藉由此氣體分析裝置19而僅分析、定量因熱劣化而產 生的低分子量、低沸點之環狀化合物的量。也就是’並非 -12- 200844431 測定因加熱而蒸發之氣體成分全部的量，而僅計測從已蒸 發的氣體成分中之環聚物（3聚物、4聚物、5聚物）的總量 〇 作爲從氣體成分採取容器1 7，取出環狀化合物至氣體 分析裝置1 9的手段，係例如可舉出：流過氮、氦、氬等的 惰性氣體。 另外，以於氣體成分採取容器1 7的內部設置作到可以 加熱器加熱之吸附劑，使已蒸發、氣化爲氣相部分的環狀 化合物之氣體成分暫時吸附之後，加熱吸附劑而將已氣化 的環狀化合物的氣體成分，藉由惰性氣體而導入氣體分析 裝置1 9，亦可有效率地取出環狀化合物。 另外，事先將3聚物、4聚物、5聚物的量、和矽膠液 的引火點等的劣化狀態的特性附上關連，而可根據藉由氣 體分析裝置1 9而得到的結果之劣化診斷。 例如：在藉由氣體分析結果而得到的分析値、或被算 出的環狀化合物之環聚物的量成爲特定値以上的情況，矽 膠液係判定爲劣化。 在本實施例的電性機器用的矽膠液之劣化診斷裝置， 係設置：如第1圖所示的判定裝置3 0、與基準値設定器3 3 、與顯示裝置32、與資料庫31。 然後，矽膠液的劣化診斷，係藉由氣體分析裝置1 9而 將已定量分析之從矽膠液使其蒸發氣化的環狀化合物的氣 體成分之測定値，輸入至判定裝置3 0，在此判定裝置3 0根 據以氣體分析裝置1 9已分析之環狀化合物的氣體成分的測 -13- 200844431 定値（分析値、或被算出的環狀化合物的環聚物的量），進 行與：從基準値設定器3 3輸入之成爲環狀化合物的劣化的 判斷基準之環聚物的基準値的比較，在環狀化合物的測定 値係超過了環聚物的基準値的情況’判斷爲矽膠液係已劣 化之物。 藉由此判定裝置30的矽膠液的劣化判斷狀況，係可從 此判定裝置30輸出而在顯示裝置32使其顯示。 另外，亦可將輸入於判定裝置30之以氣體分析裝置19 已分析的環狀化合物的氣體成分的測定値（分析値、或被 算出的環狀化合物的環聚物的量），經由該判定裝置3 0而 使其顯示於顯示裝置32，在此情況，係可將以氣體分析裝 置1 9分析的環狀化合物的氣體成分的測定値之分析値或從 氣體分析結果算出的環聚物的量，以判定裝置30監視。 另外，矽膠液的劣化，係因爲因應於電性機器的運轉 年數而進行，所以爲了正確地把握此劣化的進行狀況，使 以氣體分析裝置1 9分析的環狀化合物的氣體成分的測定値 ，經由該判定裝置3 0而於資料庫3 1與運轉期間的經過資料 一起輸入而使其先記錄。若如此進行，則如從資料庫3 1將 記憶的過去的資料叫出至前述判定裝置30而使其顯示於顯 示裝置3 2，則成爲可正確地把握因電性機器的運轉年數經 過之矽膠液的劣化狀況的變遷。 在此，關於判斷矽膠液的劣化狀況之矽膠液的性質狀 態，使用第6圖而說明。第6圖係表示被使用於矽膠液浸變 壓器之矽膠液的熱劣化促進試驗的結果之特性圖，個別表 -14- 200844431 示：橫軸爲藉由矽膠液的加熱老化試驗（250 °C x 100小時） 的老化時間、左側的縱軸係矽膠液的引火點、右側的縱軸 係被包含於矽膠液的環聚物的量。 如由第6圖明暸地，表示於矽膠液的引火點的特性曲 線，係在矽膠液爲新品的情況係3 00 °C以上，但在矽膠液 的劣化進展的老化時間經過的同時，引火點下降。 另外，表示被包含於矽膠液的環聚物（3聚物D3、4聚 物D4、5聚物D5)的量之特性曲線，係在矽膠液爲新品的 情況爲少量，但在矽膠液的劣化進展的老化時間經過的同 時急增。 然後，矽膠液的引火點，係若下降得比200 °C低，則 因爲有於電性機器引火的可能性，所以，若是將在此引火 點2 00 °C的環量體的量，例如將3 000，設定爲劣化判斷的 基準値而定量分析砂膠液並測定環聚物的量’則成爲可正 確，而且簡便地判斷矽膠液的劣化狀況。 然後在判定爲矽膠液爲劣化的狀況時，係停止電性機 器的運轉、或在日常的檢查項目確認有無電性機器的異常 、採取矽膠液而更詳細地分析狀態。 將藉由上述判定裝置30而診斷矽膠液的劣化狀況之矽 膠液的狀態，以顯示裝置3 2顯示之監視器畫面的模式圖’ 表示於第3圖。在第3圖係顯示：對於電性機器的運轉時間 而將以氣體分析裝置1 9測定之使矽膠液蒸發的氣體成分的 環聚物的量，以△表示而畫線之物、和爲了判定矽膠液的 劣化而事先適宜設定之環聚物量的基準値的値3〇〇〇(虛線） -15- 200844431 第3圖係模擬在熱劣化促進試驗以高負荷運轉的變壓 器A、與以比較低負荷而運轉的變壓器B之物’橫軸爲將 老化時間換算爲實際運轉年數而顯示。 在求取此特性時，所謂高負荷係將加熱溫度設定爲 270度C、所謂低負荷係將加熱溫度設定爲220度C ’而測 定在個別的時間軸之環聚物的量。 將至相當於現在運轉年數1 0年的點爲止之測定値，以 圓形符號和三角符號畫在圖上。一點虛線’係平滑地連結 變壓器A的測定値之假想線，同樣地，實線爲變壓器B 者。 這些假想線的延長與設定値交叉之點係成爲個別的變 壓器的矽膠液的使用界限。關於變壓器B，係可推定爲如 以L所示般地，有約7年的剩餘壽命。 在實際的變壓器，因爲如繼續進行環聚物的測定而先 保存該資料，則可求出如第3圖般的特性，所以成爲可從 連結複數的實測資料的各實測値之假想線來預測矽膠液的 交換時期。 然後，按照顯示於顯示裝置3 2的監視器畫面之砂膠液 的劣化程度，在定期檢查時等，停止電性機器時，以交換 矽膠液的一部分或全部而成爲可將電性機器之變壓器的故 障防患於未然。 另外，在診斷矽膠液的劣化時，藉由一般周知矽膠液 的劣化的手段，例如：將以判定裝置3 〇判定之矽膠液的劣 -16- 200844431 化判斷顯示於顯示裝置3 2的監視器畫面，而可容易地進行 管理。 例如：在矽膠液的環聚物量係超過了事先設定的特定 値的情況’判斷爲矽膠液已劣化而使其顯示於顯示裝置3 2 的監視圖畫面。 電性機器的矽膠液的劣化確認頻率爲一週一次、一月 一次等。因而可使前述判定裝置3 0定期運轉而在每個特定 時間進行劣化的判定。 另外，於前述判定裝置3 0，係以設置：將氣體成分採 取容器17及氣體分析裝置19的運轉操作、進行矽膠液的供 給之幫浦或閥2 1 a的操作、及加熱矽膠液的加熱器20的操 作，加以各別控制之控制裝置般地構成，藉由來自判定裝 置3 0的操作指令而使未圖示的幫浦以特定的周期作動而將 槽1內的矽膠液6採取至氣體成分採取容器17的同時，讓此 氣體成分採取容器17的加熱器20入熱而開始矽膠液6的加 熱，而且使氣體分析裝置19作動。 首先，藉由來自判定裝置3 0的操作指令而開放閥2 1 a ，從與槽1連接的採取配管1 6a採取槽1內的矽膠液6，在 關閉閥2 1 a之後作動加熱器20，加熱被採取至氣體成分採 取容器1 7的矽膠液6而使被含有於矽膠液中的環狀化合物 蒸發氣化，將此已蒸發氣化的環狀化合物在氣體分析裝置 19進行定量分析。 _ 然後，使在氣體分析裝置19分析的環狀化合物的分析 値或根據此環狀化合物的分析値而以判定裝置30判斷的矽 200844431 膠液的劣化狀況顯示於顯示裝置32。 以氣體分析裝置1 9分析環聚物量之後，藉由來自判定 裝置30的指令而將設置於氣體成分採取容器17的加熱器20 加以停止，淨化殘留於分析裝置等的成分。矽膠液6係因 爲分解物成爲少之物，所以不排出至系外，而回到槽1內 亦佳。另外，被測定的矽膠液6的量係因爲少量（例如：5 0 ml)，所以廢棄亦可。 另外，藉由一台的氣體分析裝置、判定裝置，而亦可 監視複數台的變壓器等的電性機器。 按照上述而矽膠液6的劣化的確認頻率，係因爲爲一 周一次或一月一次等，所以對於一台的分析裝置，作爲具 有數台的電性機器、和具有配管的切換裝置、電性機器用 的矽膠液的劣化診斷系統亦佳。 藉由複數台的電性機器，可採取個別的矽膠液6，把 握各電性機器的矽膠液的劣化狀態。 使用於一次的判定之矽膠液6的採取，係若矽膠液多 則可得到的氣體的定量爲容易、若少則矽膠液的加熱成爲 容易。 矽膠液6的採取係作爲1〜50ml爲理想，在1〜5ml左右 亦可充分的測定。殘留在劣化判定後之氣體成分採取容器 1 7的矽膠液6，係因爲不具有下降引火點之低分子量的化 合物，所以可回到槽1而再利用。 此時，設置將矽膠液6回流到槽1的回流配管、和於該 配管中使矽膠液6環流的幫浦爲理想。 -18- 200844431 幫浦係可藉由上述的判定裝置30而控制。而且，在判 定了劣化之後的矽膠液6，係廢棄，並按照必要而補充之 構成亦佳。 如藉由上述的構成之注入矽膠液變壓器，則因爲將： 藉由在變壓器的運轉中被收容於槽1的內部的絕緣·冷卻 媒體的矽膠液6之熱劣化而生成而溶解於矽膠液6中的環狀 化合物，藉由加熱矽膠液6而使之蒸發·氣化爲矽膠液6的 液面上的氣相部分而作爲氣體而進行分析般地進行，所以 藉由矽膠液6的熱劣化而產生的環狀化合物係因爲在現場 可效率佳、簡便地定量，所以可容易地謀求矽膠液浸變壓 器之預防保全。 被使用於矽膠液浸變壓器之絕緣·冷卻媒體的矽膠液 6，係因爲：在槽1與冷卻器8之間，經由連接於兩者的冷 卻配管9a、9b而循環，將在冷卻器8冷卻的矽膠液6，供 給於設置於槽1的內部的鐵心2、內側捲線3和外側捲線4的 捲線等而冷卻這些機器之物’所以矽膠液6的黏度低比較 理想，特別是在25°C的動黏度係數爲55mm2/s以下者爲理 想。 一般而言，砂膠液6的引火點係相依於該分子量’另 外，分子量越小、矽膠液6的黏度變得越低。因而’可預 知：黏度越低則矽膠液6的引火點係越變低’因該熱分解 之低分子量、低沸點的分解物的生成物係變得越多。 另外，在謀求：變壓器的防火性的提高、或是將運轉 溫度變高之機器的緊緻化等之下’矽膠液6係難燃性者爲 -19- 200844431 理想，特別是引火點超過2 5 0 °C者爲理想。 因而，作爲被使用於矽膠液浸變壓器之絕縁·冷卻媒 體的矽膠液6，而引火點爲超過250 °C，而且，在25 °C的動 黏度係數爲55mm2/s以下的矽膠液6爲有效。 而且，於本實施例的矽膠液6，係作到加入在鑛油浸 變壓器被使用的帶電防止劑等的添加劑亦佳。 如藉由本實施例，則因爲將由作爲矽膠液浸電性機器 的絕緣·冷卻媒體而使用的矽膠液之熱劣化而產生的低分 子量、低沸點的環狀化合物，在現場（on-site)可效率佳而 且簡便地測定，所以可實現：可正確而且簡便地診斷作爲 矽膠液浸電性機器的絕緣·冷卻媒體而使用的矽膠液的熱 劣化之，電性機器用矽膠液之劣化診斷裝置以及電性機器 用矽膠液之劣化診斷方法。 [實施例2] 接著使用第4圖而說明本發明的其他實施例的矽膠液 浸變壓器用之矽膠液的劣化診斷裝置的構成。在表示於第 4圖的本實施例之矽膠液浸變壓器之變壓器，係成爲：氣 體成分採取容器1 7爲經由與設置於冷卻器8的下部的冷卻 配管9 b連通之配管1 6 a而配設的構成。 因爲使採取此矽膠液6的配管1 6a，以不直接連通於槽 1而連通於冷卻配管9b的方式設置’所以可簡便地進行配 管1 6 a的配設。 表示於第4圖之本實施例的矽膠液浸變壓器用的矽膠 -20- 200844431 液之劣化診斷裝置的構成，係因爲與表示於第1圖之先前 的實施例1的矽膠液浸變壓器用的矽膠液之劣化診斷裝置 基本上的構成爲相同，所以省略於兩者共通的構成之說明 〇 另外，將在第4圖之因本實施例的矽膠液浸變壓器， 在運轉中因絕緣·冷卻媒體的矽膠液6之熱劣化而產生的 低分子量、低沸點的環狀化合物，在現場進行分析·定量 的作法，亦與表示於第1圖之先前的實施例1相同，所以省 略在此的說明。 藉由上述之本實施例的矽膠液浸變壓器用的矽膠液之 劣化診斷裝置，亦與記載於第1圖之先前的實施例同樣地 ，因爲將由作爲矽膠液浸電性機器的絕緣·冷卻媒體而使 用的矽膠液之熱劣化而產生的低分子量、低沸點的環狀化 合物，在現場（on-site)可效率佳而簡便地測定，所以可實 現：可正確而且簡便地診斷作爲矽膠液浸電性機器的絕緣 •冷卻媒體而使用的矽膠液的熱劣化之，電性機器用矽膠 液之劣化診斷裝置以及電性機器用矽膠液之劣化診斷方法 [實施例3] 於第5圖係表示爲本發明的更其他實施例的電性機器 用的矽膠液之劣化診斷裝置。在本例係使矽膠液6循環於 分析裝置內的例子。在本實施例，係將矽膠液6的採取口 作爲槽本體1、將矽膠液6的放出口作爲冷卻器8的配管9b -21 - 200844431 。用以矽膠液6的循環之幫浦28係設置於配管16a ° 開放設置於配管16a的閥21a、設置於配管16b的閥 2 1b，而在連通至氣體成分採取容器17的配管使矽膠液6循 環，並在此氣體成分採取容器1 7的內部的矽膠液，替換了 於測定時使用之已採取的特定量的矽膠液6之時間點，關 閉閥2 1 a、2 1 b，使氣體成分採取容器1 7內的特定量的矽膠 液6，在設置於氣體成分採取容器17的加熱器20加熱蒸發 而採取氣體成分。 接著，將在氣體成分採取容器1 7已採取的氣體成分， 以氣體分析裝置1 9分析而測定氣體成分中的環聚物量。然 後，根據在此氣體分析裝置1 9分析之氣體成分的測定値（ 分析値、或算出的環狀化合物的環聚物的量），進行與從 基準値設定器3 3輸入之成爲環狀化合物的劣化的判斷基準 之環聚物的基準値的比較，在環狀化合物的測定値係超過 了環聚物的基準値的情況，判斷爲矽膠液已劣化。 藉由此判定裝置3 0所致的矽膠液的劣化判斷狀況，係 此判疋裝置3 0輸出而在顯不裝置3 2顯示。 另外’如能作到將輸入於判定裝置3 0之以氣體分析裝 置19已分析的環狀化合物的氣體成分的測定値（分析値、 或被算出的環狀化合物的環聚物的量），經由該判定裝置 3 〇而於顯示裝置3 2使其顯示，則在此情況，係可將以氣體 为析置1 9分析的環狀化合物的氣體成分的測定値之分析 値或f皮热體分析結果算出的環聚物的量，以判定裝置3 〇臣七 視。 -22- 200844431 測定後的矽膠液6，係因爲僅環聚物減少’所以可開 放閥21a、21b而回到槽1。 另外，即使從冷卻配管9b採取矽膠液6也沒有關係’ 但爲了減輕分析時的加熱，所以從冷卻配管9a、或是從槽 1本體的上部採取者爲有效率。 另外，冷卻配管9 a、9 b係爲了矽膠液6的流速快’所 以藉由將矽膠液6的放出口作爲配管而產生循環，可省略 幫浦的一部分而爲理想。 而且，在本實施例，係附有告知矽膠液的劣化診斷裝 置的診斷結果之機能。因爲不僅顯示以氣體分析裝置1 9所 分析的環狀化合物的氣體成分之測定値（環狀化合物的環 聚物的量），而且在根據環狀化合物的氣體成分的測定値 並藉由在判定裝置3 0的比較運算而超過成爲劣化的判斷基 準之環聚物的基準値的情況，判斷爲矽膠液已劣化，而將 此矽膠液的劣化判斷結果顯示於顯示裝置3 2，所以可將爲 在氣體分析裝置1 9已分析的環狀化合物的氣體成分的測定 値之分析値、或矽膠液的劣化診斷裝置的診斷結果，以此 判定裝置30監視。 管理者，係可藉由本實施例而確認矽膠液6的劣化狀 態，進行機器的管理。例如具備：在環聚物的放出量係超 過了事先設定的特定値的情況，判斷爲矽膠液6已劣化而 發出警報的警報裝置等亦佳。 例如：作爲輸入至基準値設定器3 3的基準値，係藉由 已劣化的矽膠液而得到的測定値、或如先硏究電性傳導性 -23- 200844431 或著火溫度等的特性而設定亦佳。 而且，閥或警報裝置係可採用適宜周知之物，但在電 源停止時開放閥、警報成爲ON者爲理想。 如藉由本實施例，則因爲將由作爲矽膠液浸電性機器 的絕緣·冷卻媒體而使用的矽膠液之熱劣化而產生的低分 子量、低沸點的環狀化合物，在現場（on-site)可效率佳而 且簡便地測定，所以可實現：可正確而且簡便地診斷作爲 矽膠液浸電性機器的絕緣·冷卻媒體而使用的矽膠液的熱 劣化之，電性機器用矽膠液之劣化診斷裝置以及電性機器 用矽膠液之劣化診斷方法。 接著，說明關於在：具備了表示於第1圖、第4圖、第 5圖的矽膠液的劣化診斷裝置之矽膠液浸電性機器的劣化 診斷之運轉形式的一例。由矽膠液的劣化診斷裝置所致的 診斷，係可以一週一次或一月一次等的設定之頻率、或是 恆常反覆進行。 以下，說明使用了每週期進行之矽膠液的劣化診斷裝 置的診斷例。矽膠液的劣化診斷裝置的運轉，係主要是可 分爲測定準備、測定、清掃、恒常狀態的4階段。 -24- 200844431 表1 用以診斷劣化的運轉內容 閥 (V 卜 V2) 加熱器 (H) 時間 測定準備 配管中的矽膠液的替換 開 OFF lOmin 樣本採取、測定 將一定量的矽膠液中的環狀 化合物加熱而抽出、測定量 閉 ON lOmin 清掃 將測定後的矽膠液排出至系 外，或是回流至槽內 閉 OFF 15min 恒常時 (待機時） 停止 閉 OFF 特定期間 而且，於上述的表1的各階段必要的時間，係藉由配 管的構成、矽膠液的檢查頻率、或矽膠液的使用期間等而 可適宜調整。另外，在每次一定時間經過而進行測定的情 況，亦可藉由將複數台的電性機器與一台的分析裝置，以 配管連接，切換配管的流路而進行各電性機器的監視。 在矽膠液6的測定準備階段，係藉由來自判定裝置3 0 的操作指令而開放幫浦、閥，使與槽1連接的採取配管、 或採取矽膠液6的氣體成分採取容器17中的矽膠液6循環。 在矽膠液6的測定階段，係藉由來自判定裝置3 0的操 作指令而關閉幫浦、閥，作動加熱器20，而加熱於氣體成 分採取容器1 7已採取一定量之矽膠液6，而將已蒸發的環 狀化合物的氣體成分，以氣體分析裝置1 9進行分析，根據 已分析的環狀化合物的氣體成分的測定値而以判定裝置3 0 判斷矽膠液的劣化狀況。 在清掃階段，係藉由來自判定裝置30的操作指令而停 -25- 200844431 止加熱器2 0 ’淨化、除去殘留於分析裝置等的成分、或矽 膠液。在進行了矽膠液的劣化診斷之後的矽膠液係因爲環 聚物等被除去，分解物成爲少之物，所以不排出至系外， 而回到槽1內亦佳。另外，被測定的矽膠液6的量係因爲少 量（例如：1〜5 Oml左右），所以廢棄亦可。 根據於矽膠液的測定時已檢測的矽膠液的資訊，進行 :藉由來自判定裝置3 0的操作指令而對管理者告知矽膠液 6的劣化的手段、或停止矽膠液浸電性機器之運轉的手段 之控制，成爲可有效率地防止機器的異常而謀求預防保全 〇 如適用對於上述之本實施例的矽膠液浸電性機器的矽 膠液之劣化診斷裝置的運轉模式，則因爲將由作爲矽膠液 浸電性機器的絕緣·冷卻媒體而使用的矽膠液之熱劣化而 產生的低分子量、低沸點的環狀化合物，在現場（on-site) 可效率佳而簡便地測定，所以可實現：可正確而且簡便地 診斷作爲矽膠液浸電性機器的絕緣·冷卻媒體而使用的矽 膠液的熱劣化之，電性機器用矽膠液之劣化診斷裝置以及 電性機器用矽膠液之劣化診斷方法。 【圖式簡單說明】 第1圖係表示爲本發明的一實施例的矽膠液浸變壓器 之劣化診斷裝置的構成之模式圖。 第2圖爲表示矽膠液的加熱溫度與環聚物的離子強度 的關係之特性圖。 -26- 200844431 第3圖爲設置於第1圖的實施例之劣化診斷裝置的監示 器畫面的模式圖。 第4圖係表示爲本發明的其他實施例的矽膠液浸變壓 器之劣化診斷裝置的構成之模式圖。 第5圖係表示爲本發明的更其他實施例，使砂膠液循 環於分析裝置內的砂膠液浸變壓器之劣化診斷裝置的構成 之模式圖。 第6圖爲表示矽膠液的熱劣化之促進試驗結果的特性 圖。 【主要元件符號說明】 1 :槽 2 ··鐵心 3 :內側捲線 4 :外側捲線 5 :絕緣筒 6 :矽膠液 7 :氮氣氣體 8 :冷卻器 9a :冷卻配管 9b :冷卻配管 l〇a :固定零件 l〇b :固定零件 1 1 :絕緣物 -27- 200844431 1 2 :絕緣物 13 :絕緣物 1 4 :絕緣物 1 5 :冷卻用之液導入部 16 :配管 16a :採取配管 16b :配管 1 7 :氣體成分採取容器 1 8 :氣體配管 1 9 :氣體分析裝置 20 :加熱器 2 1 a :閥 2 1b :閥 28 :幫浦 3 0 :判定裝置 3 1 :資料庫 3 2 :顯示裝置 3 3 :基準値設定器 -28Ion Current). To 5 0~3 0 0 t: Heat the silicone liquid under He atmosphere. In Figure 2, it is shown that M/Z値207 is indicated by a dotted line, and M/Z値281 is indicated by a solid line, and M/Z値3 5 5 The result is indicated by a dotted line. Regarding any of the nucleating agents, evaporation and gasification start at about 80 to 90 ° C, and all of the cyclized bodies are released at about 22 (TC). Therefore, the heating temperature can be about 100 ° C to 220 ° C. Further, by heating to 150 ° C to 220 ° C, the observation time can be shortened, and the measurement can be performed efficiently. Further, if the temperature is set to be higher than 230 to 250 ° C, the cyclopolymer is detected again. It is predicted that the decomposition of the silicone liquid and the evaporation and gasification of the decomposition product are started as a high temperature. The gas component of the silicone liquid immersion transformer shown in Fig. 1 is taken from the container 17 by the heater 20 The specific amount of the silicone liquid 6 contained in the gas component take-up container 17 is heated, and the low molecular weight and low boiling point cyclic compound generated by the thermal deterioration of the silicone liquid 6 is evaporated and vaporized into a gas component. The gas component is formed in the gas phase on the surface of the glue on the inner surface of the liquid crystal. The means for taking a specific amount of the silicone liquid is, for example, a valve (2 1 a) that is opened for a predetermined period of time and takes a certain amount. Silicone glue, preset a means for determining the weight of the silicone liquid to be taken. The gas component of the low-molecular weight compound which is generated by the thermal deterioration of the silicone liquid 6 in the gas phase portion of the inner surface of the container 17 by evaporation and gasification as a gas component, The gas analyzer 18 is sent to the gas analyzer 19, and the gas analyzer 19 analyzes and quantifies only the amount of the low molecular weight and low boiling point cyclic compound generated by thermal deterioration. - 200844431 Measure the total amount of gas components evaporated by heating, and measure only the total amount of cyclopolymers (3, 4, 5, 5) from the evaporated gas components as taken from the gas components The means for taking out the cyclic compound to the gas analyzer 1 9 is, for example, an inert gas such as nitrogen, helium or argon. The inside of the container 17 is taken as a gas component. The adsorbent heated by the heater is used to temporarily adsorb the gas component of the cyclic compound which has been vaporized and vaporized into the gas phase portion, and then heat the adsorbent to heat the vaporized cyclic compound gas. By introducing the gas analyzer into the gas analyzer 1 by the inert gas, the cyclic compound can be efficiently taken out. In addition, the amount of the 3-mer, the 4-mer, the 5-mer, and the ignition point of the silicone liquid are previously set. The characteristic of the deteriorated state is attached, and the deterioration diagnosis based on the result obtained by the gas analyzing device 19 can be diagnosed. For example, the analysis obtained by the gas analysis result or the calculated cyclic compound of the cyclic compound When the amount of the substance is more than or equal to a specific value, the silicone liquid is determined to be deteriorated. The deterioration diagnosis device for the silicone liquid of the electric device of the present embodiment is provided with the determination device 30 shown in Fig. 1 and The reference 値 setter 3 3 , the display device 32, and the data library 31. Then, the deterioration diagnosis of the silicone liquid is a ring that is quantitatively analyzed and vaporized from the silicone liquid by the gas analysis device 19. The measurement of the gas component of the compound is input to the determination device 30, where the determination device 30 determines the gas composition of the cyclic compound analyzed by the gas analysis device 19 - 200844431 (analysis, or Comparison of the reference enthalpy of the cyclized product which is the criterion for determining the deterioration of the cyclic compound, which is input from the reference enthalpy setter 3, and the measurement of the cyclic compound When the lanthanoid exceeds the standard enthalpy of the nucleus, it is judged that the sputum liquid system has deteriorated. The deterioration determination state of the silicone liquid by the determination device 30 can be output from the determination device 30 and displayed on the display device 32. In addition, the measurement 値 (analytical enthalpy or the amount of the cyclic polymer of the cyclic compound to be calculated) of the cyclic compound analyzed by the gas analysis device 19, which is input to the determination device 30, may be determined by the determination. The device 30 is displayed on the display device 32. In this case, the measurement of the gas component of the cyclic compound analyzed by the gas analysis device 19 can be performed or the cyclopolymer can be calculated from the gas analysis result. The amount is monitored by the determination device 30. In addition, the deterioration of the silicone liquid is performed in accordance with the number of years of operation of the electrical equipment. Therefore, in order to accurately grasp the progress of the deterioration, the gas component of the cyclic compound analyzed by the gas analyzer 19 is measured. Through the determination device 30, the database 31 is input together with the passage data during the operation period to be recorded first. By doing so, when the past data of the memory is called out from the database 31 to the determination device 30 and displayed on the display device 32, it is possible to accurately grasp the number of years of operation of the electrical device. The deterioration of the deterioration of the silicone liquid. Here, the state of the state of the silicone liquid for judging the deterioration state of the silicone liquid will be described with reference to Fig. 6. Fig. 6 is a characteristic diagram showing the results of the thermal deterioration promoting test of the silicone liquid used in the silicone liquid immersed transformer, and the individual table-14-200844431 shows that the horizontal axis is the heat aging test by the silicone liquid (250 °C x The aging time of 100 hours), the ignition point of the vertical axis of the silicone liquid on the left side, and the vertical axis of the right side are the amounts of the cyclopolymer contained in the silicone liquid. As shown in Fig. 6, the characteristic curve of the ignition point of the silicone liquid is in the case where the silicone liquid is new, it is 300 ° C or more, but the ignition time is passed while the deterioration time of the deterioration of the silicone liquid progresses. decline. In addition, the characteristic curve indicating the amount of the cyclopolymer (3 polymer D3, 4 polymer D4, and 5 polymer D5) contained in the silicone liquid is a small amount in the case where the silicone liquid is new, but in the silicone liquid The aging time of deterioration progresses sharply at the same time. Then, if the ignition point of the silicone liquid is lower than 200 °C, there is a possibility that the electric machine will ignite, so if the amount of the ring body at the ignition point of 200 °C is, for example, By setting 3 000 as the reference for deterioration determination and quantitatively analyzing the sand mixture and measuring the amount of the cyclopolymer, it is possible to accurately determine the deterioration state of the silicone liquid. Then, when it is determined that the silicone liquid is in a deteriorated state, the operation of the electric machine is stopped, or the abnormality of the electrical equipment is confirmed in the daily inspection items, and the state is analyzed in more detail by taking the silicone liquid. The state of the glue solution for diagnosing the deterioration state of the silicone liquid by the above-described determination device 30 is shown in Fig. 3 as a pattern diagram of the monitor screen displayed on the display device 3 2 . In the third diagram, the amount of the cyclopolymer of the gas component which evaporates the silicone liquid measured by the gas analyzer 9 is measured by the gas analyzer, and the object of the line is drawn by Δ, and値3〇〇〇 (dashed line) of the reference amount of the amount of the nucleating agent which is appropriately set in advance of the deterioration of the silicone liquid -15- 200844431 The third figure simulates the transformer A which is operated at a high load in the thermal deterioration promoting test, and is relatively low. The horizontal axis of the transformer B that is operated by the load is displayed by converting the aging time into the actual number of years of operation. In order to obtain this characteristic, the high load system sets the heating temperature to 270 ° C, and the so-called low load sets the heating temperature to 220 ° C ' to measure the amount of the cyclic polymer on the individual time axis. The measurement 至 up to the point corresponding to the current operation year of 10 years is plotted on the graph with a circular symbol and a triangular symbol. The one-dotted line □ is a smooth connection of the imaginary line of the measurement 变压器 of the transformer A. Similarly, the solid line is the transformer B. The point at which the extension of these imaginary lines intersects with the setting enthalpy is the limit of use of the silicone fluid of the individual transformers. Regarding the transformer B, it can be estimated that there is a remaining life of about 7 years as shown by L. In the actual transformer, since the data is stored by continuing the measurement of the nucleus, the characteristics as shown in Fig. 3 can be obtained. Therefore, it is possible to predict from the imaginary line of each measured enthalpy of the measured data. The exchange period of the silicone glue. Then, in accordance with the degree of deterioration of the sanding liquid displayed on the monitor screen of the display device 32, when the electrical equipment is stopped during periodic inspection or the like, a part or all of the silicone liquid is exchanged to become a transformer capable of the electrical equipment. The failure of the problem is prevented. Further, when the deterioration of the silicone liquid is diagnosed, the deterioration of the silicone liquid is generally known, for example, the deterioration of the silicone liquid determined by the determination device 3 is judged on the monitor of the display device 3 2 . The picture can be easily managed. For example, when the amount of the nucleating agent of the silicone liquid exceeds the specific enthalpy set in advance, it is determined that the silicone liquid has deteriorated and is displayed on the monitor screen of the display device 3 2 . The deterioration frequency of the silicone liquid of the electric machine is once a week, once a month, and the like. Therefore, the determination means 30 can be periodically operated to determine the deterioration at each specific time. Further, the determination device 30 is provided with an operation operation of the container 17 and the gas analysis device 19, a pump for supplying the glue liquid, a valve 21a, and a heating of the silicone liquid. The operation of the device 20 is configured in the same manner as the control device of the respective control, and the pump (not shown) is actuated in a specific cycle by an operation command from the determining device 30 to take the silicone 6 in the tank 1 to While the gas component is taken up in the container 17, the gas component is heated by the heater 20 of the container 17, and the heating of the silicone liquid 6 is started, and the gas analyzing device 19 is actuated. First, the valve 2 1 a is opened by an operation command from the determination device 30, the glue 6 in the tank 1 is taken from the take-up pipe 16a connected to the tank 1, and the heater 20 is actuated after the valve 2 1a is closed. Heating is carried out until the gas component takes the silicone liquid 6 of the container 17 to vaporize the cyclic compound contained in the silicone liquid, and the vaporized gasified cyclic compound is quantitatively analyzed by the gas analyzer 19. Then, the analysis of the cyclic compound analyzed by the gas analyzer 19 or the deterioration of the glue of the 矽 200844431 determined by the determination device 30 based on the analysis 此 of the cyclic compound is displayed on the display device 32. After the amount of the cyclopolymer is analyzed by the gas analyzer 19, the heater 20 provided in the gas component taking container 17 is stopped by an instruction from the determining device 30, and the components remaining in the analyzer or the like are purified. Since the mash liquid 6 is a small substance because it is decomposed, it is not discharged to the outside of the system, and it is also preferable to return to the tank 1. Further, the amount of the silicone liquid 6 to be measured is a small amount (for example, 50 ml), so it may be discarded. Further, it is also possible to monitor a plurality of electrical devices such as transformers by a single gas analysis device or determination device. According to the above, the frequency of confirmation of the deterioration of the silicone liquid 6 is once a week or once a month, and therefore, for one analysis device, as an electric device having a plurality of devices, a switching device having a pipe, and an electric device The deterioration diagnosis system for the silicone liquid used is also preferred. By means of a plurality of electrical machines, individual silicone liquids 6 can be taken to hold the deteriorated state of the silicone liquid of each electrical machine. The use of the silicone liquid 6 for the determination of one time is easy to quantify the amount of gas which can be obtained if the silicone liquid is large, and if it is small, the heating of the silicone liquid is easy. It is preferable that the silicone liquid 6 is used as 1 to 50 ml, and it can be sufficiently measured at about 1 to 5 ml. The gas component remaining in the deterioration determination takes the silicone liquid 6 of the container 17, and since it does not have a low molecular weight compound which lowers the ignition point, it can be returned to the tank 1 and reused. At this time, it is preferable to provide a reflux pipe for returning the silicone liquid 6 to the tank 1, and a pump for circulating the silicone liquid 6 in the pipe. -18- 200844431 The pump system can be controlled by the above-described determination device 30. Further, it is preferable that the silicone liquid 6 after the deterioration is determined to be discarded and replenished as necessary. According to the above-described injection of the silicone fluid transformer, it is generated by the thermal deterioration of the silicone liquid 6 of the insulating/cooling medium accommodated in the inside of the tank 1 during the operation of the transformer, and is dissolved in the silicone liquid 6 The cyclic compound is heated and vaporized to the gas phase portion on the liquid surface of the silicone liquid 6 to be analyzed as a gas, so that the thermal deterioration of the silicone liquid 6 is performed. The resulting cyclic compound can be easily and quantitatively quantified in the field, so that the prevention and preservation of the silicone liquid immersion transformer can be easily achieved. The silicone liquid 6 used in the insulating/cooling medium of the silicone liquid immersed transformer is circulated between the tank 1 and the cooler 8 via the cooling pipes 9a and 9b connected to both, and is cooled in the cooler 8. The silicone liquid 6 is supplied to the core 2 provided inside the groove 1, the inner winding 3 and the winding wire 4 of the outer winding 4 to cool the contents of the machine. Therefore, the viscosity of the silicone 6 is preferably low, especially at 25 ° C. It is ideal for a dynamic viscosity coefficient of 55 mm 2 /s or less. In general, the ignition point of the mortar liquid 6 depends on the molecular weight. In addition, the smaller the molecular weight, the lower the viscosity of the silicone liquid 6. Therefore, it is expected that the lower the viscosity, the lower the ignition point of the silicone liquid 6 is, and the more the product of the low molecular weight and low boiling decomposition products which are thermally decomposed becomes. In addition, in order to improve the fire resistance of the transformer or the tightening of the machine with a high operating temperature, it is desirable that the sulphur liquid 6 is flammable, -19-200844431, especially the ignition point is more than 2 5 0 °C is ideal. Therefore, as the silicone liquid 6 used in the insulation/cooling medium of the silicone liquid immersed transformer, the ignition point is more than 250 ° C, and the silicone liquid 6 having a dynamic viscosity coefficient of 55 mm 2 /s or less at 25 ° C is effective. Further, the silicone liquid 6 of the present embodiment is preferably an additive which is added to a charging inhibitor or the like which is used in a mineral oil immersion transformer. According to the present embodiment, the low molecular weight and low boiling point cyclic compound which is produced by the thermal deterioration of the silicone liquid used as the insulating/cooling medium of the silicone liquid immersion machine can be on-site. Since it is easy to measure and is easy to measure, it is possible to accurately and easily diagnose the thermal deterioration of the silicone liquid used as the insulation/cooling medium for the silicone liquid immersion machine, and the deterioration diagnostic device for the silicone liquid for electric equipment. Diagnostic method for deterioration of silicone fluid for electrical equipment. [Embodiment 2] Next, a configuration of a deterioration diagnosis device for a silicone liquid for a silicone immersion transformer according to another embodiment of the present invention will be described with reference to Fig. 4. In the transformer of the silicone liquid immersion transformer of the present embodiment shown in Fig. 4, the gas component take-up container 17 is configured to be connected to the pipe 1 6 a which is connected to the cooling pipe 9 b provided in the lower portion of the cooler 8 The composition of the setting. Since the pipe 16a that takes the silicone liquid 6 is provided so as not to communicate with the groove 1 and communicates with the cooling pipe 9b, the arrangement of the pipe 16a can be easily performed. The composition of the silicone -20-200844431 liquid deterioration diagnostic apparatus for the silicone liquid immersion transformer of the present embodiment shown in Fig. 4 is for use in the silicone liquid immersion transformer of the first embodiment shown in Fig. 1. Since the deterioration diagnosis device of the silicone liquid is basically the same, the description of the configuration common to both is omitted. In addition, the silicone liquid-immersed transformer of the present embodiment in FIG. 4 is insulated and cooled by the medium during operation. The method of analyzing and quantifying the low-molecular weight and low-boiling cyclic compound produced by the thermal deterioration of the silicone liquid 6 in the field is also the same as that of the first embodiment shown in FIG. 1, and therefore the description thereof is omitted. . The deterioration diagnosis device for the silicone liquid for the silicone liquid immersion transformer according to the present embodiment described above is also the same as the previous embodiment described in Fig. 1, because the insulation/cooling medium is used as the silicone liquid immersion machine. The low-molecular-weight, low-boiling cyclic compound produced by the thermal deterioration of the silicone liquid used can be efficiently and easily measured on-site, so that it can be accurately and easily diagnosed as a silicone liquid immersion. The thermal deterioration of the silicone liquid used for the insulation of the electrical equipment and the cooling medium, the deterioration diagnostic apparatus for the silicone liquid for electric equipment, and the deterioration diagnosis method of the silicone liquid for electrical equipment [Example 3] is shown in Fig. 5 A deterioration diagnostic apparatus for a silicone liquid for an electric device according to still another embodiment of the present invention. In this example, the silicone liquid 6 is circulated in the analysis device. In the present embodiment, the take-up port of the silicone liquid 6 is used as the tank body 1, and the discharge port of the silicone liquid 6 is used as the pipe 9b-21-200844431 of the cooler 8. The pump 28 for circulating the silicone liquid 6 is installed in the pipe 16a at which the pipe 16a is opened, the valve 21a provided in the pipe 16a, and the pipe 21b provided in the pipe 16b, and the pipe is connected to the gas component to take the container 17 to make the silicone 6 Circulating, and taking the silicone component inside the container 17 in this gas component, replacing the specific amount of the silicone liquid 6 used in the measurement, closing the valve 2 1 a, 2 1 b, and making the gas component A specific amount of the silicone liquid 6 in the container 17 is taken and heated and evaporated by the heater 20 provided in the gas component take-up container 17 to take a gas component. Next, the gas component taken by the vessel 17 is taken from the gas component, and analyzed by the gas analyzer 19 to measure the amount of the cyclopolymer in the gas component. Then, based on the measurement of the gas component analyzed by the gas analyzer 19 (analytical enthalpy or the amount of the cyclic compound of the cyclic compound), it is introduced into the cyclic compound from the reference enthalpy setter 3 3 . When the measurement of the cyclic compound exceeds the reference enthalpy of the nucleus in the case where the measurement of the cyclic compound exceeds the reference enthalpy of the cyclic polymer, it is determined that the silicone liquid has deteriorated. By judging the state of deterioration of the silicone liquid by the device 30, the judgment device 30 outputs and displays it on the display device 32. In addition, the measurement of the gas component of the cyclic compound which has been analyzed by the gas analyzer 19, which is input to the determination device 30, can be performed (analytical enthalpy, or the amount of the cyclic compound of the cyclic compound to be calculated), When the display device 3 is displayed by the determination device 3, in this case, the measurement of the gas component of the cyclic compound analyzed by the gas deposition can be performed. The amount of the nucleus calculated by the analysis was analyzed to determine the device 3. -22- 200844431 The silicone liquid 6 after the measurement is because the cyclopolymer is reduced only, so the valves 21a and 21b can be opened and returned to the tank 1. Further, even if the silicone liquid 6 is taken from the cooling pipe 9b, it does not matter. However, in order to reduce the heating during the analysis, it is effective to take it from the cooling pipe 9a or from the upper portion of the body of the groove 1. Further, the cooling pipes 9a and 9b are arranged such that the discharge port of the silicone liquid 6 is circulated by using the discharge port of the silicone liquid 6 as a pipe, and it is preferable to omit a part of the pump. Further, in the present embodiment, the function of notifying the diagnosis result of the deterioration diagnostic device of the silicone liquid is attached. This is because not only the measurement of the gas component of the cyclic compound analyzed by the gas analyzer 19 (the amount of the cyclic polymer cyclic polymer) but also the measurement of the gas component according to the cyclic compound is determined. When the comparison calculation of the device 30 exceeds the reference enthalpy of the cyclization which is the criterion for deterioration, it is determined that the silicone liquid has deteriorated, and the deterioration determination result of the silicone liquid is displayed on the display device 32, so that it can be The measurement result of the measurement of the gas component of the cyclic compound analyzed by the gas analyzer 19 or the diagnosis result of the deterioration diagnostic device of the silicone solution is monitored by the determination device 30. The manager can confirm the deterioration state of the silicone liquid 6 by the present embodiment and manage the machine. For example, it is preferable that an alarm device that determines that the silicone liquid 6 has deteriorated and an alarm is issued when the amount of release of the nucleus exceeds a specific enthalpy set in advance. For example, the reference enthalpy input to the reference enthalpy setter 3 is set by the measurement enthalpy obtained by the deteriorated sputum liquid, or by the characteristics of the electrical conductivity -23-200844431 or the ignition temperature. Also good. Further, the valve or the alarm device may be a well-known thing, but it is preferable to open the valve when the power is stopped and the alarm is turned ON. According to the present embodiment, the low molecular weight and low boiling point cyclic compound which is produced by the thermal deterioration of the silicone liquid used as the insulating/cooling medium of the silicone liquid immersion machine can be on-site. Since it is easy to measure and is easy to measure, it is possible to accurately and easily diagnose the thermal deterioration of the silicone liquid used as the insulation/cooling medium for the silicone liquid immersion machine, and the deterioration diagnostic device for the silicone liquid for electric equipment. Diagnostic method for deterioration of silicone fluid for electrical equipment. Next, an example of an operation form of deterioration diagnosis of the silicone liquid immersion device including the deterioration diagnosis device of the silicone liquid shown in Figs. 1, 4, and 5 will be described. The diagnosis by the deterioration diagnosis device of the silicone liquid can be performed at a frequency set once a week or once a month, or repeatedly. Hereinafter, a diagnosis example using the deterioration diagnosis device for the silicone liquid per cycle will be described. The operation of the deterioration diagnosis device of the silicone liquid is mainly divided into four stages of measurement preparation, measurement, cleaning, and constant state. -24- 200844431 Table 1 Operation content valve for diagnosing deterioration (V Bu V2) Heater (H) Replacement of sputum in the time measurement preparation pipe. OFF lOmin The sample is taken and the ring in a certain amount of sputum is measured. The compound is heated and extracted, and the measured amount is closed. lOmin is cleaned and the measured silicone liquid is discharged to the outside of the system, or is returned to the inside of the tank for 15 minutes of OFF. At the constant time (in standby mode), the shutdown is closed for a specific period and, in Table 1 above. The necessary time for each stage can be appropriately adjusted by the configuration of the piping, the frequency of inspection of the silicone liquid, or the use period of the silicone liquid. Further, in the case where the measurement is performed every time a certain period of time has elapsed, it is also possible to perform monitoring of each electric device by connecting a plurality of electric devices and one analysis device to each other by piping, and switching the flow path of the pipe. In the preparation preparation stage of the silicone liquid 6, the pump and the valve are opened by an operation command from the determination device 30, and the piping which is connected to the tank 1 or the gas component of the silicone liquid 6 is taken to take the silicone in the container 17. Liquid 6 cycles. In the measuring stage of the silicone liquid 6, the pump and the valve are turned off by the operation command from the determining device 30, and the heater 20 is actuated, and the gas component is taken up to take a certain amount of the silicone liquid 6 from the gas component. The gas component of the evaporated cyclic compound is analyzed by a gas analyzer 19, and the deterioration state of the silicone liquid is judged by the determination device 30 based on the measurement of the gas component of the analyzed cyclic compound. In the cleaning phase, the heater 20 0 ' is stopped by the operation command from the determination device 30 to remove the components remaining in the analyzer or the glue solution. Since the silicone liquid after the deterioration of the silicone liquid is removed by the cyclopolymer or the like, the decomposition product becomes a small substance, so that it is not discharged to the outside of the system, and is preferably returned to the inside of the tank 1. Further, since the amount of the silicone liquid 6 to be measured is small (for example, about 1 to 5 Oml), it can be discarded. According to the information of the silicone liquid which has been detected at the time of measurement of the silicone liquid, means for notifying the manager of the deterioration of the silicone liquid 6 by the operation command from the determination device 30 or stopping the operation of the silicone liquid immersion machine Because of the control of the means, it is possible to prevent the abnormality of the machine and to prevent the maintenance. For example, the operation mode of the deterioration diagnostic device for the silicone liquid immersion machine of the above-described embodiment is applied. The low molecular weight and low boiling point cyclic compound produced by the thermal deterioration of the silicone liquid used for the insulation and cooling medium of the liquid immersion machine can be efficiently and easily measured on-site, so that: It is possible to accurately and easily diagnose the thermal deterioration of the silicone liquid used as the insulation/cooling medium for the silicone liquid immersion machine, the deterioration diagnostic device for the silicone liquid for electrical equipment, and the deterioration diagnosis method for the silicone liquid for electrical equipment. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the configuration of a deterioration diagnostic apparatus for a silicone immersion transformer according to an embodiment of the present invention. Fig. 2 is a characteristic diagram showing the relationship between the heating temperature of the silicone liquid and the ionic strength of the cyclopolymer. -26- 200844431 Fig. 3 is a schematic diagram showing a monitor screen of the deterioration diagnostic apparatus of the embodiment shown in Fig. 1. Fig. 4 is a schematic view showing the configuration of a deterioration diagnostic apparatus for a silicone liquid immersion transformer according to another embodiment of the present invention. Fig. 5 is a schematic view showing the configuration of a deterioration diagnosing device for a sand immersion transformer which circulates the sanding liquid in the analyzing device according to still another embodiment of the present invention. Fig. 6 is a characteristic diagram showing the results of the test for promoting the thermal deterioration of the silicone liquid. [Description of main components] 1 : Slot 2 · Core 3: Inner winding 4: Outer winding 5: Insulation cylinder 6: Silicone 7: Nitrogen gas 8: Cooler 9a: Cooling piping 9b: Cooling piping l〇a: Fixed Part l〇b: Fixed part 1 1 : Insulator -27- 200844431 1 2 : Insulator 13 : Insulator 1 4 : Insulator 1 5 : Liquid introduction part for cooling 16 : Pipe 16a : Pipe 16b : Pipe 1 7: Gas component taking container 1 8 : Gas piping 1 9 : Gas analyzer 20 : Heater 2 1 a : Valve 2 1b : Valve 28 : Pump 3 0 : Judging device 3 1 : Library 3 2 : Display device 3 3: Benchmark 値 Setter-28