TW408221B

TW408221B - Halide ion detection apparatus and the manufacturing method of its detecting material

Info

Publication number: TW408221B
Application number: TW85104767A
Authority: TW
Inventors: Yi-Sung Jan; Bin-Bin Tsai
Original assignee: Ind Tech Res Inst
Priority date: 1996-04-22
Filing date: 1996-04-22
Publication date: 2000-10-11

Abstract

This invention relates to a kind of halide ion detection apparatus and the manufacturing method of its detecting material. Said halide ion detection apparatus is mainly composed by the porous material where the silver dichromate (Ag2Cr2O7) or silver chromate (Ag2CrO4) is uniformly deposited on the surface of the apparatus.

Description

4Q822ii B7 五、發明説明（1 ) 本發明係有關於鹵素離子檢測裝置及其檢測材質之製造方法’特別是有關於氯離子檢測裝置及其檢測材質之製造方法。在化學檢測及分析領域中’利用分析學的原理及技術而能在各種環境中（例如：水、空氣或各種溶液等）進行特定分子或離子的檢測，於近年來已愈來愈顯得重要，其中最廣為人知的即是利用廣用試紙或石蕊試紙檢測各類水溶液的酸鹼值。現今又以具有固態、可攜帶、可現場檢測及可拋棄等特性之檢測裝置最為人廣用，亦成長最快。人類很早就開始了解鹵素離子對人體及各類物質所產生的危害，尤其是氣離子對人體健康、飲用水的適飲性、以及存在於工業用水内而對輸送管和鍋爐所造成的腐蝕或存在於混凝土内而對鋼筋所造成的侵敍都有著密不可分的關係。因此能設計出一種簡易、可現場檢測、價格便宜以及可拋棄式的鹵素離子檢測裝置，不論在商業上或實用上都是相當重要的。經濟部_央標準局貝工消費合作社印袈舉例而言’由於近年來國内各項工程大興土木，在國内河砂被大量採用後，已呈不足之現象，隨之就有業者引用海砂做為建材使用，但海砂内的氣離子含量相當大，並會使鋼筋遭受嚴重的侵蚀，而導致建築物的安全性堪慮。不過’海砂可經由水洗而降低氯離子的濃度，進而減輕對鋼筋的侵蝕。在此情形下，若能使用具備有上述特點之齒素離子檢測裝置而直接對海砂進行氯離子濃度的檢測，將是相當便利與實用的。 __ 3 83. 3.10,000 (請先閏讀背面之注$項#填寫本頁) 本紙張足及通用中國國家橾準（CNS ) M洗格（2〖0><297公釐）經濟部中央標準局負工消资合作社印裝 408221 A7 B7 五、發明説明（2 ) 大體而言，固態檢測裝置大致可分為兩類··（1)將試劑塗佈或吸附於紙上後，#紙放入含待測物的溶液中，並藉由試劑顏色的變化而定量或半定量出溶液中待測物的含量；（2)利用多孔性材質吸附試劑後，將多孔性材質裝填入具有固定體積的容器中，利用毛細現象或其他外力（壓力或真空吸力）使一定量的溶液進入容器中，亦可藉由試劑顏色的變化而定量或半定量溶液中待測物的含量。用以檢測氯離子濃度的習知方法與裝置將在以下予以敘述： (1)美國專利第5229299號曾揭露利用硝酸銀（AgN03) 與重鉻酸鉀（K2Cr207)相互反應使在多孔性材質上形成重鉻酸銀（Ag2Cr207)並裝填入容器令，當氣離子與重鉻酸銀接觸時會發生反應並使重鉻酸銀的顏色產生變化，藉此可檢測出氯離子的含量。但其缺點在於製程複雜，並需要加入其他的陽離子，否則會在鹼性待測溶液中形成黑色的氧化銀沈澱（Ag20)而影響檢測準確度；（2)前人曾提出在薄膜上塗佈重鉻酸銀而用來檢測海水、淡水交接處的鹽度（Rian, Zhengxu, et al.，Chin. J. Oceanol. Limnol. 1990,8(3),213-19)，但由於並未使用容器，故在定量上的準確度不高；（3) 歐洲專利189809號則揭露利用濾紙將鉻酸銀（Ag2Cr04)吸附，或加入納-角又聚糖（Na Carrageenan)，利用鉻酸銀與氯離子反應成氣化銀（AgCl)而產生顏色之變化進而定量出氣離子濃度，但與前例相同，由於鉻酸銀並非裝填入容器内而是塗佈在薄膜上，因此定量的準確性亦不高，並且在 83. 3.10,000 (請先閏讀背面之注意事項再填寫本頁)4Q822ii B7 V. Description of the invention (1) The present invention relates to a method for manufacturing a halogen ion detection device and its detection material ', and particularly to a method for manufacturing a chloride ion detection device and its detection material. In the field of chemical detection and analysis, 'the use of analytical principles and techniques to detect specific molecules or ions in various environments (such as water, air or various solutions, etc.) has become increasingly important in recent years. Among them, the most widely known is the use of widely used test paper or litmus paper to detect the pH value of various aqueous solutions. Nowadays, detection devices with solid, portable, on-site detection, and disposable characteristics are the most widely used and the fastest growing. Humans have long understood the harm caused by halogen ions to the human body and various substances, especially the gas ions on human health, the drinkability of drinking water, and the corrosion caused by pipelines and boilers in industrial water. Or it exists in the concrete and has an inseparable relationship with the invasion of steel bars. Therefore, it is important to design a simple, field-testable, inexpensive, and disposable halogen ion detection device, whether commercially or practically. Ministry of Economic Affairs_Central Bureau of Standards, Shellfish Consumer Cooperative, India, for example, 'Because of the large-scale construction of various domestic projects in recent years, after the large-scale use of domestic river sand, it has become insufficient. It is used for building materials, but the content of gas ions in the sea sand is quite large, and it will cause serious corrosion of the steel bars, which will cause the safety of the building. However, 'sea sand' can reduce the concentration of chloride ions by washing with water, thereby reducing the erosion of steel bars. In this case, it would be quite convenient and practical to directly detect the chloride ion concentration of sea sand using a tooth ion detection device with the above characteristics. __ 3 83. 3.10,000 (Please read the note on the back of the page first # Fill in this page) This paper is sufficient and GM China National Standards (CNS) M Zhege (2 〖0 > < 297mm) Ministry of Economic Affairs Printed by the Central Bureau of Standards for Consumers and Cooperatives 408221 A7 B7 V. Description of the invention (2) Generally speaking, solid-state detection devices can be roughly divided into two categories ... (1) After coating or adsorbing reagents on paper, # 纸Put it in the solution containing the test substance, and quantitatively or semi-quantitatively determine the content of the test substance in the solution by changing the color of the reagent; (2) After adsorbing the reagent with the porous material, fill the porous material with In a fixed volume container, a certain amount of solution is introduced into the container using capillary phenomenon or other external forces (pressure or vacuum suction). The content of the test substance in the solution can also be quantified or semi-quantified by the change in the color of the reagent. The conventional method and device for detecting the chloride ion concentration will be described as follows: (1) US Patent No. 5229299 has disclosed that the use of silver nitrate (AgN03) and potassium dichromate (K2Cr207) react with each other to form on a porous material Silver dichromate (Ag2Cr207) is filled into a container, and when gas ions come in contact with silver dichromate, a reaction occurs and the color of silver dichromate changes, thereby detecting the content of chloride ions. However, the disadvantage is that the manufacturing process is complicated and other cations need to be added, otherwise black silver oxide precipitates (Ag20) will be formed in the alkaline test solution and affect the detection accuracy; (2) previous people have proposed coating on thin films Silver dichromate was used to measure salinity at seawater and freshwater junctions (Rian, Zhengxu, et al., Chin. J. Oceanol. Limnol. 1990, 8 (3), 213-19), but it was not used (3) European Patent No. 189809 discloses the use of filter paper to adsorb silver chromate (Ag2Cr04), or adding Na-carrageenan (Na Carrageenan), using silver chromate and The chloride ion reacts to form silver chloride (AgCl) to produce a color change to quantify the gas ion concentration, but the same as the previous example, because the silver chromate is not filled in the container but coated on the film, the accuracy of the quantification is also Not high and at 83. 3.10,000 (Please read the notes on the back before filling this page)

T 408221 A7 B7 ^ 五、發明説明（3 ) 製程中加入鈉-角叉聚糖更增加了製造成本與複雜性，並由於其製程與第（1)例大致相同，故亦有氧化銀黑色沈澱發生的困擾；（4)美國專利第4444193號則發明一種平面式貼絆 (flat patch)以放置在人體皮膚上測量人體汗液中的氣離子濃度，但由於只能用來檢測人體而不能應用於溶液或混凝土中；（5)另有人提出利用混凝土中的氣離子與鉻酸銀進行置換反應，而溶出CrO^ ’再使用硼酸鹽作為緩衝溶液而使溶液pH值維持在7〜9，並以分光光度計測量Cr042·的含量以反推出氣離子濃度，其檢測範圍為1 -90ppxxi(Yamada Akifumi,et al‘，Bunseki Kagaku 1990,39(5),295-9)，但缺點是需要利用分光光度計，故無法進行現場的檢測；（6)與前例相同，曾有人提出利用混凝土中的氯離子與鉻酸銀進行置換反應而溶出淡黃色Cr〇42·並在pH 6~7的環境下以分光光度計在波長405nm處測量Cr042-的含量以反推出氣離子 ?辰度’其檢測犯圍為0 · 1 _70ρρπι ’而其缺點跟前項相同，亦為無法進行現場檢測（Denki Kagaku oyobi Kogyo Butsuri Kagaku，1990,58(3)，255-8); (7)美國專利第 4211532 號則是將鉻酸鉀（K2Cr04)、硝酸銀（AgN03)及界面活性劑 (Polyoxyethylene Sorbitan mono laurate)三者混合後形成絡酸銀膠態溶液，並將試紙浸入溶液後烘乾，再浸入由檸檬酸（citric acid)所配製成的缓衝溶液中（pH 2~7)以製成一檢測棒，但其缺點在於利用硝酸銀與鉻酸鉀反應生成鉻酸銀而塗佈在濾紙時，為不使在檢測過程中有氧化銀黑色沈澱發生’則溶液的pH值須調整至2~7，但鉻酸銀在此酸鹼範 ____________ 5_____ 本紙伕从適用中關家標丰（CNS ) A4^_ ( 2敝297公·^) ~ - Γ. I - -. n In - - rE-a-s—s i - —ΙΙί. - - - 1 , (诗先閏讀背面之注意事項再填寫本s·) 經濟部中央標準局貝工消費合作社印S- 經濟部中央標準局貝工消費合作社印裝 4^S22t A7 B7 五、發明説明（4 ) 圍内卻會轉變成溶解度極大的重鉻酸銀，致使製程複雜。本發明的目的即在提供一種將路酸銀或重鉻酸銀形成在多孔性材質之表面的新穎方法，並能解決習知技術的種種缺陷。本發明所利用的方法可簡化製造程序，並降低干擾物對檢測系統的干擾’例如解決習知技術中在硝酸銀與重鉻酸鉀反應形成重鉻酸銀後會在鹼性環境下形成氧化銀黑色沈澱物而影響檢測的準確度。本發明的另一目的即是提供簡易的鹵素離子檢測裝置，藉由將鉻酸銀或重鉻酸銀以一次步驟而形成在多孔性材貝上並裝填入鹵素離子檢測管，或將路酸銀或重鉻酸銀以一次步驟而形成在濾紙上而製成兩邊有開口的檢測膠片。本發明的優點在於製程簡單，而檢測裝置具有可攜帶、可現場檢測、價格低簾、可拋棄等優越特性，不論在任何地點皆可對水溶液或混凝土中的氣離子做快速與準確的定量分析。本發明的另一優點是除了可以將該裝置應用於溶液或混凝土内氣離子的檢測外’尚可應用於其他鹵素離子 (氟、溴、碘離子）的檢測’甚或溶液内氰離子（CN-)和硫氰根離子（SCN—)的檢測。此外’本發明亦可用來檢測空氣中鹽酸(HC1)、氫氟酸(HF)、氫溴酸(HBr)、氫蛾酸(HI)等物質，以及血液、尿液中氣離子的濃度。本發明的再一優點為對氣離子檢測的再現性良好，益且在鹼性環境下亦無習知技術中形成氧化銀黑色沈澱的困 6 本紙張尺度適用中囷國家標隼（CNS ) A4规格（210X297公楚） 83. 3. !0,〇〇〇 ---------衣— (請先閱讀背面之注意事3丹填讀衣耳j _.ψ A7 B7 408221 五、發明説明（5 ) 擾。利用鉻酸銀或重鉻鹸銀進行對氣離子濃度的檢測，其原理在於鉻酸銀或重鉻酸銀極易與氣離子反應而生成白色的氯化銀沈澱，並同時生成淡黃色的鉻酸根離子（Cr042—) 或橙紅色的重鉻酸根離子（Cr2 0 72_)，其反應式如下： Ag2Cr〇4 + 2C1' ^ 2AgCl 十 Cr042· (暗紅色）（白色）（淡黃色）T 408221 A7 B7 ^ V. Description of the invention (3) The addition of sodium-carrageenan in the manufacturing process further increases the manufacturing cost and complexity, and because the manufacturing process is roughly the same as in (1), there is also a black precipitate of silver oxide. (4) U.S. Patent No. 4,444,193 invented a flat patch to be placed on human skin to measure the concentration of gas ions in human sweat, but it cannot be applied because it can only be used to detect the human body Solution or concrete; (5) someone else proposed to use gas ions in the concrete to replace the silver chromate, and dissolve CrO ^ 'and then use borate as a buffer solution to maintain the pH of the solution at 7-9, and The spectrophotometer measures the content of Cr042 · to infer the gas ion concentration, and its detection range is 1-90ppxxi (Yamada Akifumi, et al ', Bunseki Kagaku 1990, 39 (5), 295-9), but the disadvantage is that it requires the use of spectrophotometry (6) Same as the previous example, it was proposed to use chloride ion in the concrete to replace the silver chromate to dissolve pale yellow Cr〇42 · under the environment of pH 6 ~ 7 Spectroscopy The photometer measures the content of Cr042- at a wavelength of 405nm to infer the gas ions. The degree of detection is 0. 1 _70ρρπι. The disadvantages are the same as the previous item, and it is impossible to perform on-site detection. (1990, 58 (3), 255-8); (7) U.S. Patent No. 4,211,532 is formed by mixing potassium chromate (K2Cr04), silver nitrate (AgN03), and surfactant (Polyoxyethylene Sorbitan mono laurate). Complex silver colloidal solution, dip the test paper into the solution and dry it, then dip it into a buffer solution (pH 2 ~ 7) made of citric acid to make a test rod, but its disadvantages When the silver nitrate is reacted with potassium chromate to form silver chromate and coated on filter paper, in order to prevent black oxide silver precipitation during the detection process, the pH value of the solution must be adjusted to 2-7, but the silver chromate This acid-base range ____________ 5_____ This paper 伕 from the application of Guan Jiabiaofeng (CNS) A4 ^ _ (2 敝 297 公 · ^) ~-Γ. I--. N In--rE-as—si-—ΙΙί.- --1, (Read the notes on the back of the poem before filling in this s.) Bureau of Consumer Cooperatives quasi HIGHLAND India S- Ministry of Economic Affairs Bureau of Standards HIGHLAND consumer cooperatives India with 4 ^ S22t A7 B7 V. invention is described in (4) it will change in the solubility surrounded by great silver dichromate, resulting in process complexity. The object of the present invention is to provide a novel method for forming silver gallate or silver dichromate on the surface of a porous material, and to solve various defects of the conventional technology. The method used by the present invention can simplify the manufacturing process and reduce the interference of interferences on the detection system. For example, in the conventional technology, silver oxide is formed by reacting silver nitrate with potassium dichromate to form silver dichromate. Black deposits affect the accuracy of the test. Another object of the present invention is to provide a simple halogen ion detection device. The silver chromate or silver dichromate is formed on a porous material in one step and filled into a halogen ion detection tube. Silver acid or silver dichromate is formed on the filter paper in one step to make a detection film with openings on both sides. The advantage of the invention is that the manufacturing process is simple, and the detection device has the advantages of being portable, on-site detection, low price, and disposable. It can quickly and accurately quantify gas ions in aqueous solution or concrete at any place. . Another advantage of the present invention is that in addition to applying the device to the detection of gas ions in solutions or concrete, 'it can also be applied to the detection of other halogen ions (fluorine, bromine, iodide ions)' or even cyanide ions (CN- ) And thiocyanate ion (SCN—). In addition, the invention can also be used to detect the concentrations of hydrochloric acid (HC1), hydrofluoric acid (HF), hydrobromic acid (HBr), hydrolysate (HI) in the air, and the concentration of gas ions in blood and urine. Another advantage of the present invention is that the gas ion detection has good reproducibility, and it is difficult to form a black precipitate of silver oxide in the conventional technology even in an alkaline environment. 6 This paper is applicable to the Chinese National Standard (CNS) A4 Specifications （210X297 公楚） 83. 3.! 0, 〇〇〇 --------- Clothing — (Please read the note on the back 3 Dan fill in the clothing ear j _.ψ A7 B7 408221 V. Description of the invention (5) Disturbance. The detection of gas ion concentration using silver chromate or dichromium silver is based on the principle that silver chromate or silver dichromate can easily react with gas ions to form a white silver chloride precipitate. At the same time, light yellow chromate ions (Cr042—) or orange red dichromate ions (Cr2 0 72_) are generated at the same time, the reaction formula is as follows: Ag2Cr〇4 + 2C1 '^ 2AgCl ten Cr042 · (dark red) (white) (Light yellow)

Ag2Cf2〇7 + 2 Cl —> 2AgCl + 〇Γ2〇7^ (暗紅色）（白色）（燈紅色）本發明用以將鉻酸銀或重鉻酸銀成功且均勻地形成在多孔性材質上的方法共有四種不同方式： (a) 將鉻酸銀（Ag2Cr04)溶解於稀釋的氨水中，並加入多孔性材質後，加熱以使水和氨水蒸發，則鉻酸銀即能均勻地形成在多孔性材質上； (b) 將鉻酸銀溶解於稀硝酸中，此時鉻酸銀會轉變成重鉻酸銀，其反應式如下：Ag2Cf2〇7 + 2 Cl —> 2AgCl + 〇Γ2〇7 ^ (dark red) (white) (light red) The present invention is used to successfully and uniformly form silver chromate or silver dichromate on a porous material. There are four different methods: (a) Dissolve silver chromate (Ag2Cr04) in diluted ammonia water, add a porous material, and heat to evaporate the water and ammonia water, then silver chromate can be uniformly formed in Porous materials; (b) Dissolve silver chromate in dilute nitric acid. At this time, silver chromate will be transformed into silver dichromate. The reaction formula is as follows:

Ag2Cr2〇7 OH- 加入多孔性材質後，加熱使水蒸發，則重鉻酸銀即可均勻形成在多孔性材質上； (C)將鉻酸銀溶解於稀釋的氨水中，並加入pH 7〜10的緩衝溶液，如：蝴酸鹽、填酸鹽，在加入多孔性材質後，加熱使水及氨水蒸發，即可使鉻酸銀與緩衝劑均勻地形成在多孔性材質上；以及本紙乐尺度逍用中國國家標隼（CNS ) A4说格（2丨0X297公釐）Ag2Cr2〇7 OH- After adding the porous material and heating to evaporate the water, the silver dichromate can be uniformly formed on the porous material; (C) Dissolve the silver chromate in diluted ammonia water and add pH 7 ~ 10 Buffer solutions, such as: phosphonates and salt fillers, after adding porous materials, heating to evaporate water and ammonia water, silver chromate and buffering agents can be uniformly formed on porous materials; and the paper scale Free use of Chinese National Standard (CNS) A4 grid (2 丨 0X297 mm)

----------衣____1__:訂 (請先閏請背面之注意事項再填寫本WO---------- Cloth ____1__: Order (Please 闰 Please note on the back before filling in this WO

Ag2Cr04 經濟部中央標隼局貞工消費合作社印策 83. 3,10,000 4GG22 經濟部中央標準局貝工消費合作社印装 A7 B7 五、發明説明（6 )Ag2Cr04 Printing policy of Zhengong Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs 83. 3,10,000 4GG22 Printed by Shelling Consumer Cooperative, Central Standards Bureau, Ministry of Economic Affairs A7 B7 V. Description of Invention (6)

I (d)將鉻酸銀溶解於稀硝酸中，此時鉻酸銀轉變成重鉻酸銀’並加入pH 2〜7的緩衝溶液，如：硼酸鹽、磷酸鹽，在加入多孔性材質後，加熱使水蒸發，則重鉻酸銀與緩衝劑即可均句地形成在多孔性枯質上。接著將以實施例並配合圖示給予本發明詳盡的說明：圖示之簡要說明：第1圖所示為依據本發明所製成之一種鹵素離子檢測裝置；第2A圖至第2C圖所示為依據本發明所製成之另一種鹵素離子檢測裝置及其檢測程序；以及第3A圖至第3B圖所示為依據本發明所製成之另一種鹵素離子檢測裝置及其檢測程序。參照號碼之簡要說明：第1圖：參照號碼1為一派勒克斯（pyrex)玻璃管：參照號碼2為棉花；參照號碼3為吸水性高分子；參照號碼4為依據本發明所製成的含絡酸銀或重絡酸銀之多孔性材質與石夕砂的混合物質；參照號碼5為石夕砂；參照號碼6為上、下刻痕；以及參照號碼7為定量用刻度。第2A圖至第2C圖： _ 8 本紙張尺度適用中囷國家標準（CNS ) A4故格（210X297公笼） 83. 3. 10,000 (請先S讀背面之注意事項再填寫本頁)I (d) Dissolve silver chromate in dilute nitric acid. At this time, silver chromate is converted into silver dichromate 'and a buffer solution with a pH of 2 to 7 is added, such as borate and phosphate. After adding a porous material After heating to evaporate the water, the silver dichromate and the buffer can be uniformly formed on the porous dry matter. Next, the present invention will be described in detail with examples and drawings: Brief description of the figures: Figure 1 shows a halogen ion detection device made according to the present invention; Figures 2A to 2C show Another halogen ion detection device and its detection program made according to the present invention; and FIGS. 3A to 3B show another halogen ion detection device and its detection program made according to the present invention. Brief description of the reference number: Figure 1: Reference number 1 is a pyrex glass tube: Reference number 2 is cotton; Reference number 3 is a water-absorbing polymer; Reference number 4 is an encapsulation made according to the present invention. The mixed material of porous material of acid silver or double complex silver and Shi Xisha; reference number 5 is Shi Xisha; reference number 6 is the upper and lower score; and reference number 7 is a quantitative scale. Figures 2A to 2C: _ 8 This paper size is subject to the Chinese National Standard (CNS) A4 old grid (210X297 male cage) 83. 3. 10,000 (Please read the precautions on the back before filling this page)

If 經濟部中央標準局另工消资合作社印裝 408221 a? B7 五、發明説明（7 ) 參照號碼21為一玻璃管；參照號碼22為依據本發明所製成的含重鉻酸銀或鉻酸銀之多孔性材質；參照號碼23為棉花；以及參照號碼24為含重鉻酸銀或鉻酸銀之多孔性材質與氯離子反應所生成之氯化銀。第3A圖至第3B圖：參照號碼35為塑膠片；參照號碼36為一細線；參照號碼37為依據本發明所製成的含鉻酸銀或重鉻酸銀之多孔性材質；以及參照號碼38為含鉻酸銀或重鉻酸銀之多孔性材質與氯離子反應所生成之氯化銀。實施例一將0.001莫耳之鉻酸銀溶解於30毫升的氨水（1N) 中，並加入30克的多孔性材質（如矽膠、濾紙等），於70 °C下加熱使水與氨水蒸發，蒸發完全後，鉻酸銀即可均勻地形成在多孔性材質上。實施例二將0.001莫耳之鉻酸銀溶解於1N的稀硝酸中，並加入30克的多孔性材質（如矽膠、濾紙等），此時鉻酸銀會轉變成重鉻酸銀，在70°C下加熱使水及稀硝酸蒸發，蒸發完全後，重鉻酸銀即可均勻地形成在多孔性材質上。實施例三本紙張尺度適用中國囤家標车（CNS ) A4软^ ( 210X297公嫠） 83. 3.10,000 ------------- (請先閏讀背面之注意事項再填寫本頁) 訂經濟部中央標準局貝工消費合作社印裝 408221 A7 B7 五、發明説明（8) 將0.001莫耳之鉻酸銀溶解於30毫升的氨水（IN) 内，並加入10毫升的緩'衝溶液（pH 7〜10)，此緩衝溶液可為硼酸鹽溶液（0.1莫耳硼酸氫鈉（Na2HB03)和0.1莫耳硼酸鈉（Na3B03)混合而成）或磷酸鹽溶液（0.1莫耳磷酸氫鈉 (Na2HP04)和0.1莫耳磷酸鈉（Na3P04)混合而成），再加入 30克的多孔性材質（如矽膠、濾紙等），於70°C下加熱使水和氨水蒸發，蒸發完全後，鉻酸銀與緩衝劑即可均勻地形成在多孔性材質上。實施例四將0.001莫耳之鉻酸銀溶解於1N的稀硝酸中，此時鉻酸銀已轉變成重鉻酸銀，並加入10毫升的緩衝溶液（pH 2〜7)，此緩衝溶液可為硼酸鹽溶液（0.1莫耳硼酸二氫鈉 (NaH2B〇3)和0.1莫耳棚酸(H3BO3)混合而，成）或鱗酸鹽溶液 (0.1莫耳磷酸二氫鈉（NaH2P04)和0.1莫耳磷酸(H3P〇4)混合而成），再加入3 0克的多孔性材質（如砂耀、渡紙等），在70°C下加熱使水及稀硝酸蒸發，蒸發完全後，重鉻酸銀與缓衝劑即可均勻地形成在多孔性材質上。實施例五將實施例一至實施例四所製成的含重鉻酸銀或鉻酸銀之多孔性材質填入一透明管狀殼件内（如第2A圖所示），此透明管狀殼件可由玻璃、聚乙烯或聚苯乙烯所構成，在填入多孔性材質後，於透明管狀殼件的兩端裝填入棉花、纸或其他吸水性材料，並在透明管狀殼件上劃上刻度，則一鹵素離子檢測裝置即裝配完成（如第2 A圖所示）。 __1Ό_ 本&張尺度適用中国國家搮準（CNS )八4说格（210X297公釐) 83. 3. 10,000 (請先閱讀背面之注意事項再填寫本莧)If printed by the Central Bureau of Standards of the Ministry of Economic Affairs and other consumer and consumer cooperatives 408221 a? B7 V. Description of the invention (7) Reference number 21 is a glass tube; Reference number 22 is silver dichromate or chromium containing dichromate made according to the present invention Porous material of acid silver; reference number 23 is cotton; and reference number 24 is silver chloride produced by the reaction of a porous material containing silver dichromate or silver chromate with chloride ions. 3A to 3B: Reference number 35 is a plastic sheet; reference number 36 is a thin line; reference number 37 is a porous material containing silver chromate or silver dichromate made according to the present invention; and reference number 38 is silver chloride produced by the reaction between a porous material containing silver chromate or silver dichromate and chloride ions. Example 1 Dissolve 0.001 mole of silver chromate in 30 ml of ammonia water (1N), add 30 g of porous material (such as silicon gel, filter paper, etc.), and heat at 70 ° C to evaporate the water and ammonia water. After the evaporation is complete, silver chromate can be uniformly formed on the porous material. Example 2 Dissolve 0.001 mole of silver chromate in 1N dilute nitric acid, and add 30 grams of porous materials (such as silicone, filter paper, etc.). At this time, silver chromate will be converted into silver dichromate. Heating at ° C will evaporate water and dilute nitric acid. After the evaporation is complete, silver dichromate can be uniformly formed on the porous material. Example 3 This paper size is applicable to Chinese standard car (CNS) A4 soft ^ (210X297) 嫠 83. 3.10,000 ------------- (Please read the notes on the back first (Fill in this page again.) Order printed by the Central Standards Bureau of the Ministry of Economic Affairs, Shellfish Consumer Cooperative, 408221 A7 B7. 5. Description of the invention (8) Dissolve 0.001 mol of silver chromate in 30 ml of ammonia (IN) and add 10 ml. Buffer solution (pH 7 ~ 10), this buffer solution can be a borate solution (mixed with 0.1 mol sodium hydrogen borate (Na2HB03) and 0.1 mol sodium borate (Na3B03)) or a phosphate solution (0.1 mol A mixture of sodium hydrogen phosphate (Na2HP04) and 0.1 mol sodium phosphate (Na3P04)), and then add 30 grams of porous materials (such as silicone, filter paper, etc.), heated at 70 ° C to evaporate water and ammonia water, evaporated After completion, the silver chromate and the buffer can be uniformly formed on the porous material. Example 4: 0.001 mole of silver chromate was dissolved in 1N dilute nitric acid. At this time, silver chromate had been converted into silver dichromate, and 10 ml of a buffer solution (pH 2 ~ 7) was added. It is a borate solution (a mixture of 0.1 mol sodium dihydrogen borate (NaH2B03) and 0.1 mol acid (H3BO3)) or a phosphonate solution (0.1 mol sodium dihydrogen phosphate (NaH2P04) and 0.1 mol O3 phosphoric acid (H3P〇4) is mixed), and then add 30 grams of porous materials (such as sand, paper, etc.), heated at 70 ° C to evaporate water and dilute nitric acid, after evaporation is complete, heavy chromium The silver acid and the buffer can be uniformly formed on the porous material. Embodiment 5 The porous material containing silver dichromate or silver chromate prepared in Examples 1 to 4 is filled into a transparent tubular shell (as shown in FIG. 2A). The transparent tubular shell can be made of It is made of glass, polyethylene or polystyrene. After filling the porous material, cotton, paper or other water-absorbing materials are filled at the two ends of the transparent tubular shell, and the transparent tubular shell is marked with a scale. Then a halogen ion detection device is assembled (as shown in Figure 2A). __1Ό_ This & Zhang scale is applicable to China National Standards Standard (CNS) 8 and 4 (210X297 mm) 83. 3. 10,000 (Please read the notes on the back before filling in this card)

408221 A7 -------B7 五、發明説明（9 ) 實施例六將實施例一至實施’例四所製成的含重鉻酸銀或鉻酸銀之多孔性材質。夾在兩片透明或一邊透明的塑膠材料中並在泫塑膠材料上劃上刻度，則一鹵素離子檢測裝置即裝配完成（如第3 A圖所示）。此多孔性材質的形狀為平板狀，如遽紙或紙帶，而該塑耀材料可為聚乙婦、聚丙稀、聚越、美拉薄膜（Mylar film)或其他不透水的材料所構成。實施例七，在檢測混凝土或其他溶液中的氣離子濃度時，將實施例五或實施例六所裝配之鹵素離子檢測裝置的上端（約2分分）置入待測物中，此時氯離子會與重鉻酸銀或鉻酸銀反應並形成白色氣化銀（如第2B圖所示），藉由觀察檢測裝置中重鉻酸銀或鉻酸銀轉變成白色氯化銀的分界線，再經由裝置上的刻度即可5賣出氣離子在待測物中所含的濃度（如第2c 圖及第3B圖所示）。經濟部中央標準局男工消費合作社印裝雖然本發明已以若干較佳實施例揭露如上，然其並非用以限定本發明’任何熟習此項技藝者，在不脫離本發明之精神和範圍内’當可作些許之更動與潤飾，因此本發明之保遵範圍當視後附之申請專利範圍所界定者為準。 11 81 3.10t000 (請先閏請背面之注意事項再填寫本頁) 本紙張尺度適用中囷國家標隼（CNS ) A4规格（2丨OX297公釐）408221 A7 ------- B7 V. Description of the invention (9) Example 6 A porous material containing silver dichromate or silver chromate prepared in Examples 1 to ′ Example 4. If it is sandwiched between two pieces of transparent or transparent plastic material and a mark is made on the plastic material, a halogen ion detection device is assembled (as shown in Figure 3A). The shape of the porous material is a flat plate, such as a paper or a paper tape, and the plastic material can be made of polyethylene, polypropylene, polycondensation, Mylar film, or other water-impermeable materials. In the seventh embodiment, when the concentration of gas ions in concrete or other solutions is detected, the upper end (about 2 minutes) of the halogen ion detection device assembled in the fifth or sixth embodiment is placed in the object to be tested. At this time, the chlorine Ions will react with silver dichromate or silver chromate to form white vaporized silver (as shown in Figure 2B). By observing the detection device, silver dichromate or silver chromate is converted into white silver chloride. , And then the scale on the device can be sold 5 concentration of gas ions in the test object (as shown in Figure 2c and Figure 3B). Printed by the Men ’s Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. Although the present invention has been disclosed above in a number of preferred embodiments, it is not intended to limit the present invention. 'When some changes and retouching can be made, the scope of guarantee of the present invention shall be determined by the scope of the attached patent application. 11 81 3.10t000 (Please fill in this page with the precautions on the back first) This paper size is applicable to China National Standard (CNS) A4 (2 丨 OX297 mm)

Claims

md 4082|fL 六、申請專利範圍 1. 一種將鉻酸銀均勻形成於多孔性材質上的方法，包括： (a) 將格酸銀溶解於氨永中，以形成一混合溶液； (b) 將多孔性材質浸入該混合溶液中，其中該多孔性材質係選自滤紙、活性馨土、矽膠、矽砂或其衍生物所組成的族群中之其中一種材質； (C)加熱該混合溶液’加熱溫度低於9〇〇c :以及 (d)持續加熱直到將水與該氨水蒸發完全，則該鉻酸銀即可均勻地形成在該多孔性材質上。 2. 如申請專利範圍第1項之方法，其中，該氨水的濃度為 0.1 〜6N。 3. 如申請專利範圍第i項之方法，其中，該⑷步驟的加熱溫度範圍為60〜9〇。(3。 4. 一種將重鉻酸銀均勻形成於多孔性材質上的方法，包括： (a) 將絡酸銀溶解於稀硝酸中’以形成一重鉻酸銀混合溶液； (b) 將多孔性材質浸入該混合溶液中，其中該多孔性材質經濟部中央標準局員工消费合作社印裝 (請先閱讀背面之注意事項再填寫本育) 係選自遽紙 '活性礬土、矽膠、矽砂或其衍生物所組成的族群中之其中一種材質； (c) 加熱該混合溶液，加熱溫度低於90°C ;以及 (d) 持續加熱直到將水蒸發完全，則該重鉻酸銀即可均勻地形成在該多孔性材質上。 5-如申請專利範圍第4項之方法，其中，該稀硝酸的濃度為0，1〜6N。 7 二乂一____ 12 本紙乐从適用十國g家裙準（CNS〉M規格（21〇><297公褒） md 4082|fL 六、申請專利範圍 1. 一種將鉻酸銀均勻形成於多孔性材質上的方法，包括： (a) 將格酸銀溶解於氨永中，以形成一混合溶液； (b) 將多孔性材質浸入該混合溶液中，其中該多孔性材質係選自滤紙、活性馨土、矽膠、矽砂或其衍生物所組成的族群中之其中一種材質； (C)加熱該混合溶液’加熱溫度低於9〇〇c :以及 (d)持續加熱直到將水與該氨水蒸發完全，則該鉻酸銀即可均勻地形成在該多孔性材質上。 2. 如申請專利範圍第1項之方法，其中，該氨水的濃度為 0.1 〜6N。 3. 如申請專利範圍第i項之方法，其中，該⑷步驟的加熱溫度範圍為60〜9〇。(3。 4. 一種將重鉻酸銀均勻形成於多孔性材質上的方法，包括： (a) 將絡酸銀溶解於稀硝酸中’以形成一重鉻酸銀混合溶液； (b) 將多孔性材質浸入該混合溶液中，其中該多孔性材質經濟部中央標準局員工消费合作社印裝 (請先閱讀背面之注意事項再填寫本育) 係選自遽紙 '活性礬土、矽膠、矽砂或其衍生物所組成的族群中之其中一種材質； (c) 加熱該混合溶液，加熱溫度低於90°C ;以及 (d) 持續加熱直到將水蒸發完全，則該重鉻酸銀即可均勻地形成在該多孔性材質上。 5-如申請專利範圍第4項之方法，其中，該稀硝酸的濃度為0，1〜6N。 7 二乂一____ 12 本紙乐从適用十國g家裙準（CNS〉M規格（21〇><297公褒） A8 B8 CS D8 經濟部申央標隼局負工消资合作社印敦 408221 7'申請專利範園 …6.如申請專利範圍帛4項之方法’該⑷步驟的加熱溫度魏圍為60〜90°C ° ' 7‘一種將鉻酸銀均勻形成於多孔性材質上的方法，包括： U)將鉻酸銀溶解於氨水中； (b)加入一緩衝溶液於該氨水中，以形成一混合溶液； ^ (c)將多孔性材質浸入該混合溶液中，其中該多孔性材質係選自濾紙、活性礬土、矽膠、矽砂或其衍生物所組成的族群中中一種材質；熱該混合溶液’加熱溫度低於90。(：；以及熱直到將水與該氨水蒸發完全，則該鉻酸銀與緩衝劑即f均勻地形成在該多孔性材質上。 8.如申請專利範圍第7項之方法，其中，該氨水的濃度為〇.1 〜6N。 9. 如申請專利範圍第7項之方法’其中，該緩衝溶液可為蝴酸鹽溶液或磷酸鹽溶液，並且該緩衝溶液的酸鹼值為pH 7 〜12 〇 10. 如申請專利範圍第7項之方法，其中，該（d)步驟的加熱溫度範圍為60〜90°C。 11. 一種將重鉻酸銀均句形成於多孔性材質上的方法，包括： (a) 將鉻酸銀溶解於稀硝酸中； (b) 加入一緩衝溶液於該稀硝酸中，以形成一重鉻酸銀混合溶液； (c) 將多孔性材質浸入該混合溶液中，其中該多孔性材質 13 本紙乐尺度逋用中國國家標準（CNS ) A4現格（2丨0X29?公釐）、" (請先閲讀背面之注意事項再填寫本頁)md 4082 | fL 6. Application scope 1. A method for uniformly forming silver chromate on a porous material, comprising: (a) dissolving silver lattice acid in ammonia to form a mixed solution; (b) A porous material is immersed in the mixed solution, wherein the porous material is one of a material selected from the group consisting of filter paper, activated earth, silicone, silica sand, or a derivative thereof; (C) heating the mixed solution ' The heating temperature is lower than 900c: and (d) heating is continued until the water and the ammonia water are completely evaporated, and then the silver chromate can be uniformly formed on the porous material. 2. The method according to item 1 of the patent application range, wherein the concentration of the ammonia water is 0.1 to 6N. 3. The method according to item i of the patent scope, wherein the heating temperature range of this step is 60 ~ 90. (3. 4. A method for uniformly forming silver dichromate on a porous material, comprising: (a) dissolving silver complex acid in dilute nitric acid 'to form a mixed solution of silver dichromate; (b) porous The porous material is immersed in the mixed solution, in which the porous material is printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs (please read the precautions on the back before filling in this education). It is selected from the group of 'paper' activated alumina, silicone, and silica sand. One of the materials of the group consisting of or its derivatives; (c) heating the mixed solution, the heating temperature is lower than 90 ° C; and (d) continuously heating until the water is completely evaporated, the silver dichromate can be It is uniformly formed on the porous material. 5- As in the method in the scope of patent application No. 4, wherein the concentration of the dilute nitric acid is 0,1 ~ 6N. 7 乂一 ____ 12 This paper is suitable for Shikoku g Home skirt standard (CNS> M specification (21〇 > < 297 gong)) md 4082 | fL 6. Application scope of patent 1. A method for uniformly forming silver chromate on a porous material, including: (a) Dissolve silver lattice acid in ammonia to form a mixed solvent Liquid; (b) immersing a porous material in the mixed solution, wherein the porous material is one of the materials selected from the group consisting of filter paper, activated earth, silica gel, silica sand, or derivatives thereof; (C) The mixed solution is heated, if the heating temperature is lower than 900 ° C, and (d) heating is continued until the water and the ammonia water are completely evaporated, the silver chromate can be uniformly formed on the porous material. The method according to item 1 of the patent scope, wherein the concentration of the ammonia water is 0.1 to 6N. 3. The method according to item i of the patent scope, wherein the heating temperature range of the step ⑷ is 60 to 90. (3.4. A method for uniformly forming silver dichromate on a porous material, comprising: (a) dissolving silver complex acid in dilute nitric acid 'to form a mixed solution of silver dichromate; (b) immersing a porous material in the In the mixed solution, the porous material is printed by the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs (please read the precautions on the back before filling in this education). It is selected from the group consisting of “paper” activated alumina, silica gel, silica sand, or derivatives thereof. Group of people One of the materials; (c) heating the mixed solution at a temperature lower than 90 ° C; and (d) continuously heating until the water is completely evaporated, the silver dichromate can be uniformly formed on the porous material 5- The method according to item 4 of the scope of patent application, wherein the concentration of the dilute nitric acid is 0,1 ~ 6N. 7 乂一 ____ 12 This paper Lecong applies to the ten countries g family skirt standards (CNS> M specifications ( 21〇 > < 297 public money) A8 B8 CS D8 Shenyang Standards Bureau, Ministry of Economic Affairs, Consumers and Consumers Cooperatives, India 408221 7 'Patent application for patent garden ... 6. If the scope of patent application is 帛 4, the method of this step The heating temperature is 60 ~ 90 ° C ° '7'. A method for uniformly forming silver chromate on a porous material includes: U) dissolving silver chromate in ammonia water; (b) adding a buffer solution to The ammonia water to form a mixed solution; ^ (c) immersing a porous material into the mixed solution, wherein the porous material is selected from the group consisting of filter paper, activated alumina, silicon rubber, silica sand or derivatives thereof One of the materials; heat the mixed solution 'heating temperature below 90. (:; And until the water and the ammonia water are completely evaporated, the silver chromate and the buffering agent f are uniformly formed on the porous material. 8. The method according to item 7 of the patent application scope, wherein the ammonia water The concentration is 0.1 to 6N. 9. As described in the method of the scope of the patent application No. 7 'wherein, the buffer solution may be a phosphonate solution or a phosphate solution, and the pH value of the buffer solution is pH 7 to 12 〇10. The method according to item 7 of the scope of patent application, wherein the heating temperature range of step (d) is 60 ~ 90 ° C. 11. A method of forming silver dichromate homogeneous sentence on a porous material, Including: (a) dissolving silver chromate in dilute nitric acid; (b) adding a buffer solution to the dilute nitric acid to form a mixed solution of silver dichromate; (c) immersing a porous material in the mixed solution, Among them, the porous material is 13 paper scales, using Chinese National Standard (CNS) A4 (2 丨 0X29? Mm), " (Please read the precautions on the back before filling this page)

ABCD 經濟部中央標準局員工消費合作社印裝 * «ΛPrinted by ABCD Employee Consumer Cooperatives, Central Standards Bureau, Ministry of Economic Affairs * «Λ

408221 六、申請專利範園係選自濾紙、活性礬土、矽膠、矽砂或其衍生物所組成的族群中之其中一種材質； · (d)加熱該混合溶液，加熱溫度低於9〇乞；以及 0)持續加熱直到將水蒸發完全，則該重鉻酸銀與緩衝劑即可均勻形成在該多孔性材質上。 12,如申請專利範圍第丨丨項之方法，其中，該稀硝酸的濃度為0 _ 1〜6N。 I3·如申請專利範圍第11項之方法，其中，該緩衝溶液可為硼酸鹽溶液或磷酸鹽溶液，並且該緩衝溶液的酸鹼值為 2~7 〇 I4·如申清專利範圍第11項之方法，其中，該（d)步驟的加熱溫度範圍為60〜901。 15. —種鹵素離子檢測裝置，包括： (a) —劃有刻度之透明管狀殼件，· (b) —裝填於該圓柱形材料的刻度範圍内之表面已均勻形成有重鉻酸銀或鉻酸銀的多孔性材質；以及 / (c) —裴填於該多孔性材質兩端的吸水性材料。、16·如申請專利範圍第15項之鹵素離子檢測裝置，其中，該透明官狀殼件乃由玻璃、聚_、聚苯乙烯或纖維質材料所製成。 17.如申請專利範圍第15項之齒素離子檢測裝置，发中該吸水性材料可為棉花、其他紙製品或其他可吸水的村料。’ 18· —種鹵素離子檢測裝置，包括： (幻一對不透水並已劃上刻度的等面積之透明材料 (請先閲讀背面之注意事項再填寫本頁)408221 VI. The patent application range is one of the materials selected from the group consisting of filter paper, activated alumina, silica gel, silica sand or its derivatives; (d) Heating the mixed solution at a heating temperature below 90 ° And 0) continue heating until the water is completely evaporated, the silver dichromate and the buffering agent can be uniformly formed on the porous material. 12. The method according to item 丨丨 of the scope of patent application, wherein the concentration of the dilute nitric acid is 0 -1 to 6N. I3. The method of claim 11 in the scope of patent application, wherein the buffer solution can be a borate solution or a phosphate solution, and the buffer solution has an acid-base value of 2-7. I4. The scope of claim 11 in the scope of patent application The method, wherein the heating temperature in the step (d) ranges from 60 to 901. 15. A halogen ion detection device, including: (a)-a marked transparent tubular shell, (b)-a surface filled with the cylindrical material within the scale range has been uniformly formed with silver dichromate or A porous material of silver chromate; and / (c)-a water-absorbing material filled with two ends of the porous material. 16. The halogen ion detection device according to item 15 of the application, wherein the transparent shell-like shell is made of glass, polystyrene, polystyrene, or fibrous material. 17. If the tooth ion detection device of item 15 of the patent application scope, the water-absorbing material in the hair may be cotton, other paper products, or other water-absorbing village materials. ‘18 · — A kind of halogen ion detection device, including: (a pair of transparent materials of equal area that are impermeable to water and have been scaled (please read the precautions on the back before filling this page)

經濟部中央標率局貝工消費合作社印製 il C8 六申魏聲以及 (b)—爽置於該對透明材料片内之表面已均勻形成有重鉻酸銀或鉻酸銀的條狀多孔性材質。 19.如申請專利範圍第18項之鹵素離子檢測裝置，其中，該透明材料片可為塑膠、美拉薄膜、聚乙烯、聚丙烯、聚醚或其他不透水的透明材料所製成D 2〇·—種鹵素離子檢測裝置，係自一具刻痕及刻度的派勒克斯圓开> 玻璃管内的一端依序裝填棉花、矽砂、重絡酸銀或鉻酸銀與矽砂之混合物、吸水性高分子以及棉花所構成。本紙張尺度逋用中國國家標芈（CNS ) A4規格（210X 297公釐） (請先閲讀背面之注意事項再填寫本頁)Printed by il C8 Liushen Weisheng and (b) —Strips of porous material with silver dichromate or silver chromate uniformly formed on the surface of the pair of transparent material sheets . 19. The halogen ion detection device according to item 18 of the application, wherein the transparent material sheet may be made of plastic, mellar film, polyethylene, polypropylene, polyether, or other water-impermeable and transparent materials. · —A kind of halogen ion detection device, which is filled with cotton, silica sand, double complex acid silver or silver chromate and silica sand, and absorb water from one end of a Plexus circle with a score and a scale. Polymer and cotton. This paper uses the Chinese National Standard (CNS) A4 size (210X 297 mm) (Please read the precautions on the back before filling this page)